Grazing Incidence X-ray Diffraction Data Research Articles

Structure of liquid-vapor interfaces: Perspectives from liquid state theory, large-scale simulations, and potential grazing-incidence x-ray diffraction.

Grazing-incidence x-ray diffraction (GIXRD) is a scattering technique that allows one to characterize the structure of fluid interfaces down to the molecular scale, including the measurement of surface tension and interface roughness. However, the corresponding standard data analysis at nonzero wave numbers has been criticized as to be inconclusive because the scattering intensity is polluted by the unavoidable scattering from the bulk. Here, we overcome this ambiguity by proposing a physically consistent model of the bulk contribution based on a minimal set of assumptions of experimental relevance. To this end, we derive an explicit integral expression for the background scattering, which can be determined numerically from the static structure factors of the coexisting bulk phases as independent input. Concerning the interpretation of GIXRD data inferred from computer simulations, we extend the model to account also for the finite sizes of the bulk phases, which are unavoidable in simulations. The corresponding leading-order correction beyond the dominant contribution to the scattered intensity is revealed by asymptotic analysis, which is characterized by the competition between the linear system size and the x-ray penetration depth in the case of simulations. Specifically, we have calculated the expected GIXRD intensity for scattering at the planar liquid-vapor interface of Lennard-Jones fluids with truncated pair interactions via extensive, high-precision computer simulations. The reported data cover interfacial and bulk properties of fluid states along the whole liquid-vapor coexistence line. A sensitivity analysis shows that our findings are robust with respect to the detailed definition of the mean interface position. We conclude that previous claims of an enhanced surface tension at mesoscopic scales are amenable to unambiguous tests via scattering experiments.

Identifying the Internal Network Structure of a New Copper Isonicotinate Thin‐Film Polymorph Obtained via Chemical Vapor Deposition

AbstractThe preparation of thin films is often associated with the appearance of unknown polymorphs, as both the substrate and deposition method can heavily influence crystallization processes. Here, chemical vapor deposition is used to obtain thin films of a copper‐isonicotinate (Cu‐INA) metal–organic framework (MOF). Starting from copper‐based precursor layers (copper oxide and hydroxide), a solid‐vapor conversion with vaporized isonicotinic acid in either a dry or humidified atmosphere, yields a new Cu‐INA MOF polymorph. It is found that the crystalline order of the precursor layer has a strong impact on the texture of Cu‐INA thin films. Furthermore, a novel methodology is introduced to determine the structure of a previously unknown thin‐film phase of Cu‐INA. Although only a few diffraction peaks are found via synchrotron grazing incidence X‐ray diffraction (GIXRD), a triclinic unit cell can be determined, and Patterson functions can be calculated. The latter reveals the position of the copper atoms within the unit cell and the alignment of the INA linkers defining the coordination network structure. This work introduces how the combination of GIXRD data with Patterson functions can be used to identify the structure of an unknown thin‐film MOF polymorph.

Development of Benzobisoxazole-Based Novel Conjugated Polymers for Organic Thin-Film Transistors.

Benzo[1,2-d:4,5-d']bis(oxazole) (BBO) is a heterocyclic aromatic ring composed of one benzene ring and two oxazole rings, which has unique advantages on the facile synthesis without any column chromatography purification, high solubility on the common organic solvents and planar fused aromatic ring structure. However, BBO conjugated building block has rarely been used to develop conjugated polymers for organic thin film transistors (OTFTs). Three BBO-based monomers, BBO without π-spacer, BBO with non-alkylated thiophene π-spacer and BBO with alkylated thiophene π-spacer, were newly synthesized and they were copolymerized with a strong electron-donating cyclopentadithiophene conjugated building block to give three p-type BBO-based polymers. The polymer containing non-alkylated thiophene π-spacer showed the highest hole mobility of 2.2 × 10-2 cm2 V-1 s-1, which was 100 times higher than the other polymers. From the 2D grazing incidence X-ray diffraction data and simulated polymeric structures, we found that the intercalation of alkyl side chains on the polymer backbones was crucial to determine the intermolecular ordering in the film states, and the introduction of non-alkylated thiophene π-spacer to polymer backbone was the most effective to promote the intercalation of alkyl side chains in the film states and hole mobility in the devices.

Evolution of local atomic structure accompanying devitrification of amorphous Ni-Zr alloy thin films

Thin film metallic glasses undergoing devitrification can form partially crystallized or fully crystallized materials with novel structural and magnetic properties. The development of desired and tunable properties of such systems drives the need to understand the mechanism of their thermal evolution at the atomic level. Co-sputtered amorphous Ni-Zr alloy thin films which were thermally annealed in steps of 200°C from room temperature up to 800°C, were observed to undergo an amorphous-to-crystalline transformation. Evolutions in local atomic structure, including oxide formation and depletion during this devitrification process, were determined using a combination of X-ray reflectivity (XRR), grazing incidence X-ray diffraction (GIXRD) and Extended X-ray Absorption Fine Structure (EXAFS) techniques. The most probable phase of the alloy was determined as Ni7Zr2; undergoing a polymorphous transformation. The slight oxide content in the films was also noted to decrease rapidly as annealing proceeded; leaving the crystallization pathway unhindered. modeling and analyses of XRR and GIXRD data showed that film thickness decreased with annealing while long range order increased. Pair distribution function peak widths were observed to decrease with annealing, indicating a control over structural disorder in the system as it transitioned from the amorphous to crystalline state. Partial atomic distribution in the environment of each constituent was examined at every stage of annealing through EXAFS measurements, which gave proper insight into atomic scale changes to the order present. Detailed analyses through these techniques gave coherent results, thus providing a true picture of the thermal evolution process of devitrification in this technologically useful material.

Capabilities of Grazing Incidence X-ray Diffraction in the Investigation of Amorphous Mixed Oxides with Variable Composition.

X-ray Diffraction has been fully exploited as a probe to investigate crystalline materials. However, very little research has been carried out to unveil its potentialities towards amorphous materials. In this work, we demonstrated the capabilities of Grazing Incidence X-ray Diffraction (GIXRD) as a simple and fast tool to obtain quantitative information about the composition of amorphous mixed oxides. In particular, we evidenced that low angle scattering features, associated with local structure parameters, show a significant trend as a function of the oxide composition. This evolution can be quantified by interpolating GIXRD data with a linear combination of basic analytical functions, making it possible to build up GIXRD peak-sample composition calibration curves. As a case study, the present method was demonstrated on Ta2O5–SiO2 amorphous films deposited by RF-magnetron sputtering. GIXRD results were validated by independent measurement of the oxide composition using Rutherford Backscattering Spectrometry (RBS). These materials are attracting interest in different industrial sectors and, in particular, in photovoltaics as anti-reflection coatings. Eventually, the optical properties measured by spectroscopic ellipsometry were correlated to the chemical composition of the film. The obtained results highlighted not only a correlation between diffraction features and the composition of amorphous films but also revealed a simple and fast strategy to characterize amorphous thin oxides of industrial interest.

Effect of bias voltages on microstructure and properties of (TiVCrNbSiTaBY)N high entropy alloy nitride coatings deposited by RF magnetron sputtering

(TiVCrNbSiTaBY)N high entropy alloy nitride (HEAN) coatings have been deposited onto Si (100) and cemented carbide substrates by radio frequency magnetron sputtering. The deposition is carried out at different bias voltages to study its influence on microstructure, morphology, mechanical properties and tribological behaviour of the coatings. Grazing Incidence X-Ray Diffraction (GIXRD) technique shows that all coatings exhibit single NaCl-type face-centered cubic (FCC) crystal structure, while the preferred orientation of the crystal structure is greatly affected by the bias voltages. High resolution transmission electron microscopy (TEM) reveals that the structure of the coatings is a mixture of amorphous-like phase and FCC crystal structure, which is in agreement with GIXRD data. Cross-sectional Scanning Electron Microscopy (SEM) images exhibit that the columnar structure of the coatings gradually transforms into a featureless dense structure with the increase of bias voltage. SEM and Atomic Force Microscopy reveal that the surface morphology become smoother with increasing bias voltage. The (TiVCrNbSiTaBY)N HEAN coating deposited at a specific bias voltage exhibit a high hardness of 32.2 GPa. The friction coefficient is significantly influenced by the variation of the coatings surface roughness. Tribological tests for coating deposited without and at low bias voltage show that the wear behavior of the coatings is severe abrasive wear and adhesive wear, while at high bias voltage the slight abrasive wear appears. By applying the substrate bias voltage, the (TiVCrNbSiTaBY)N coatings exhibit excellent mechanical and tribological performance, which can be a promising candidate for protective coating in cutting tools or components.

An efficient method for indexing grazing-incidence X-ray diffraction data of epitaxially grown thin films

An efficient method for indexing grazing-incidence X-ray diffraction data of epitaxially grown thin films

GIDInd: an automated indexing software for grazing-incidence X-ray diffraction data

<i>GIDInd</i>: an automated indexing software for grazing-incidence X-ray diffraction data

GIDInd: an automated indexing software for grazing-incidence X-ray diffraction data.

Grazing-incidence X-ray diffraction (GIXD) is a widely used technique for the crystallographic characterization of thin films. The identification of a specific phase or the discovery of an unknown polymorph always requires indexing of the associated diffraction pattern. However, despite the importance of this procedure, only a few approaches have been developed so far. Recently, an advanced mathematical framework for indexing of these specific diffraction patterns has been developed. Here, the successful implementation of this framework in the form of an automated indexing software, named GIDInd, is introduced. GIDInd is based on the assumption of a triclinic unit cell with six lattice constants and a distinct contact plane parallel to the substrate surface. Two approaches are chosen: (i) using only diffraction peaks of the GIXD pattern and (ii) combining the GIXD pattern with a specular diffraction peak. In the first approach the six unknown lattice parameters have to be determined by a single fitting procedure, while in the second approach two successive fitting procedures are used with three unknown parameters each. The output unit cells are reduced cells according to approved crystallographic conventions. Unit-cell solutions are additionally numerically optimized. The computational toolkit is compiled in the form of a MATLAB executable and presented within a user-friendly graphical user interface. The program is demonstrated by application on two independent examples of thin organic films.

Influence of Stereochemistry on the Monolayer Characteristics of N-alkanoyl-Substituted Threonine and Serine Amphiphiles at the Air-Water Interface.

Thermodynamic and structural properties of the N-alkanoyl-substituted α-amino acids threonine and serine, differing only by one CH3 group in the head group, are determined and compared. Detailed characterization of the influence of stereochemistry proves that all enantiomers form an oblique monolayer lattice structure whereas the corresponding racemates build orthorhombic lattice structures due to dominating heterochiral interactions, except N-C16-dl-serine-ME as first example of dominating homochiral interactions in a racemic mixture of N-alkanoyl-substituted α-amino acids. In all cases, the liquid expanded–liquid condensed (LE/LC) transition pressure of the racemic mixtures is above that of the corresponding enantiomers. Phase diagrams are proposed. Using the program Hardpack to predict tilt angles and cross-sectional area of the alkyl chains shows reasonable agreement with the experimental grazing incidence X-ray diffraction (GIXD) data.

Quantifying non-centrosymmetric orthorhombic phase fraction in 10 nm ferroelectric Hf0.5Zr0.5O2 films

In this Letter, we report the percentage of the ferroelectric phase in a 10-nm-thick Hf0.5Zr0.5O2 (HZO) film deposited in a metal-insulator-metal stack by atomic layer deposition. The ferroelectric behavior was confirmed by polarization measurements and piezoresponse force microscopy. Ferroelectric behavior in this material has been attributed most likely to the formation of the polar non-centrosymmetric orthorhombic phase [Müller et al., Appl. Phys. Lett. 99, 102903 (2011)], which is difficult to distinguish from the tetragonal phase in x-ray diffraction due to peak overlap. Using a model for each of the crystal phases of hafnia-zirconia, the phase percentages were estimated using a Rietveld refinement method applied to grazing incidence x-ray diffraction data and a linear combination fit analysis procedure [McBriarty et al., Phys. Status Solidi 257, 1900285 (2020)] applied to grazing incidence extended x-ray absorption fine structure data. Using these methods, it was found that the tetragonal (P42/nmc) phase is the most prevalent at 48–60% followed by the polar non-centrosymmetric orthorhombic (Pca21) phase at 35%–40% with the remainder consisting of the monoclinic (P21/c) phase. Understanding the details of the effect of the phase structure on the electrical properties of these materials is extremely important for device engineering of HZO for logic and emerging nonvolatile memory applications.

A scalable method for preparing Cu electrocatalysts that convert CO2 into C2+ products

Development of efficient catalysts for selective electroreduction of CO2 to high-value products is essential for the deployment of carbon utilization technologies. Here we present a scalable method for preparing Cu electrocatalysts that favor CO2 conversion to C2+ products with faradaic efficiencies up to 72%. Grazing-incidence X-ray diffraction data confirms that anodic halogenation of electropolished Cu foils in aqueous solutions of KCl, KBr, or KI creates surfaces of CuCl, CuBr, or CuI, respectively. Scanning electron microscopy and energy dispersive X-ray spectroscopy studies show that significant changes to the morphology of Cu occur during anodic halogenation and subsequent oxide-formation and reduction, resulting in catalysts with a high density of defect sites but relatively low roughness. This work shows that efficient conversion of CO2 to C2+ products requires a Cu catalyst with a high density of defect sites that promote adsorption of carbon intermediates and C–C coupling reactions while minimizing roughness.

High Temperature Stable Anatase Phase Titanium Dioxide Films Synthesized by Mist Chemical Vapor Deposition

Pure anatase-phase titanium dioxide films stable up to high temperatures were successfully fabricated by the mist chemical vapor deposition method. A post-annealing treatment of the synthesized films was carried out in oxygen atmosphere in the temperature range from 600 to 1100 °C and no anatase to rutile transformation was observed up to 1000 °C. Based on the grazing incidence X-ray diffraction data, the average crystallite size of the titanium dioxide films increased gradually with increasing annealing temperature. The structural analysis revealed that the high thermal stability of the anatase phase can be attributed to the small crystallite size and a sheet-like grain structure. An incomplete anatase to rutile transformation was observed after annealing at 1100 °C.

An efficient method for indexing grazing-incidence X-ray diffraction data of epitaxially grown thin films.

Crystal structure identification of thin organic films entails a number of technical and methodological challenges. In particular, if molecular crystals are epitaxially grown on single-crystalline substrates a complex scenario of multiple preferred orientations of the adsorbate, several symmetry-related in-plane alignments and the occurrence of unknown polymorphs is frequently observed. In theory, the parameters of the reduced unit cell and its orientation can simply be obtained from the matrix of three linearly independent reciprocal-space vectors. However, if the sample exhibits unit cells in various orientations and/or with different lattice parameters, it is necessary to assign all experimentally obtained reflections to their associated individual origin. In the present work, an effective algorithm is described to accomplish this task in order to determine the unit-cell parameters of complex systems comprising different orientations and polymorphs. This method is applied to a polycrystalline thin film of the conjugated organic material 6,13-pentacenequinone (PQ) epitaxially grown on an Ag(111) surface. All reciprocal vectors can be allocated to unit cells of the same lattice constants but grown in various orientations [sixfold rotational symmetry for the contact planes (102) and (102)]. The as-determined unit cell is identical to that reported in a previous study determined for a fibre-textured PQ film. Preliminary results further indicate that the algorithm is especially effective in analysing epitaxially grown crystallites not only for various orientations, but also if different polymorphs are present in the film.

Surface Induced Phenytoin Polymorph. 2. Structure Validation by Comparing Experimental and Density Functional Theory Raman Spectra

A method for structure solution in thin films that combines grazing incidence X-ray diffraction data analysis and crystal structure prediction was presented in a recent work (Braun et al. Cryst. Growth Des.2019, DOI: 10.1021/acs.cgd.9b00857). Applied to phenytoin form II, which is only detected in films, the approach gave a very reasonable, but not fully confirmed, candidate structure with Z = 4 and Z′ = 2. In the present work, we demonstrate how, by calculating and measuring the crystal Raman spectrum in the low wavenumber energy region with the aim of validating the candidate structure, this can be further refined. In fact, we find it to correspond to a saddle point of the energy landscape of the system, from which a minimum of lower symmetry may be reached. With the new structure, with Z = 4 and Z′ = 2, we finally obtain an excellent agreement between experimental and calculated Raman spectra.

GIDVis: a comprehensive software tool for geometry-independent grazing-incidence X-ray diffraction data analysis and pole-figure calculations.

GIDVis is a software package based on MATLAB specialized for, but not limited to, the visualization and analysis of grazing-incidence thin-film X-ray diffraction data obtained during sample rotation around the surface normal. GIDVis allows the user to perform detector calibration, data stitching, intensity corrections, standard data evaluation (e.g. cuts and integrations along specific reciprocal-space directions), crystal phase analysis etc. To take full advantage of the measured data in the case of sample rotation, pole figures can easily be calculated from the experimental data for any value of the scattering angle covered. As an example, GIDVis is applied to phase analysis and the evaluation of the epitaxial alignment of pentacene-quinone crystallites on a single-crystalline Au(111) surface.

Low temperature chemical vapor deposition of superconducting molybdenum carbonitride thin films

Thin films of molybdenum carbonitride, MoCxNy, are deposited by low temperature chemical vapor deposition from Mo(CO)6 and NH3 in the temperature range 150–300 °C. At a substrate temperature of 200 °C and Mo(CO)6 pressure of 0.01 mTorr, the composition varies from MoC0.48N0.20 to MoC0.36N0.33 (i.e., greater nitrogen and less carbon content) upon increasing the ammonia pressure from 0.3 to 3.3 mTorr. At a constant Mo(CO)6 pressure of 0.01 mTorr and an NH3 pressure of 2 mTorr, the composition varies from MoC0.50N0.30 to MoC0.12N0.40 with increasing substrate temperature from 150 to 300 °C. Selected films grown at substrate temperatures of 150, 200, and 250 °C are superconducting with critical temperatures of 4.7, 4.5, and 5.2 K, respectively. Grazing incidence x-ray diffraction data indicate that the films are crystalline and isomorphous with the cubic phases of Mo2N and Mo2C. With a forward-directed flux of precursors toward the surface, film growth is highly conformal in microtrenches of aspect ratio 6, with step coverages of ∼0.85 and 0.80 at growth temperatures of 150 and 200 °C, respectively.

Indexing of grazing-incidence X-ray diffraction patterns: the case of fibre-textured thin films.

Crystal structure solutions from thin films are often performed by grazing-incidence X-ray diffraction (GIXD) experiments. In particular, on isotropic substrates the thin film crystallites grow in a fibre texture showing a well defined crystallographic plane oriented parallel to the substrate surface with random in-plane order of the microcrystallites forming the film. In the present work, analytical mathematical expressions are derived for indexing experimental diffraction patterns, a highly challenging task which hitherto mainly relied on trial-and-error approaches. The six lattice constants a, b, c, α, β and γ of the crystallographic unit cell are thereby determined, as well as the rotation parameters due to the unknown preferred orientation of the crystals with respect to the substrate surface. The mathematical analysis exploits a combination of GIXD data and information acquired by the specular X-ray diffraction. The presence of a sole specular diffraction peak series reveals fibre-textured growth with a crystallographic plane parallel to the substrate, which allows establishment of the Miller indices u, v and w as the rotation parameters. Mathematical expressions are derived which reduce the system of unknown parameters from the three- to the two-dimensional space. Thus, in the first part of the indexing routine, the integers u and v as well as the Laue indices h and k of the experimentally observed diffraction peaks are assigned by systematically varying the integer variables, and by calculating the three lattice parameters a, b and γ. Because of the symmetry of the derived equations, determining the missing parameters then becomes feasible: (i) w of the surface parallel plane, (ii) the Laue indices l of the diffraction peak and (iii) analogously the lattice constants c, α and ß. In a subsequent step, the reduced unit-cell geometry can be identified. Finally, the methodology is demonstrated by application to an example, indexing the diffraction pattern of a thin film of the organic semiconductor pentacenequinone grown on the (0001) surface of highly oriented pyrolytic graphite. The preferred orientation of the crystallites, the lattice constants of the triclinic unit cell and finally, by molecular modelling, the full crystal structure solution of the as-yet-unknown polymorph of pentacenequinone are determined.

Effect of Zr content on structure property relations of Ni-Zr alloy thin films with mixed nanocrystalline and amorphous structure

A comparative study has been carried out on microstructural evolution, surface roughness, nanoindentation and scratch behavior, electrical resistivity, and corrosion resistance of Ni1-xZrx (0.13 ≤ x ≤ 0.40) thin films deposited on Si-(100) substrate by DC magnetron co-sputtering of high purity elemental targets in argon atmosphere. The film compositions have been examined by energy dispersive X-ray and Auger electron spectroscopy. Grazing incidence X-ray diffraction (GIXRD) studies have shown presence of Ni-rich solid solution, Ni3Zr and amorphous phase in all the films, with Ni5Zr being additionally observed in the Ni87Zr13 film. Analysis of GIXRD data along with transmission electron microscopic studies have shown that volume fractions of both amorphous phase and Ni3Zr are increased, whereas the average crystallite size is decreased with increase in Zr concentration. Nanoindentation hardness and Young's modulus as well as electrical resistivity measured by Van-der Pauw four-probe method are influenced by volume fractions of both Ni3Zr and amorphous phase. Surface roughness and coefficient of friction obtained from atomic force microscopy and nano-scratch experiments, respectively decrease, whereas corrosion resistance in 3.5 wt% NaCl solution increase with Zr concentration primarily due to increase in amorphous phase content. Resistance to pitting corrosion is facilitated by formation of ZrO2-rich passive film, as confirmed by X-ray photoelectron spectroscopy.

Effect of Surface Modification on In-Depth Transformations and Flexural Strength of Zirconia Ceramics.

Chairside surface adjustments of zirconia dental restorations enhance the toughening stress-induced tetragonal-to-monoclinic phase transformation and domain reorientation by ferro-elastic domain switching (FDS), but also trigger subsurface damage, which could compromise long-term clinical performance. The purpose of this study was to assess the depth of phase transformation, associated FDS, and flexural strength of dental zirconia (BruxZir HT 2.0), after chairside surface treatments. Square specimens were sectioned from CAD/CAM blocks and sintered according to manufacturer's recommendations (n = 30). They were left as-sintered (AS; control), air abraded with fine (AAF) or coarse (AAC) alumina particles, ground (G) or ground and polished (GP). Roughness was measured by profilometry. Crystalline phases were investigated by grazing incidence X-ray diffraction (GIXRD) (n = 3). GIXRD data were fit using semi-log regression protocols to assess transformation depth and extent of FDS. The mean biaxial flexural strength was measured according to ISO 6872. Subsurface damage was assessed from SEM images using a bonded polished interface configuration. Flaw distribution was assessed by Weibull analysis. Results were analyzed by Kruskal-Wallis with Tukey's adjustment for multiple comparisons (p < 0.05). Air-abraded and ground groups exhibited higher mean surface roughness than control. AAF group exhibited the highest flexural strength (1662.6 ± 202.6 MPa) with flaw size (5.9 ± 1.8 μm) smaller than transformation (14.5 ± 1.2 μm) or FDS depth (19.3 ± 1.1 μm), followed by GP group (1567.2 ± 209.7 MPa) with smallest FDS depth (9.3 ± 2.0 μm) and flaw size (2.6 ± 1.8 μm), but without m-phase. AAC group (1371.4 ± 147.6 MPa) had the largest flaw size (40.3 ± 20.3 μm), transformation depth (47.2 ± 3.0 μm) and FDS depth (41.2 ± 2.2 μm). G group (1357.0 ± 196.7 MPa) had the smallest transformation depth (8.6 ± 1.5 μm), and mean FDS depth (19.8 ± 3.7 μm) and flaw size (18.6 ± 3.1 μm). AAC and AAF exhibited the highest Weibull modulus (11.2 ± 0.4 and 9.8 ± 0.3 μm, respectively). Variations in mean biaxial flexural strength were explained by the balance between the depth of toughening mechanisms (phase transformation and FDS) and subsurface damage. AAF and GP groups were the most efficient surface adjustments in promoting the highest mean biaxial flexural strength.