Synchrotron Radiation-grazing Incidence X-ray Diffraction Research Articles

Research on the structure-activity relationship of Fe-Cr alloy in marine environment based on synchrotron radiation: Effect of Cr content

A solid-liquid interface will form on the surface of metal materials when immersed in the marine, which determines the corrosion resistance. Alloying is one of the most effective approaches to protect materials from corrosion failure by tuning the structure-activity relationship of the solid-liquid interface. Chromium is the decisive element in determining the corrosion resistance of iron-based alloys because it can increase electrode potential and promote passivation. However, up to date, the effect of chromium on materials service safety has not been adequately validated, which restricted the precise design and application of the corrosion resistance alloys. Herein, we probed the effect of Cr on structure-activity relationship with multiple characterization means including electrochemistry, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), surface enhanced Raman spectroscopy (SERS), synchrotron radiation grazing-incidence X-ray diffraction (GIXRD), and X-ray absorption fine structure (XAFS). The solid-liquid interface is mostly amorphous, with some nanocrystals. The addition of Cr can promote the increase of FeOOH and formation of FeCr2O4, with first increase and then decrease of Cr2O3. The enrichment of FeOOH and Cr2O3 improves corrosion resistance when Cr content is less than 30 wt.%. The formation of FeCr2O4 leads to the transformation from corrosion products to passive film when Cr content exceeds 18 wt.%. In addition, the lack of Cr2O3 and the formation of FeCr2O4 result in the descend of corrosion resistance at 40 wt.% Cr content.

On the transformation of "zincone"-like into porous ZnO thin films from sub-saturated plasma enhanced atomic layer deposition.

The synthesis of nanoporous ZnO thin films is achieved through annealing of zinc-alkoxide (“zincone”-like) layers obtained by plasma-enhanced atomic layer deposition (PE-ALD). The zincone-like layers are deposited through sub-saturated PE-ALD adopting diethylzinc and O2 plasma with doses below self-limiting values. Nanoporous ZnO thin films were subsequently obtained by calcination of the zincone-like layers between 100–600 °C. Spectroscopic ellipsometry (SE) and X-ray diffraction (XRD) were adopted in situ during calcination to investigate the removal of carbon impurities, development of controlled porosity, and formation and growth of ZnO crystallites. The layers developed controlled nanoporosity in the range of 1–5%, with pore sizes between 0.27 and 2.00 nm as measured with ellipsometric porosimetry (EP), as a function of the plasma dose and post-annealing temperature. Moreover, the crystallinity and crystallite orientation could be tuned, ranging from a powder-like to a (100) preferential growth in the out-of-plane direction, as measured by synchrotron-radiation grazing incidence XRD. Calcination temperature ranges were identified in which pore formation and subsequent crystal growth occurred, giving insights in the manufacturing of nanoporous ZnO from Zn-based hybrid materials.

Development of an electrochemically integrated SR-GIXRD flow cell to study FeCO3 formation kinetics.

An electrochemically integrated Synchrotron Radiation-Grazing Incidence X-Ray Diffraction (SR-GIXRD) flow cell for studying corrosion product formation on carbon steel in carbon dioxide (CO2)-containing brines typical of oil and gas production has been developed. The system is capable of generating flow velocities of up to 2 m/s at temperatures in excess of 80 °C during SR-GIXRD measurements of the steel surface, enabling flow to be maintained over the course of the experiment while diffraction patterns are being collected. The design of the flow cell is presented, along with electrochemical and diffraction pattern transients collected from an initial experiment which examined the precipitation of FeCO3 onto X65 carbon steel in a CO2-saturated 3.5 wt. % NaCl brine at 80 °C and 0.1 m/s. The flow cell is used to follow the nucleation and growth kinetics of FeCO3 using SR-GIXRD linked to the simultaneous electrochemical response of the steel surface which were collected in the form of linear polarisation resistance measurements to decipher in situ corrosion rates. The results show that FeCO3 nucleation could be detected consistently and well before its inhibitive effect on the general corrosion rate of the system. In situ measurements are compared with ex situ scanning electron microscopy (SEM) observations showing the development of an FeCO3 layer on the corroding steel surface over time confirming the in situ interpretations. The results presented demonstrate that under the specific conditions evaluated, FeCO3 was the only crystalline phase to form in the system, with no crystalline precursors being apparent. The numerous capabilities of the flow cell are highlighted and presented in this paper.

Electrochemical and Surface Analysis Studies on the Carbon Dioxide Corrosion of X‐65 Carbon Steel

AbstractA comprehensive study of the CO2 corrosion of carbon steel (X‐65) at low partial pressures of CO2 is reported in this paper. Field emission scanning electron microscopy (FESEM), Raman spectroscopy (RS), synchrotron radiation‐grazing incidence X‐ray diffraction (SR‐GIXRD), and electrode kinetic studies have confirmed that chukanovite, magnetite and siderite are the main corrosion products at low partial pressures of CO2. Chukanovite forms predominantly in the presence of CO2, while magnetite was found to be the major corrosion product in the absence of CO2, although the majority of previous work based on conventional ex‐situ materials characterization techniques has implied that siderite is the main corrosion product. Here, it is shown that the nature of corrosion products is strongly dependent on the experimental conditions at low pressures of CO2, which has not been elucidated in previous studies. Accordingly, this study has made a significant contribution to identifying the true nature of corrosion scales formed at low partial pressures of CO2 allowing the development of effective anti‐corrosive agents for the control and prevention of carbon steel corrosion at low CO2 partial pressures.

Understanding Complex Electrochemical Impedance Spectroscopy in Corrosion Systems Using in‐situ Synchrotron Radiation Grazing Incidence X‐ray Diffraction

AbstractThe difficulty in interpreting electrochemical impedance spectroscopy (EIS) data has limited the potential of the method despite its utility as an electrochemical method for studies of electrode reactions and interfacial structures. Taking the test case of the carbon dioxide corrosion of carbon steel, in‐situ synchrotron radiation grazing incidence X‐ray diffraction (SR‐GIXRD) has been demonstrated to be a powerful technique for validating and understanding the interfacial structures associated with complex EIS data. Carbon dioxide corrosion was found to occur in several steps, which may only be surmised by EIS, but the use of SR‐GIXRD in conjunction with EIS has enabled the establishment of a link between EIS time constants and structural changes associated with the evolution of corrosion products with time. By comparison to previous studies by the authors and others in this field, this communication provides the first direct experimental evidence linking SR‐GIXRD surface compositional data to otherwise indistinctive EIS time constants.

Low thermal conductivity and improved thermoelectric performance of nanocrystalline silicon germanium films by sputtering

SixGe1−x alloys are well-known thermoelectric materials with a high figure of merit at high temperatures. In this work, metal-induced crystallization (MIC) has been used to grow Si0.8Ge0.2 films that present improved thermoelectric performance (zT = 5.6 × 10−4 at room temperature)—according to previously reported values on films—with a relatively large power factor (σ · S2 = 16 μW · m−1 · K−2). More importantly, a reduction in the thermal conductivity at room temperature (κ = 1.13 ± 0.12 W · m−1 · K−1) compared to other Si–Ge films (∼3 W · m−1 · K−1) has been found. Whereas the usual crystallization of amorphous SiGe (a-SiGe) is achieved at high temperatures and for long times, which triggers dopant loss, MIC reduces the crystallization temperature and the heating time. The associated dopant loss is thus avoided, resulting in a nanostructuration of the film. Using this method, we obtained Si0.8Ge0.2 films (grown by DC plasma sputtering) with appropriate compositional and structural properties. Different thermal treatments were tested in situ (by heating the sample inside the deposition chamber) and ex situ (annealed in an external furnace with controlled conditions). From the studies of the films by: x-ray diffraction (XRD), synchrotron radiation grazing incidence x-ray diffraction (SR-GIXRD), micro Raman, scanning electron microscopy (SEM), x-ray photoemission spectroscopy (XPS), Hall effect, Seebeck coefficient, electrical and thermal conductivity measurements, we observed that the in situ films at 500 °C presented the best zT values with no gold contamination.

Effect of halogen-terminated additives on the performance and the nanostructure of all-polymer solar cells

Here, we report the influence of halogen-terminated additives on the performance and the nanostructure of all-polymer solar cells that are made with bulk heterojunction (BHJ) films of poly(3-hexylthiophene) (P3HT) (as an electron donor) and poly(9,9-dioctylfluorene-co-benzothiadiazole) (F8BT) (as an electron acceptor). Diiodooctane (DIO) and dibromooctane (DBO) were employed as additives in order to compare the effect of different halogen groups (bromine and iodine). Results showed that the power conversion efficiency of devices was slightly (∼15%) improved by using additives due to the increased open-circuit voltage and fill factor. The synchrotron radiation grazing-incidence X-ray diffraction (GIXD) measurements disclosed that the performance improvement was closely related to the relatively well-evolved nanostructures in the P3HT:F8BT films caused by the additives.

Fully coherent growth of Ge on free-standing Si(001) nanomesas

We investigate the structural properties of Ge nanostructures selectively grown on Si. Defect-free nanostructures with a lateral size of 100 nm and surrounded by a thick (\ensuremath{\sim}20 times larger than the coherent-film limit) Ge layer are achieved as demonstrated by transmission electron microscopy. As demonstrated by modeling based on elasticity theory solved by finite element methods, the peculiar combination of morphology and chemical composition of the nanostructures allows for a very efficient elastic relaxation of the heteroepitaxial strain. We demonstrate that, despite the relatively large size of the nanostructures, even a single dislocation would raise the energy of the system. A direct comparison between the strain field predicted by modeling and measured by energy-dispersive synchrotron-radiation grazing incidence x-ray diffraction shows substantial agreement.

A Combined Voltammetric and Synchrotron Radiation-Grazing Incidence X-ray Diffraction Study of the Electrocrystallization of Zinc Tetracyanoquinodimethane

The in situ electrocrystallization of zinc tetracyanoquinodimethane (TCNQ) has been explored using synchrotron radiation-grazing incidence X-ray diffraction (SR-GIXRD) at potentials in the region of the cyclic voltammetric peak where reduction of TCNQ to TCNQ– occurs at a Pt electrode in acetonitrile (0.1 M [NBu4][PF6]) solution containing Zn(NO3)2·6H2O. The in situ SR-GIXRD data along with ex situ IR and Raman spectroscopy results all confirmed the formation of the kinetically favoured phase of Zn[TCNQ]2(H2O)2 as the product.

A flow cell for transient voltammetry and in situ grazing incidence X-ray diffraction characterization of electrocrystallized cadmium(II) tetracyanoquinodimethane

An easy to fabricate and versatile cell that can be used with a variety of electrochemical techniques, also meeting the stringent requirement for undertaking cyclic voltammetry under transient conditions in in situ electrocrystallization studies and total external reflection X-ray analysis, has been developed. Application is demonstrated through an in situ synchrotron radiation-grazing incidence X-ray diffraction (SR-GIXRD) characterization of electrocrystallized cadmium (II)-tetracyanoquinodimethane material, Cd(TCNQ) 2, from acetonitrile (0.1 mol dm −3 [NBu 4][PF 6]). Importantly, this versatile cell design makes SR-GIXRD suitable for almost any combination of total external reflection X-ray analysis (e.g., GIXRF and GIXRD) and electrochemical perturbation, also allowing its application in acidic, basic, aqueous, non-aqueous, low and high flow pressure conditions. Nevertheless, the cell design separates the functions of transient voltammetry and SR-GIXRD measurements, viz., voltammetry is performed at high flow rates with a substantially distended window to minimize the IR (Ohmic) drop of the electrolyte, while SR-GIXRD is undertaken using stop-flow conditions with a very thin layer of electrolyte to minimize X-ray absorption and scattering by the solution.

Engineering the semiconductor/oxide interaction for stacking twin suppression in single crystalline epitaxial silicon(111)/insulator/Si(111) heterostructures

The integration of alternative semiconductor layers on the Si material platform via oxide heterostructures is of interest to increase the performance and/or functionality of future Si-based integrated circuits. The single crystalline quality of epitaxial (epi) semiconductor–insulator–Si heterostructures is however limited by too high defect densities, mainly due to a lack of knowledge about the fundamental physics of the heteroepitaxy mechanisms at work. To shed light on the physics of stacking twin formation as one of the major defect mechanisms in (111)-oriented fcc-related heterostructures on Si(111), we report a detailed experimental and theoretical study on the structure and defect properties of epi-Si(111)/Y2O3/Pr2O3/Si(111) heterostructures. Synchrotron radiation-grazing incidence x-ray diffraction (SR-GIXRD) proves that the engineered Y2O3/Pr2O3 buffer dielectric heterostructure on Si(111) allows control of the stacking sequence of the overgrowing single crystalline epi-Si(111) layers. The epitaxy relationship of the epi-Si(111)/insulator/Si(111) heterostructure is characterized by a type A/B/A stacking configuration. Theoretical ab initio calculations show that this stacking sequence control of the heterostructure is mainly achieved by electrostatic interaction effects across the ionic oxide/covalent Si interface (IF). Transmission electron microscopy (TEM) studies detect only a small population of misaligned type B epi-Si(111) stacking twins whose location is limited to the oxide/epi-Si IF region. Engineering the oxide/semiconductor IF physics by using tailored oxide systems opens thus a promising approach to grow heterostructures with well-controlled properties.

Understanding barium sulfate precipitation onto stainless steel

This paper investigates the influence of barium sulfate scaling and scaling inhibitors on the electrochemical behaviour of stainless steel. The results of a synchrotron radiation grazing incidence X-ray diffraction (SR-GIXRD) and electrochemical impedance spectroscopy (EIS) study on stainless steel shows that different scaling inhibitors interact uniquely with the substrate when barium sulfate is precipitated on the electrode surface. The main effect of the substrate in the presence of inhibitor is a tendency to form smaller barium sulfate particles. The SR-GIXRD patterns obtained in the presence of the two inhibitors were different to each other and to the control, with the carboxylate showing greater amounts of barite solids precipitated together with iron(III) and (II) sulfate, while the phosphonate showed low amounts of barite solid were precipitated. The presence of iron sulfates on the electrode surface as detected by SR-GIXRD, in the case of NTA, suggests that scaling inhibitors are not always benign, and can promote the dissolution of iron species from the substrate.

Study of stacking fault effect on magnetic anisotropy of CoPtCr–SiO2 perpendicular media by synchrotron radiation x-ray diffraction

Thin films of CoPtCr and CoPtCr–SiO2, perpendicular magnetic media materials, were investigated by synchrotron radiation grazing-incidence x-ray diffraction. The analysis of diffraction peaks in a reciprocal space provided the variation of stacking faults as functions of Pt content in these materials. It was found that stacking faults start increasing at 15–20 and 25–30at.% Pt for CoPtCr–SiO2 and CoPtCr films, respectively. These results can well explain the phenomenon whereby the magnetic anisotropy of CoPtCr–SiO2 increases with an increasing Pt content and decreases above 20at.% Pt, whereas that of CoPtCr increases up to 30at.% Pt and then decreases.

A complex x-ray characterization of epitaxially grown high-K gate dielectrics

Different x-ray techniques are used to characterize Pr2O3 layers epitaxially grown on Si substrates. X-ray reflectometry is the preferred technique to determine the layer thickness and to detect and characterize possible interface layers. With standard x-ray diffraction (XRD), we found for 100 Si substrates that Pr2O3 grows in its cubic phase with the 110 direction perpendicular to the surface, while the hexagonal phase in 0001 orientation is preferred for 111 Si. In the thickness range of microelectronics applications, Pr2O3 layers can be considered as well-ordered heteroepitaxial structures. The relaxation of the oxide layer from pseudomorphism to bulk behaviour was studied in the technologically important thickness range (1–10 nm) by synchrotron radiation grazing incidence XRD.

Structure and strain relaxation mechanisms of ultrathin epitaxial Pr2O3 films on Si(111)

The structure of ultrathin epitaxial Pr2O3 films on Si(111) was studied by synchrotron radiation-grazing incidence x-ray diffraction. The oxide film grows as hexagonal Pr2O3 phase with its (0001) plane attached to the Si(111) substrate. The hexagonal (0001) Pr2O3 plane matches the in-plane symmetry of the hexagonal Si(111) surface unit cell by aligning the ⟨101¯0⟩Pr2O3 along the ⟨112¯⟩ Si directions. The small lattice mismatch of 0.5% results in the growth of pseudomorphic oxide films of high crystalline quality with an average domain size of about 50 nm. The critical thickness tc for pseudomorphic growth amounts to 3.0±0.5nm. The relaxation of the oxide film from pseudomorphism to bulk behavior beyond tc causes the introduction of misfit dislocations, the formation of an in-plane small angle mosaicity structure, and the occurence of a phase transition towards a (111) oriented cubic Pr2O3 film structure. The observed phase transition highlights the influence of the epitaxial interface energy on the stability of Pr2O3 phases on Si(111). A mechanism is proposed which transforms the hexagonal (0001) into the cubic (111) Pr2O3 epilayer structure by rearranging the oxygen network but leaving the Pr sublattice almost unmodified.

Structure and thickness-dependent lattice parameters of ultrathin epitaxial Pr2O3 films on Si(001)

Pr 2 O 3 grown heteroepitaxially on Si(001) is a promising candidate for applications as a high-k dielectric in future silicon-based microelectronics devices. The technologically important thickness range from 1to10nm has been investigated by synchrotron radiation-grazing incidence x-ray diffraction. The oxide film grows as cubic Pr2O3 phase with its (101) plane on the Si(001) substrate in form of two orthogonal rotation domains. Monitoring the evolution of the oxide unit-cell lattice parameters as a function of film thickness from 1to10nm, the transition from almost perfect pseudomorphism to bulk values is detected.

A multi-technique surface study of the mercury(II) chalcogenide ion-selective electrode in saline media.

X-ray photoelectron spectroscopy (XPS), secondary ion mass spectrometry (SIMS), rotating disc electrode-electrochemical impedance spectroscopy (RDE-EIS) and synchrotron radiation-grazing incidence X-ray diffraction (SR-GIXRD) have been used to study the response mechanism of the mercury(II) chalcogenide ion-selective electrode (ISE) in saline media. XPS and SIMS have shown that the chalcogenide surface is poisoned by silver chloride, or a mixture of silver halides, on continuous exposure to synthetic and real seawater. Significantly, the in-situ SR-GIXRD study demonstrated that electrode fouling in synthetic seawater is linked to the formation of poorly crystalline or amorphous silver chloride, and that the low level of free mercury(II) in a calibration buffer (i.e., 10(-14) M) is able to undergo metathesis with silver(II) sulfide in the membrane generating mercury(II) sulfide. Significantly, the results of this detailed surface study have shown that silver chloride fouling of the electrode is ameliorated in real seawater comprising natural organic ligands, and this has been attributed to the peptization of silver chloride by the surfactant-like nature of seawater ligands at pH 8. RDE-EIS aging studies have revealed that the chalcogenide membrane experiences a sluggish charge transfer reaction in seawater, and contrary to a previous report for a static electrode, the seawater matrix does not passivate the RDE. The results of this XPS, SIMS, RDE-EIS and SR-GIXRD study have elucidated the response mechanism of the mercury(II) ISE in saline media.