Cr2O3 Film Research Articles

Antiferromagnetic Nanoscale Bit Arrays of Magnetoelectric Cr2O3 Thin Films.

Magnetism of oxide antiferromagnets (AFMs) has been studied in single crystals and extended thin films. The properties of AFM nanostructures still remain underexplored. Here, we report on the fabrication and magnetic imaging of granular 100 nm-thick magnetoelectric Cr2O3 films patterned in circular bits with diameters ranging from 500 down to 100 nm. With the change of the lateral size, the domain structure evolves from a multidomain state for larger bits to a single domain state for the smallest bits. Based on spin-lattice simulations, we show that the physics of the domain pattern formation in granular AFM bits is primarily determined by the energy dissipation upon cooling, which results in motion and expelling of AFM domain walls of the bit. Our results provide a way toward the fabrication of single domain AFM-bit-patterned memory devices and the exploration of the interplay between AFM nanostructures and their geometric shape.

Enhanced accident tolerance properties of AlCrCuFeMoNbx high entropy coating for nuclear fuel cladding

High entropy alloy AlCrCuFeMoNbx (x=0.5, 0.8, 1.4, 2.0) coatings were deposited on Zr-1Nb alloy substrates by magnetron co-sputtering to improve the accident tolerance capability of the nuclear fuel cladding. The structural and accidental tolerant properties of high-entropy alloy coatings have been investigated comprehensively. The results show that coatings with varying Nb contents exhibit amorphous structures. The hardness and elastic modulus of the coatings increase with the Nb content, reaching their maximum values at x = 2.0, which are 11.38GPa and 186.05GPa, respectively. In both the simulated normal operating and accident environment of the nuclear fuel cladding, the oxidation resistance of the coating has been investigated. The best oxidation resistance was achieved at x=0.8 in pure water at 360℃under 18.6MPa for 3 days. The dense Cr2O3 and CrNbO4 oxide films generated on the surface hinder the diffusion of oxygen ions, and account for the lower weight gain 5.10mg/dm2, decreased by 56.4% compared to that of the uncoated zirconium alloy. The coating with x=0.5 showed a drastic reduction in oxidized weight gain by 84.02% compared to the uncoated zirconium alloy in water steam at 1200℃, demonstrating excellent accident tolerance, which is due to the dense α-Al2O3 and CrNbO4 protective layer generated on the surface of the coating. These findings suggest that high entropy alloy coatings have promising accidental tolerance capabilities for nuclear fuel cladding.

Comparative study of corrosion behaviors of SS310 stainless steel in NaCl-KCl-MgCl2 and NaCl-KCl-CaCl2 molten salts

Concentrated solar power plants using chloride molten salt as heat transfer fluids imply high corrosion risks. The corrosion behaviour of SS310 stainless steel in NaCl-KCl-MgCl2 and NaCl-KCl-CaCl2 molten salts was comparatively studied. MgCl2 exhibits remarkably higher hygroscopicity than CaCl2, inducing a significant difference in the concentration of HCl that directly results in the matrix corrosion. The hydrolysis of MgCl2 produces large amounts of MgO that destroys Cr2O3 film and produce less-protective MgCr2O4. Correspondingly, a heterogeneous oxide bilayer is formed in NaCl-KCl-MgCl2. In NaCl-KCl-CaCl2, a lamellar oxide layer composed of primarily Ni(Fe,Cr)2O4 can effectively block the corrosive species H2O and HCl.

Atomic layer deposition, mechanical, wear resistance, and optical properties of (Cr1-xAlx)2O3 films on Si (100)

This study presents the comparison of microstructure, mechanical, tribological, and optical properties of the ternary chromium-aluminum oxide films ((Cr1-xAlx)2O3) with binary Cr2O3 and Al2O3 films, deposited by atomic layer deposition at 275 °C. The atomic growth per cycle of the Al atoms increased from 3.1 to 8.5 atoms/nm2 on chromium oxide film. The Al2O3 films were X-ray amorphous. The Cr2O3 films contained crystallites of the eskolaite phase. Nano-size (diameter from 3 to 5 nm) crystallites with cubic symmetry and matching with that of cubic γ-Al2O3 or η-Al2O3 phases were observed in (Cr1-xAlx)2O3 films. The ternary film with Al/(Al + Cr) of 0.40 showed the highest hardness (18.4 GPa) and elastic modulus (169.4 GPa), whereas the wear rate of this film decreased by ∼80 % compared with Cr2O3 films. Optical band gap energy values corresponding to the indirect transition model decreased from 2.93 eV for the Cr2O3 film to 2.58 eV for the Cr-Al-O films.

Effects of Nb on Creep Properties and Hot Corrosion Resistance of New Alumina-Forming Austenitic Steels at 700 °C

Effects of Nb on the creep resistance and hot corrosion behavior of the Fe-25Cr-35Ni-2.5Al-xNb (x = 0, 0.6, 1.2) Alumina-Forming Austenitic stainless steels (AFA steels) at 700 °C were investigated. The addition of Nb promoted the precipitation of both nanoscale NbC and γ′-Ni3(Al, Nb) phases, which exhibited very low coarsening rate constants. The nanoscale NbC and γ′-Ni3(Al, Nb) phases effectively impeded the migration of dislocations and led to an improvement in creep performance of the Nb-addition AFA steel. The corrosion of AFA steels in Na2SO4-25%K2SO4 at 700 °C was primarily driven by an “oxidation-sulfidation” mechanism. The addition of Nb, serving as a third element, facilitated the formation of protective Cr2O3 and Al2O3 films, which improved the hot corrosion resistance performance. However, the formation Nb2O5 was found to compromise the compactness of the oxide film, which adversely affected the corrosion resistance.

High-temperature corrosion behavior of 316 H stainless steel in lead-bismuth eutectic containing cesium

The influence of Cs on the corrosion of 316 H stainless steel pipework when exposed to liquid lead–bismuth eutectic (LBE) coolant, specifically LBE containing 0.5 wt% Cs at high temperature, is investigated. The addition of Cs in LBE can significantly accelerate the corrosion of 316 H stainless steel. Cs in LBE first destroys the Cr2O3 film on the surface of the stainless steel and reacts with Cr23C6 enriched at grain boundaries. Finally, the reaction between Cs and FeCr2O4 creates pores in inner oxide layer (IOL), thus destroying the protection provided to 316 H stainless steel by the IOL.

Palladium enhanced electrochemical supercapacitive performance of chromium oxide thin films synthesized by sputtering process

Recently, the use of transition metal oxide electrodes for supercapacitor applications has increased due to the possibility of variable mixed valence states. The present study has established the use of Pd-Cr2O3 composite thin films as a working electrode for high-performance supercapacitors. The reactive dc magnetron co-sputtering method has been used for the fabrication of thin film of Cr2O3 and Pd-Cr2O3 on SS-304 substrate. X-ray diffraction and X-ray photoemission spectroscopy techniques were used to examine the surface chemistry and phase purity of chromium oxide and Pd-Cr2O3 composite thin films. The incorporation of Pd in Cr2O3 delivers a drastic change in the surface morphology. Due to the modified morphology and electronic properties, a noticeable improvement in the electrochemical properties of Pd-Cr2O3 electrode is observed. The obtained value of specific capacitance for this electrode is 401 Fg−1 at 0.1 mAcm−2 scan rate and within the potential window range 0 to +1.2 V. This value of specific capacitance is almost twice in comparison to the Cr2O3 based electrode. The Pd-Cr2O3 composite thin film shows a good cycle retention capability of 8000 cycles with 87.5 % retention. The obtained value of energy density and power density for Pd-Cr2O3 electrode was 80.2 Whkg−1 and 3.23 kWkg−1, respectively at 0.1 mAcm−2. Consequently, this composite material electrode can be seen as a promising advancement for electrodes in supercapacitor devices.

Electrochemical corrosion and tribocorrosion behavior of CrN and CrAlN coatings in artificial seawater

AbstractThis study investigated the corrosion and tribocorrosion behavior of CrN and CrAlN coatings deposited on steel through direct current magnetron sputtering. Additionally, the effects of Al addition on the microstructure, corrosion inhibition, and tribocorrosion behavior of CrN coatings were evaluated. Compared with the CrN coating, the CrAlN coating exhibited a denser columnar crystal structure and a higher hardness of 23.8 GPa. The CrAlN coating reacted with water to form Al2O3 and Cr2O3 films, which enhanced its corrosion resistance. Moreover, the addition of Al enhanced the wear resistance of the CrN coating and reduced the material loss due to corrosion, wear, and their synergistic effects. The CrAlN coating exhibited a low corrosion current density of 1.14 × 10−8 A/cm2, indicating a 92% reduction compared with the CrN coating. Furthermore, under either open circuit potential or anodic accelerated tribocorrosion conditions, the CrAlN coating featured significantly lower total material loss and synergistic material loss than the CrN coating, demonstrating higher corrosion and tribocorrosion protection.

Wafer-scale development, characterization, and high temperature stabilization of epitaxial Cr2O3 films grown on Ru(0001).

This work outlines conditions suitable for the heteroepitaxial growth of Cr2O3(0001) films (1.5-20nm thick) on a Ru(0001)-terminated substrate. Optimized growth is achieved by sputter deposition of Cr within a 4mTorr Ar/O2 20% ambient at Ru temperatures ranging from 450 to 600 °C. The Cr2O3 film adopts a 30° rotated honeycomb configuration with respect to the underlying Ru(0001) substrate and exhibits a hexagonal lattice parameter consistent with that for bulk Cr2O3(0001). Heating to 700 °C within the same environment during film preparation leads to Ru oxidation. Exposure to temperatures at or above 400 °C in a vacuum, Ar, or Ar/H2 3% leads to chromia film degradation characterized by increased Ru 3d XPS intensity coupled with concomitant Cr 2p and O 1s peak attenuations when compared to data collected from unannealed films. An ill-defined but hexagonally well-ordered RuxCryOz surface structure is noted after heating the film in this manner. Heating within a wet Ar/H2 3% environment preserves the Cr2O3(0001)/Ru(0001) heterolayer structure to temperatures of at least 950 °C. Heating an Ru-Cr2O3-Ru heterostacked film to 950 °C within this environment is shown by cross-sectional scanning/transmission electron microscopy (S/TEM) to provide clear evidence of retained epitaxial bicrystalline oxide interlayer structure, interlayer immiscibility, and epitaxial registry between the top and bottom Ru layers. Subtle effects marked by O enrichment and O 1s and Cr 2p shifts to increased binding energies are noted by XPS in the near-Ru regions of Cr2O3(0001)/Ru(0001) and Ru(0001)/Cr2O3(0001)/Ru(0001) films after annealing to different temperatures in different sets of environmental conditions.

Intergranular corrosion of Ni-30Cr in high-temperature hydrogenated water after removing surface passivating film

High-resolution transmission electron microscopy and atom probe tomography are used to characterize the initial passivation and subsequent intergranular corrosion of degraded grain boundaries in a model Ni-30Cr alloy exposed to 360 °C hydrogenated water. Upon initial exposure for 1000 h, the alloy surface directly above the grain boundary forms a thin passivating film of Cr2O3, protecting the underlying grain boundary from intergranular corrosion. However, the metal grain boundary experiences severe Cr depletion and grain boundary migration during this initial exposure. To understand how Cr depletion affects further corrosion, the local protective film was sputtered away using a glancing angle focused ion beam. Upon further exposure, the surface fails to repassivate, and intergranular corrosion is observed through the Cr-depleted region. Through this combination of high-resolution microscopy and localized passive film removal, we show that, although high-Cr alloys are resistant to intergranular attack and stress corrosion cracking, degradation-induced changes in the underlying metal at grain boundaries make the material more susceptible once the initial passive film is breached.

The role of magnetic anisotropy in the magnetoresistance of Cr2O3/Al2O3 thin film antiferromagnets

The magnetic states of antiferromagnetic insulating thin films are a promising medium for information storage, but characterization of these states has proven to be challenging. One approach is via magnetotransport measurements in an adjacent heavy metal layer. To this end, we synthesized and characterized a series of Cr2O3 films and bilayers on Al2O3 substrates with three different orientations: m-plane, a-plane, and c-plane. X-ray diffraction results demonstrated orientation control of the Cr2O3 thin film, with m-plane films displaying a higher degree of mosaic spread than the a- and c-plane films. Reciprocal space maps showed that the films are mostly relaxed, although there was a small and different degree of strain in each orientation. The m-plane films were under 2% compressive strain, the a-plane film was under 0.5% compressive strain, and the c-plane film was completely relaxed to bulk values. To probe the magnetic state of the films, we measured the angular dependent magnetoresistance of Cr2O3/Pt bilayers for each orientation. We found a nontrivial temperature dependence of the sign of the magnetoresistance, pointing to the complex interplay between the exchange and anisotropy energies that vary with orientation. We propose that strain and mosaic spread may contribute to a difference in magnetic anisotropies among the samples and the resulting temperature dependence of the magnetoresistance. This work demonstrates the importance of considering the competition between antiferromagnetic exchange and magnetic anisotropy when storing information in the spin state of an antiferromagnetic insulator.

Photoluminescence of combinatorically sputtered Al2O3–Y2O3 thin films with a Cr3+ and Nd3+ co-doping concentration gradient

The characterization of a wide range of luminescent thin films can be a long and tedious endeavor. With reactive combinatorial sputtering of multiple metal targets, it possible to fabricate thin films with a gradient in composition simply by not rotating the substrate. In this work, combinatorically sputtered thin films of Cr3+ and Nd3+ doped in the Al2O3–Y2O3 system (YAlO) are studied for thin film based luminescent solar concentrators (TFLSCs) application. Contrary to mm's thick plate type LSC's, TFLSCs of just several 100 nm thick require much higher Cr3+ concentration to achieve 40% absorption which can enable several 10's of W/m2 LSC power efficiencies. Our transmission measurements on a Cr2O3 film with a thickness gradient result in an absorption cross section at 460 nm of 1.3 ± 0.7 × 10−19 cm2 showing that the TFLSC absorption requirement can be fulfilled provided that the Cr3+ concentration is in the order of 1022 ions/cm3. The Y:Al ratio of the YAlO host in our films ranged between 0.5 and 3.5, thereby including the monoclinic (Y4Al2O9), perovskite (YAlO3) and garnet (Y3Al5O12) stoichiometry's on a single film. Position dependent XRD, EDX, excitation, emission and lifetime measurements of Cr3+ and Nd3+ show that the unique gradient film sputtering method is able to characterize thin films as a function of host composition and doping concentration. Energy transfer between Cr3+ and Nd3+ in co-doped YAlO films is concluded from Cr3+ excitation bands observed while monitoring Nd3+ emission and from the matching of the rise-time of Nd3+ 1340 nm emission (4F3/2 ->4I11/2) and the decay time of Cr3+ 840 nm emission (4T2 ->4A2). Nd3+ lifetime systematically decreases from 0.24 to 0.05 ms with increasing Cr3+ concentration in Y3Al5-xCrxO12:Nd (0.05 < x < 2). The constraints of heavily doped Cr3+ thin films for enabling adequate absorption and energy transfer to Nd3+ in TFLSC applications are the subjects of the discussion.

Tuning optical and electrical characteristics through Cu doping in spray pyrolysis fabricated Cr2O3 thin films

This study focuses on the physical properties of thin films of Cr2O3 and Cu-doped Cr2O3 (1−4 % Cu), with a thickness of approximately ∼500 nm. These films were deposited on preheated soda-lime glass substrates using the spray pyrolysis technique. The characterization of the thin films was carried out through Raman spectroscopy, UV–visible spectroscopy, and the four-point probe technique. The Raman analysis revealed vibrational modes associated with Eg and A1g symmetries in Cr2O3. The optical band gap energy exhibited a decrease from 2.92 eV to 2.6 eV with an increase in Cu content. The study also involved the evaluation of extinction coefficient, refractive index, dielectric constants, and optical conductivity of the thin films. The dispersion of the refractive index was studied using the single oscillator model (Wemple-DiDomenico). The electrical resistivity values decreased from 1000 Ω-cm to 33 Ω-cm with increasing Cu content. Notably, Cr2O3 thin films with 4 % Cu content demonstrated the best figure of merit, recording a value of 4.66 M Ω−1.

Interfacial modulation of magnetic relaxation and electrical characteristic in RuO2/CrO2 antiferromagnet-half metal bilayer

Half-metallic chromium dioxide (CrO2) is a promising candidate in magnetic random-access memory (MRAM) devices due to its nearly full spin polarization and ultralow Gilbert damping at room temperature. In this study, we succeeded in fabricating (110) and (100)-oriented RuO2/CrO2 bilayers with different thicknesses of CrO2 film using two-step method. The CrO2 film epitaxially grown on a RuO2 layer exhibits a perfect in-plane magnetic uniaxial anisotropy. The magnetic relaxation of CrO2 films can be strongly modulated via the proximity to RuO2 layer, which may relate to the enhancement of the two-magnon scattering due to effects of antiferromagnetic order in RuO2 film. In addition, electronic transport measurements indicate that the electronic characteristic is strongly related to the film growth orientation, and a linear magnetoresistance is observed stemming from intergrain tunneling magnetoresistance and double-exchange mechanism. Angle-dependent ferromagnetic resonance measurements indicates that the uniaxial anisotropy in CrO2 film is strongly related to the strain effect, which is consistent with reciprocal space mapping results. This work lays a foundation for current-drive MRAM based on RuO2/CrO2 bilayer and provides a feasible damping modulation method for CrO2 film.

Atomic origin of CO2-promoted oxidation dynamics of chromia-forming alloys

The development of atomic imperfections within oxide films from high-temperature oxidation of heat-resistant alloys significantly limits the self-protectiveness of the surface oxide, contributing to the failure of energy generating system components such as turbines, engines, and heat exchanges. Directly probing the dynamics of such atomic defects is challenging because of the extreme thermochemical conditions of high-temperature oxidation. Using environmental transmission electron microscopy observations, here we directly capture atomic-scale dynamics of vacancies in growing Cr2O3 film during high-temperature oxidation of NiCr alloy in CO2. Coordinated with theory modeling, we delineate the atomistic mechanisms associated with the effect of interstitial carbon derived from CO2 on promoting the formation, migration and clustering of atomic vacancies to result in the enhanced alloy oxidation. The identified oxidation mechanism can find broader applicability in utilizing the atmosphere to tune the formation and evolution of atomic-scale defects, thereby affecting the mass transport properties of the growing oxide film.

Effect of aging temperature on corrosion resistance of 316L stainless steel in simulated proton exchange membrane fuel cell cathode environment

The effects of aging temperature on the corrosion behavior of 316 L stainless steel in a simulated cathodic environment of a proton exchange membrane fuel cell (PEMFC) were investigated by potentiodynamic polarization curves, electrochemical impedance spectroscopy (EIS), double-loop electrochemical potential response (DL-EPR). The results show that the corrosion resistance of 316 L is significantly degraded after aging at 750–900 °C for 1 h in the simulated cathodic environment of PEMFC. A strong sensitivity to intergranular corrosion takes place after aging at 850 °C, and chromium rich M23C6 carbides precipitate on grain boundaries. The precipitation of M23C6 leads to discontinuity of the passivation film near the grain boundaries, resulting in Cr-depleted zones at the grain boundaries, increasing intergranular corrosion, and decreasing corrosion resistance. When the aging temperature exceeds 950 °C, grain boundary precipitation of M23C6 does not occur and the corrosion resistance is improved. At an aging temperature of 1050 °C, a dense Cr2O3 film is formed on the surface of the alloy during the polarization test, giving it the best corrosion resistance in the simulated cathodic environment of PEMFC.

Post Deposition Interfacial Néel Temperature Tuning in Magnetoelectric B:Cr2O3

AbstractBoron (B) alloying transforms the magnetoelectric antiferromagnet Cr2O3 into a multifunctional single‐phase material which enables electric field driven π/2 rotation of the Néel vector. Nonvolatile, voltage‐controlled Néel vector rotation is a much‐desired material property in the context of antiferromagnetic spintronics enabling ultralow power, ultrafast, nonvolatile memory, and logic device applications. Néel vector rotation is detected with the help of heavy metal (Pt) Hall‐bars in proximity of pulsed laser deposited B:Cr2O3 films. To facilitate operation of B:Cr2O3‐based devices in CMOS (compementary metal‐oxide semiconductor) environments, the Néel temperature, TN, of the functional film must be tunable to values significantly above room temperature. Cold neutron depth profiling and X‐ray photoemission spectroscopy depth profiling reveal thermally activated B‐accumulation at the B:Cr2O3/ vacuum interface in thin films deposited on Al2O3 substrates. The B‐enrichment is attributed to surface segregation. Magnetotransport data confirm B‐accumulation at the interface within a layer of ≈50 nm thick where the device properties reside. Here TN enhances from 334 K prior to annealing, to 477 K after annealing for several hours. Scaling analysis determines TN as a function of the annealing temperature. Stability of post‐annealing device properties is evident from reproducible Néel vector rotation at 370 K performed over the course of weeks.

Mechanical and Optical Properties of Cr2O3 Thin Films Grown by Atomic Layer Deposition Method Using Cr(thd)3 and Ozone.

Cr2O3 thin films were grown on a Si (1 0 0) substrate using Cr(thd)3 and O3 by atomic layer deposition (ALD) at substrate temperatures (TG) from 200 to 300 °C. X-ray amorphous films were deposited at a TG ≤ 225 °C, whereas at higher temperatures (TG ≥ 250 °C), the eskolaite phase was observed in the films. The growth rate of the films increased from 0.003 to 0.01 nm/cycle by increasing TG from 200 to 275 °C. The relatively low growth rate of Cr(thd)3-O3 makes it appropriate for the ALD of precisely controllable solid solution-type ternary-component thin films. The Ti-doped Cr2O3 film showed higher hardness (16.7 GPa) compared with that of the undoped film (12.8 GPa) with similar thickness. The band gap values of the pure Cr2O3 corresponding to the indirect transition model showed no dependence on TG; however, doping the Cr2O3 with Ti decreased its band gap energy value from 3.1 to 2.2 eV.

Tuning the phase structure and surface morphology of Cr2O3:CuO thin film by annealing for enhanced ammonia sensing performance at room temperature

Driven by global environmental concerns, there is currently a strong need to identify real-time sensing materials for sensor devices. In this work, we mainly report the observation of an annealing-induced enhancement in room temperature ammonia sensing performance of binary composite metal oxide thin films of Cr2O3:CuO by tuning the phase structure and surface morphology. The activation energy of Cr2O3:CuO film was estimated from the Arrhenius plot and its magnitudes varied between 0.182 eV and 0.186 eV upon the variation of annealing temperature from 300 to 1000 °C. X-ray diffraction patterns of annealed Cr2O3:CuO film showed the existence of two different phases such as tetragonal CuCr2O4 and orthogonal CuCrO4. Fascinatingly, the CuCr2O4/CuCrO4 thin film prepared on quartz substrate exhibits a clearly visible cumin seed-like morphology with clear boundaries, which support the observed improvement in gas sensing performance. The sensitivity and detection limit (DL) of CuCr2O4/CuCrO4 thin film for ammonia gas were measured to be 5.77 and 1.9 ppm, respectively. The CuCr2O4/CuCrO4 film shows good response to different concentrations of NH3 and the film has a competence to retort for very low NH3 level (1 ppm). In addition, the prepared film retains 95 % of its initial response to ammonia even after 1-year duration. The observed results provide a probe for designing good and reliable room temperature sensor for ammonia gas at room temperature.

TEM characterization of an epitaxial CrO2 film deposited by the CVD method and the transition interface

Epitaxial chromium dioxide (CrO2) film was grown on sapphire Al2O3 by the chemical vapor deposition (CVD) method. The interfacial structure of the epitaxial CrO2 was characterized by transmission electron microscopy (TEM), and the spatial distribution of the chromium valence in the film was qualitatively analyzed by electron energy loss spectroscopy (EELS). An uneven transition layer with a diffraction pattern consistent with that of Cr2O3 but with an anomalously large oxygen concentration (Cr/O ≈ 0.2–0.3) was found between the CrO2 film and the substrate.