Segregation Of Atoms Research Articles

Structure patterns of one-step synthesis of CuNi nanopowders in air environment: Experiment and atomistic simulations

A possibility for one-step synthesis of bimetallic CuNi nanopowders in a different ratio of Ni to Cu by solution combustion synthesis technique under normal air atmosphere without any post reduction is reported. The effect of different types of fuels like citric acid and glycine on the combustion process and characteristics of resultant solid products were investigated. XRD results showed the existing of CuNi as a main phase and small amounts of CuO and (Ni,Cu)4N. Determined CuNi particle sizes were in the range of up to 50 nm. Computer simulation was performed using the molecular dynamics method for similar concentration compositions, but in size range of 4.5–5.5 nm, as a result of cooling the system from 1700 K to 300 K. In addition, two types of melting scenario of binary CuNi NPs were studied: 1) heterogeneous melting of monocrystalline Cu and Ni NPs; 2) melting of the crystallization products of binary NPs. Melting temperatures weakly depend on the choice of the above-mentioned melting scenario. However, the nature of subsequent crystallization can be influenced by the initial energy of the system, which is higher for case 1. The characteristic temperatures of phase transitions of melting and crystallization are determined based on the analysis of hysteresis loops of the specific potential part of the internal energy of NPs. The patterns of atomic and structural segregation in binary CuNi NPs were studied.

The Effect of Solute Elements Co-Segregation on Grain Boundary Energy and the Mechanical Properties of Aluminum by First-Principles Calculation

The segregation of solute atoms at grain boundary (GB) has an important effect on the GB characteristics and the properties of materials. The study of multielement co-segregation in GBs is still in progress and deserves further research at the atomic scale. In this work, first-principles calculations were carried out to investigate the effect of Mg and Cu co-segregation on the energetic and mechanical properties of the Al Σ5(210) GB. The segregation tendency of Mg at the GB in the presence of Cu is characterized, indicating a preference for substitutional segregation far away from Cu atoms. Cu segregation can facilitate the segregation of Mg due to their mutual attractive energy. The GB energy results show that Mg and Cu co-segregation significantly decreases GB energy and thus enhances the stability of the Al Σ5(210) GB. First-principles tensile test calculations indicate that Cu effectively counteracts the weakening effect of Mg segregation in the GB, particularly with the high concentration of Cu segregation. The phenomenon of Cu compensating the strength of the GB is attributed to an increase of charge density and the formation of newly formed Cu-Al bonds. Conversely, Mg segregation weakens the strengthening effect of Cu on the GB, but it can increase the strength of the GB when high concentrations of Cu atoms are present in the GB. The ICOHP and Bader charge analysis exhibits that the strengthening effect of Mg is attributed to charge transfer with surrounding Al and Cu, which enhances the Cu-Al and Al-Al bonds. The results provide a further understanding of the interplay between co-segregated elements and its influence on the energetic and mechanical properties of grain boundary.

Surface segregation on Ag@MNi (M = Pd, Pt, Rh, and Ru) core–shell nanocrystals for enhancing the oxygen reduction performance

Synthesis of cost-effective electrocatalysts for oxygen reduction reaction (ORR) has received wide attention due to their sluggish kinetics, which limits the development and application of fuel cell technique. In this work, we report a versatile synthetic approach to prepare a series of small-sized Ag@MNi (M = Pd, Pt, Rh, Ru) nanocrystals with core–shell structures by a simple solvothermal method. According to characterization analysis, surface segregation of Pd was proved in the outermost layer with the Pd-rich shell layer, which can regulate the adsorption energy of *OH. Electrochemical results show that the onset potential and half-wave potential of Ag@PdNi nanocrystals (Ag@PdNi NCs) are 1.005 and 0.913 V vs. RHE (reversible hydrogen electrode), respectively, with a Tafel slope of 55.31 mV dec-1 and strong ORR catalytic durability, which is similar to Ag@MNi (M = Pt, Rh, Ru) NCs and slightly higher than that of PdAg alloy nanoparticles (PdAg alloy NPs), PdNi alloy nanoparticles (PdNi alloy NPs), commercial Pd black and even commercial Pt/C, in alkaline medium. Density Functional (DFT) calculations show that the presence of Agcore effectively promotes the segregation of Pd atoms to the outer shell surface, where Ni provides better segregated substitution sites for Pd, which significantly improves the ORR activity and durability due to the electronic synergistic effect between Agcore nuclei and Pdshell can reduce the adsorption strength of OHads.

Thermally-induced diffusion and structural phase transitions in Pt/Mn and Pt/Mn/Pt thin films

We demonstrate the possibility of diffusion formation of the chemically ordered L1 0-MnPt phase through the vacuum annealing of Pt(24 nm)/Mn(20 nm) and Pt(12 nm)/Mn(20 nm)/Pt(12 nm) layered stacks at 400 °C for 30 min. For the bi-layered stack annealed at 400 °C, the effect of Pt atoms segregation at the film/substrate interface was detected, which remained after annealing even at higher temperatures (500 °C and 600 °C) and prevented the whole homogenization of the chemical composition through the film depth. By contrast, for the tri-layered stack annealed at 400 °C, the presence of the additional Pt bottom layer enabled to change the rate and mechanism of reactive diffusion, leading to homogeneous distribution of components and enhanced crystallinity of the ordered L1 0-MnPt phase compared to the bi-layered sample. An explanation of the obtained experimental data is provided based on the fundamentals of mass transfer theory and its quantitative parameters (e.g. activation energy and diffusion coefficients).

Elementary steps of catalytic reactions occurring on metallic alloy nanoparticles

Catalytic reactions occurring in an adsorbed overlayer on metallic alloy nanoparticles are of high interest in the context of applications in the chemical industry. The understanding of the corresponding kinetics is, however, still limited. One of the reasons of this state of the art is the interplay between adsorption and adsorbate‐influenced segregation of metal atoms inside alloy nanoparticles. I scrutinize this interplay by using a generic field model of segregation and the mean‐field approximation in order to describe adsorption, desorption, and elementary catalytic reactions. Under steady‐state conditions, the segregation is demonstrated to be manifested in the change of the dependence of the activation energies of desorption or elementary reactions on coverage, and the sign of this change is positive. The effect of this change on the apparent reaction orders is briefly discussed as well.

Learning grain boundary segregation behavior through fingerprinting complex atomic environments

Although continuum-scale segregation is a well-documented behavior in multi-species materials, detailed site-specific behavior remains largely unexplored. This is partially due to the complexity of analyzing materials at the requisite time and length scales for describing segregation with full atomic accuracy. Here, we better evaluate the segregation behavior of disordered grain boundary (GB) atomic environments through leveraging a set of Strain Functional Descriptors (SFDs) to generate an atomic descriptor (i.e., fingerprint). Using this atomic fingerprint, we resolve key relationships between atomic structure and segregation energy. Machine learning (ML) techniques are utilized in concert with this SFD fingerprint to elucidate complex relationships relating segregation potential to changes in specific features of the local Gaussian density captured by the SFDs. Finally, we identify relationships that indicate both individual and joint structure-property correlations. Linking atomic segregation energy to key structural features demonstrates the value of higher-order descriptors for uncovering complex structure-property relationships at an atomic scale.

Alloying and Segregation in PdRe/Al2O3 Bimetallic Catalysts for Selective Hydrogenation of Furfural

X-ray absorption fine structure (XAFS) spectroscopy, temperature-programmed reduction (TPR), and temperature-programmed hydride decomposition (TPHD) were employed to elucidate the structures of a series of PdRe/Al2O3 bimetallic catalysts for the selective hydrogenation of furfural. TPR evidenced low-temperature Re reduction in the bimetallic catalysts consistent of the migration of [ReO4]− (perrhenate) species to hydrogen-covered Pd nanoparticles on highly hydroxylated γ-Al2O3. TPHD revealed a strong suppression of β-PdHx formation in the reduced catalysts prepared by (i) co-impregnation and (ii) [HReO4] impregnation of the reduced Pd/Al2O3, indicating the formation of Pd-rich alloy nanoparticles; however, reduced catalysts prepared by (iii) [Pd(NH3)4]2+ impregnation of calcined Re/Al2O3 and subsequent re-calcination did not. Re LIII X-ray absorption edge shifts were used to determine the average Re oxidation states after reduction at 400 °C. XAFS spectroscopy and high-angle annular dark field (HAADF)-scanning transmission electron microscopy (STEM) revealed that a reduced 5 wt.% Re/Al2O3 catalyst contained small Re clusters and nanoparticles comprising Re atoms in low positive oxidation states (~1.5+) and incompletely reduced Re species (primarily Re4+). XAFS spectroscopy of the bimetallic catalysts evidenced Pd-Re bonding consistent with Pd-rich alloy formation. The Pd and Re total first-shell coordination numbers suggest that either Re is segregated to the surface (and Pd to the core) of alloy nanoparticles and/or segregated Pd nanoparticles are larger than Re nanoparticles (or clusters). The Cowley short-range order parameters are strongly positive indicating a high degree of heterogeneity (clustering or segregation of metal atoms) in these bimetallic catalysts. Catalysts prepared using the Pd(NH3)4[ReO4]2 double complex salt (DCS) exhibit greater Pd-Re intermixing but remain heterogeneous on the atomic scale.

Basics of the reaction kinetics on metallic alloys.

Kinetics of heterogeneous catalytic reactions are often complicated by various factors, and from the perspective of statistical physics the development of the corresponding models is frequently challenging especially in the case of practically important alloy catalysts. To extend the basics in this area, I use a generic kinetic model of N_{2} formation inthe NO reaction with such species as CO or H_{2}. The focus is onthe reaction on the surface of a bimetallic alloy with low integral fraction of one of the metals so that the alloy is formed only at the surface. The main goal is to illustrate the specifics of the reaction kinetics and to clarify the accuracy of various approximations which are often inevitable for the analysis of such systems. The key results are as follows. (i) In the baseline one-metal case with the Langmuir-type equations, the model predicts the existence of the optimal adsorbate binding energy corresponding to the maximal reaction rate. (ii) With suitable substitution of the symbols, the equations employed for a uniform surface [item (i)] can be used for the mean-field description of reaction on the surface of a random alloy. In particular, the maximum in the dependence of the reaction rate on the binding energy is converted to the maximum with respect to the alloy composition. (iii) The reaction kinetics on the random-alloy surface have been described exactly. The corresponding maximum in the reaction rate is lower and somewhat smeared compared to that predicted in the mean-field approximation for an alloy or for the optimal monometallic catalyst. (iv) The reaction kinetics have been scrutinized also in the case of two-dimensional (2D) segregation of metal atoms at the surface in the limits of slow and rapid adsorbate diffusion between the spots. The kinetics are shown to be qualitatively different in these limits and also compared to the random-alloy case. (v) The thermodynamic criteria for 2D segregation of metal atoms at the surface have been derived as well.

Machine learning-assisted wire arc additive manufacturing and heat input effect on mechanical and corrosion behaviour of 316 L stainless steels

Predicting the track forming factor or height-to-width ratio (H/W) in wire arc additive manufacturing is crucial for optimal path planning, heat distribution, structural integrity, distortion control, process efficiency, and defect prevention, ensuring high-quality and reliable components. Different analytical and numerical modeling methods have been introduced to predict the H/W ratio. However, the accuracy of these predictions is relatively low due to the challenges associated with handling complex and non-linear regression equations. This study addressed the challenges by implementing data-driven predictive modeling to predict the H/W ratio from the input process parameters. A stacking ensemble learning approach is employed, where a meta-model integrates predictions from multiple base learners to enhance overall performance. The model performance was evaluated by Coefficient of determination (R2), mean squared error (MSE), and mean absolute error (MAE). The model was validated by comparing the experimental and predicted values based on which five thin walls are printed with different heat inputs. The study also explores the impact of heat input on microstructure, mechanical, and corrosion properties. The findings indicate that a significantly low heat input (178 J/mm) and higher heat inputs (> 356 J/mm) decrease the wire utilization. With increasing heat input, ferrite content increases, microstructures become coarser, dendritic spacing increases, and ferrite transitions from lathy to skeletal. Further, lower heat input (235 J/mm) reduces δ-ferrite, suppresses atomic segregation, and increases Cr and Mo in the matrix. YS and UTS decrease with higher heat inputs, anisotropy decreases, and Vickers microhardness drops from 228 (178 J/mm) to 194 Hv (586 J/mm). Additionally, the corrosion resistance deteriorates with increasing heat input, as evidenced by higher pitting potential (Epit: 0.389 V vs. 0.368 V vs. −0.023 V) and lower corrosion current density (Icorr: 6.76 ×10−7 A/cm2 vs. 7.946 ×10−7 A/cm2 vs. 8.91 ×10−7 A/cm2) for heat inputs of 235 J/mm, 281 J/mm, and 356 J/mm, respectively.

Processing and microstructure development of reactive sintered (Ti-Zr-Nb-Hf-Ta)B2 + (Ti-Zr-Nb-Hf-Ta)C high-entropy ceramics

A novel dual-phase (Ti-Zr-Nb-Hf-Ta)B2 + (Ti-Zr-Nb-Hf-Ta)C high-entropy, compositionally complex composite was synthesized by reactive spark plasma sintering using commercial ZrB2, NbB2, HfB2, TaB2 and TiC powders as starting materials. The composite with high density, consists predominantly of boride (∼39.7 vol%) and carbide (∼56.4 vol%) phases and with residual amount of (Hf-Zr)O2. The microstructure is homogenous and relatively fine due to the reaction and solid solution coupling effect with average grain sizes of 3.4 μm and 2.2 μm of the boride and carbide phases, respectively. Large-area SEM analyses confirmed no microcracks or micropore formation and no presence of large grains or clusters. Investigation from micro to nano and atomic level, focused on local chemical composition and spatial distribution of constituent elements, revealed that Ti preferentially dissolves into the boride and all other elements to the carbide phase creating a (Ti0.82Zr0.04Nb0.08Hf0.03Ta0.03)B2 + (Ti0.49Zr0.12Nb0.13Hf0.11Ta0.15)C system. The analysis of grain and phase boundary interfaces revealed a continuous, <1.5 nm wide, segregation of impurity atoms of Fe and Co. Continuous (>20 nm) and atomically flat basal interfacial termination planes (001) decorated with monoatomic Zr enriched layer in the boride phase were observed. Triple points at grain and phase boundaries exhibit metal-rich composition due to impurities from the starting raw powders.

Effect of rare earth elements scandium on Sn-0.7Cu brazing metal: First-principles calculation

In this paper, the effects of rare earth element Sc on the thermal and mechanical properties of precipitates (Cu6Sn5), (Cu3Sn) and Sn matrix in Sn-0.7Cu brazing metal, as well as the interface bonding strength between stable precipitates (Cu6Sn5) and Sn matrix were investigated based on first-principles calculations. The results show that the electronic structure of the precipitated phase and the matrix changes to a certain extent, the atomic bonding mode recombines, and the electron orbitals of the matrix atoms and the rare earth elements hybridize. In addition, rare earth elements improve the mechanical properties of precipitated phase and matrix, increase the plasticity of precipitated phase and enhance the strength of matrix. Rare-earth elements improve the thermodynamic properties of the matrix and precipitated phase to some extent, increase the heat capacity of the precipitated phase and the matrix, and reduce the melting point. At the same time, rare earth elements enhance the mechanical properties and thermodynamic stability of the interface between the precipitated phase and the matrix, and improve the oxidation resistance of the matrix. Transmission electron microscope (TEM) observation shows that there is a segregation of Cu atoms at the interface between precipitated phase and matrix. Other experimental results show that: Rare-earth element Sc has a positive effect on the mechanical properties, melting characteristics and oxidation resistance of the filler metal alloy. When the addition of Sc is 0.1 % (wt), the tensile strength and elongation of the alloy are significantly increased, the melting point is reduced, the surface oxidation resistance is increased, and the comprehensive properties of the alloy are the best.

Global Optimization of Cation Ordering in Perovskites by Recommendation-Based Basin-Hopping.

Cation ordering in multication perovskites is related to many important material properties and performances, but computational determination of the cation ordering remains a major challenge. Here, we propose a new computational approach by introducing a machine learning recommender system into the basin-hopping framework (RBH) for optimizing cation ordering. Taking the electrocatalyst Ba0.5Sr0.5Co0.8Fe0.2O3 (BSCF5582) as a showcase example, we found that the efficiency of RBH in identifying low-energy configurations outperforms the methods of cluster expansion and conventional basin-hopping. The RBH results revealed that the BSCF5582 catalyst tended to have a layered ordering of A-site cations and disordered B-site cations both in bulk and on the surfaces. Further, on the A-site-terminated surface, we found the segregation of large Ba atoms. Similarly, on the A-site- terminated surface of the recently developed Cs0.2Sr0.8Co0.4Fe0.6O3 (CSCF2846) catalyst, layered ordering at the A-site and surface enrichment of large Cs atoms were also found. The layered ordering was robust against thermal effects, as found from molecular dynamics simulations at 800 K. This work provides a new approach for thermodynamic global optimization of chemical ordering in multicomponent materials.

Restructuring dynamics of surface species in bimetallic nanoparticles probed by modulation excitation spectroscopy

Restructuring of metal components on bimetallic nanoparticle surfaces in response to the changes in reactive environment is a ubiquitous phenomenon whose potential for the design of tunable catalysts is underexplored. The main challenge is the lack of knowledge of the structure, composition, and evolution of species on the nanoparticle surfaces during reaction. We apply a modulation excitation approach to the X-ray absorption spectroscopy of the 30 atomic % Pd in Au supported nanocatalysts via the gas (H2 and O2) concentration modulation. For interpreting restructuring kinetics, we correlate the phase-sensitive detection with the time-domain analysis aided by a denoising algorithm. Here we show that the surface and near-surface species such as Pd oxides and atomically dispersed Pd restructured periodically, featuring different time delays. We propose a model that Pd oxide formation is preceded by the build-up of Pd regions caused by oxygen-driven segregation of Pd atoms towards the surface. During the H2 pulse, rapid reduction and dissolution of Pd follows an induction period which we attribute to H2 dissociation. Periodic perturbations of nanocatalysts by gases can, therefore, enable variations in the stoichiometry of the surface and near-surface oxides and dynamically tune the degree of oxidation/reduction of metals at/near the catalyst surface.

Structural evolution and mechanical response of multiple Al Σ5(210) grain boundaries with segregation of solute atoms: First-principles study

Grain boundary (GB) segregation of solute atoms is a key factor affecting the microstructure and macroscopic properties of materials. In this study, first-principles calculations were carried out to investigate the effect of solute atoms (Mg and Cu) segregation on the structural evolution and mechanical response of Al ground-state Σ5(210) GB (GB-Ⅰ) and metastable Σ5(210) GBs (GB-Ⅱ and GB-Ⅲ). The GB energy, segregation energy, and the theoretical tensile strength of the multiple Σ5(210) GBs were calculated. The results show that both Mg and Cu atoms tend to segregate in the boundary plane, thus reducing GB energy and improving GB stability. The segregation of Cu atoms reduced the GB energy more significantly than that of Mg atoms. The segregation of solute atoms can change the symmetric GB structure into an asymmetric one or induce GB phase transformation. The theoretical strength of GB-I is weaker than that of the metastable GB-II with higher GB energy, suggesting that grain boundaries with higher energy are not necessarily unstable. In addition, the effect of solute atom segregation on the GB strength depends not only on the type of element but also on the specific GB structure. The weakening effect of Mg segregation in GB-I and GB-II is due to the weak MgAl bond which enlarges the low charge density region of GB and increases the free volume of GB. The strengthening of GB-I and GB-II by Cu segregation mainly depends on the stronger AlCu bond than AlAl bond along the GB fracture path. The enhanced strength of GB-III with Mg and Cu segregation is attributed to the GB structural phase transformation caused by the segregation of solute atoms. The calculation results further elucidate the relationship between element segregation and grain boundary characteristics.

Chemical Orderings in CuCo Nanoparticles: Topological Modeling Using DFT Calculations.

The orderings of atoms in bimetallic 1.6-2.1 nm-large CuCo nanoparticles, important as catalytic and magnetic materials, were studied using a combination of DFT calculations with a topological approach. The structure and magnetism of Cu50Co151, Cu101Co100, Cu151Co50, and Cu303Co102 nanoparticles; their resistance to disintegrating into separate Cu and Co species; as well as the exposed surface sites, were quantified and analyzed, showing a clear preference for Cu atoms to occupy surface positions while the Co atoms tended to form a compact cluster in the interior of the nanoparticles. The surface segregation of Co atoms that are encapsulated by less-active Cu atoms, induced by the adsorption of CO molecules, was already enabled at a low coverage of adsorbed CO, providing the energy required to displace the entire compact Co species inside the Cu matrices due to a notable adsorption preference of CO for the Co sites over the Cu ones. The calculated adsorption energies and vibrational frequencies of adsorbed CO should be helpful indicators for experimentally monitoring the nature of the surface sites of CuCo nanoparticles, especially in the case of active Co surface sites emerging in the presence of CO.

Deformation Behavior of AZ31 Magnesium Alloy with Pre-Twins under Biaxial Tension.

In the present study, the mechanical response and deformation behavior of a Mg AZ31 plate with different types of pre-twins was systematically investigated under biaxial tension along the normal direction (ND) and transverse direction (TD) with different stress ratios. The results show that significant hardening was observed under biaxial tension. The yield values in the direction of larger stress values were higher than those under uniaxial loading conditions, and the solute atom segregation at twin boundaries generates more obvious strengthening effect. Noting that, for TRH (with cross compression along the rolling direction (RD) and TD and annealing at 180 °C for about 0.5 h) sample, the strength effect of the RD yield stress σRD:σND = 2:1 was higher than that of the ND yield stress under stress ratio σRD:σND = 1:2. There is a complex competition between twinning and detwinning under biaxal tension along the ND and TD of the pre-twinned samples with the variation in the stress ratio along the TD and RD. The variation in the twin volume fractions for all samples under biaxial firstly decreases and then increases with a higher stress ratio along the ND. As for the TDH sample (precompression along the TD and annealing), the changes of the twin volume fraction were lower than that of the TR sample (cross compression along the TD and RD). However, the amplitude of variation in twin volume fraction of the TRH sample is higher than that of the TR sample. This is because the relative activity of detwinning decreases and that of twinning increases, as the ND stress mainly leads to the growth of pre-twins and the TD stress often promotes detwinning of primary twins. With a higher stress ratio along the ND, the activity of twinning deformation increases and that of detwinning decreases.

Unraveling oxygen-driven surface segregation dynamics in platinum-gold alloys

In this study we use high-energy resolution and fast X-ray Photoelectron Spectroscopy (XPS) measurements combined with Density Functional Theory (DFT) calculations to investigate the interplay between surface segregation and bulk migration of Pt atoms on Au(111) in an oxygen environment. We demonstrate that the segregation of Pt atoms is significantly influenced by the oxygen partial pressure and identify a range of O2 pressure where PtAu surface alloy formation is inhibited while promoting the formation of Au oxide. These findings are essential to understand the compositional changes in the bimetallic surface alloy, which could potentially lead to modifying the catalytic properties of PtAu up to catalyst deactivation. Our results offer a strategy to control Pt surface coverage on Au(111), a quantity that is of paramount relevance given the applications of PtAu alloys as catalysts in reactions such as the oxygen reduction reaction or the oxidation of methanol and carbon monoxide. Additionally, our findings indicate a method for controlling the composition and properties of the surface of PtAu catalysts through adjustments made during the formation of the PtAu alloy.

Thermodynamic, structural, surface and transport properties of Au-Cu melt

Thermodynamic, structural, surface and transport properties of Au-Cu liquid alloy were calculated on the basis of different theoretical modeling equations. The thermodynamic properties, such as excess Gibbs free energy of mixing, enthapy of mixing and activity were estimated and compared with the available experimental and literature data on the basis of simple theory of mixing (STM). The best fit values of model parameters were estimated using the experimental values of excess Gibbs free energy of mixing and enthalpy of mixing of the system at 1550 K. Using the same model parameters and frame, the concentration fluctuation in long wave-length limit and Warren-Cowley short range order parameter were calculated and analysed to understand the local arrangement of atoms in the liquid mixture. The surface tension and extent of surface segregation of atoms in the initial melt were computed using Butler’s model. In transport properties, the ratio of mutual to intrinsic diffusion coefficients was calculated using STM and viscosity was calculated using Kaptay equation. The system showed complete ordering tendency at its melting temperature.

InGaAs/AlGaAs MQWs grown by MBE: Optimizing GaAs insertion layer thickness to enhance interface quality and luminescent property

The refinement of interface structure in InGaAs/AlGaAs multiple quantum wells (MQWs) through molecular beam epitaxy (MBE) is crucial for enhancing their luminescence performance. The influencing mechanisms of the GaAs insertion layer (ISL) thicknesses on the interface structure and luminescence properties of InGaAs/AlGaAs MQWs were investigated by varying the GaAs ISL thickness variations and optimizing growth parameters. In our designed InGaAs/AlGaAs MQWs structures, GaAs ISL with thickness variables of 0 nm, 0.5 nm, 1 nm, 2 nm, and 4 nm were inserted between the interfaces of the InGaAs well layer and the AlGaAs barrier layer. Through experimental characterizations. The introduction of the GaAs ISL resulted in a gradual transition of the MQWs surface morphology from a three-dimensional (3D) island structure to a typical step-flow surface morphology, leading to the reduction in surface roughness and enhancement of hetero-interfaces quality. Moreover, the GaAs ISL with thickness exceeding 2 nm effectively inhibited the segregation of indium atoms, promoting the ordering of interface alloys and decreasing the polarization degrees from 3.76 % to 2.09 %. Temperature-dependent PL measurements indicated that the GaAs ISL could reduce interface defects and the density of non-radiative recombination centers, thereby enhancing the radiative recombination efficiency of MQWs and ultimately increasing the peak intensity of photoluminescence by 3.4 times. This work is significance for understanding the luminescent properties of InGaAs/AlGaAs MQWs, which provides reference highly efficient optoelectronic devices development.

Ligand-Induced Atomically Segregation-Tunable Alloy Nanoprobes for Enhanced Magnetic Resonance Imaging.

Bimetallic iron-noble metal alloy nanoparticles have emerged as promising contrast agents for magnetic resonance imaging (MRI) due to their biocompatibility and facile control over the element distribution. However, the inherent surface energy discrepancy between iron and noble metal often leads to Fe atom segregation within the nanoparticle, resulting in limited iron-water molecule interactions and, consequently, diminished relaxometric performance. In this study, we present the development of a class of ligand-induced atomically segregation-tunable alloy nanoprobes (STAN) composed of bimetallic iron-gold nanoparticles. By manipulating the oxidation state of Fe on the particle surface through varying molar ratios of oleic acid and oleylamine ligands, we successfully achieve surface Fe enrichment. Under the application of a 9 T MRI system, the optimized STAN formulation, characterized by a surface Fe content of 60.1 at %, exhibits an impressive r1 value of 2.28 mM-1·s-1, along with a low r2/r1 ratio of 6.2. This exceptional performance allows for the clear visualization of hepatic tumors as small as 0.7 mm in diameter in vivo, highlighting the immense potential of STAN as a next-generation contrast agent for highly sensitive MR imaging.