Solid Solution Phase Research Articles

Nanowires made of ternary alloys – synthesis features and magnetic properties

Nanowires of FexCoyCu(100–x–y) and FexNiyCu(100–x–y) alloys have been studied. The features of obtaining such structures by the matrix synthesis method have been investigated. Elemental analysis of nanowires grown at sequentially increasing voltages revealed a significant decrease in the amount of copper, as well as a change in the ratio of the main magnetic elements. X-ray phase analysis showed that FeCoCu is a three-component solid solution, while FeNiCu contains three phases of solid solutions: FeCu with copper content up to 80%, FeNi with high iron content, and NiCu in an amorphous or fine-crystalline state with nickel content up to 80%. Mössbauer spectroscopy revealed that the addition of copper can lead to a change in the angle of magnetic moment misalignment in nanowires, which correlates with magnetometry data.

Rhombohedral phase high-entropy alloy of AlMnCuZnBi as a photo-Fenton catalyst for methyl orange degradation

The formation of solid solutions with five or more elements having nearly equiatomic contributions termed as high entropy alloys (HEA), is recent strategy for the development of new materials. Such alloys have displayed superior properties than the conventional ones. The prepared alloys are generally face- or body-centered cubic structures with a few exceptions for orthorhombic and hexagonal close packed structure. In this, we report the synthesis of HEA of AlMnCuZnBi having rhombohedral crystal structure. The material was prepared by vacuum arc melting route. Both the diffractions (X-ray and electron) confirm its structure. The calculated thermodynamic empirical parameters e.g. ΔSmix, ΔHmix, δ, VEC and Ω even validate the feasibility of this single phase solid solution. The HEA had shown feeble ferromagnetic behaviour. The rhombohedral structured HEA may open up new possibilities for various emerging applications. The proposed HEA acted as a catalyst for photo-Fenton like reaction and could degraded methyl orange dye completely in 170 minutes.

Enhanced hydration reaction of synthesized C4A0.81F1.19 with the use of different grinding agents

Tetracalcium aluminoferrite (C4AF) presents in ordinary Portland cement (OPC) as a solid solution phase, as C4AxF2−x (0.7 ≤ x ≤ 1.1). There is a limited understanding of the hydration reactions of C4AF, particularly regarding the influence of alkanolamines (AA) on C4AF, which can substantially alter OPC hydration. In this study, synthesized C4A0.81F1.19 was subjected to grinding, using three different AA (triisopropanolamine, ethanol diisopropanolamine, and diethanol isopropanolamine) at dosages of 0, 0.1, and 0.3%. It was experimentally confirmed that the crystal structure of unhydrated C4AF was partially changed during the grinding process, and the hydration properties of C4AF were modified. From these results, the compressive strength improved significantly, and the rate of strength enhancement was the highest with 0.1% of diethanol isopropanolamine. More specifically, it was revealed that both Fe and Al sources were proficiently activated, leading to the production of Al/Fe-containing AFm phases and efficiently enhanced mechanical properties.

Mechanical properties of CoCrFeNi-X (X = Ti,Sn) high entropy alloy and tribological properties in simulated seawater environment

Five multimajor element CoCrFeNi-X(X = Ti,Sn) high entropy alloys (HEA) were prepared by vacuum hot press sintering. The phase composition, mechanical properties and tribological properties of CoCrFeNi-X(X = Ti,Sn) alloys in simulated seawater were investigated. The phase structure of CoCrFeNiTi high-entropy alloy is solid solution FCC phase, R phase, σ phase, and Laves phase. But after addition Sn elements, the phase structure become the FCC phase and Ni-Sn solid solution phase. CoCrFeNiTi alloy has lower density (7.17 g/cm3) and higher hardness (750 HV) than that of CoCrFeNiSn. The compressive yield strength of CoCrFeNiTi HEA is better than CoCrFeNiSn HEA. The CoCrFeNiSn high-entropy alloys showed lower wear rates. The main reason is that SnO2 is generated on the wear scar surface, which has good wetting and corrosion inhibition effects, so CoCrFeNiSn HEA shows better wear resistance in simulated seawater. The main wear mechanism of the CoCrFeNiSn HEA is abrasive wear, oxidative wear, exfoliation wear and corrosive wear.

Effect of plasma nitriding on microstructure and wear behavior of electrodeposited FeCoNiCr coating

An (FeCoNiCr)N high-entropy alloy coating with a single FCC phase was fabricated on 304 stainless steel by electrodeposition and plasma nitriding. The results indicated that the FeCoNiCr coating exhibited typical granular morphologies and a nearly equiatomic ratio of four elemental compositions. After nitriding, the coating primarily consisted of a high-entropy solid solution phase and a CrN phase, with the microstructure of the (FeCoNiCr)N coating being significantly refined due to the effect of crystallization. The microhardness of the (FeCoNiCr)N coating was 781.30 ± 20.3 HV0.5, considerably higher than that of the FeCoNiCr coating, which was 496.48 ± 21.82 HV0.5. Additionally, the (FeCoNiCr)N coating demonstrated a low friction coefficient and a wear rate of 0.59 and 6.8 × 10−8 mm3/N mm, respectively. The fine microstructure and high resistance to plastic deformation, attributed to solid solution strengthening and dispersion strengthening, were the primary factors contributing to the excellent wear performance of the (FeCoNiCr)N coating.

Solution and Surface Solvation of Nitrate Anions with Iron(III) and Aluminum(III) in Aqueous Environments: A Raman and Vibrational Sum Frequency Generation Study.

Hydrated trivalent metal nitrate salts, Fe(NO3)3·9H2O and Al(NO3)3·9H2O, in both solid and aqueous phases are investigated. Raman and surface-selective vibrational sum frequency generation (SFG) spectroscopy, are used to shed light on ion-ion interactions and hydration in several spectral regions spanning low frequency (440-550 cm-1) to higher frequency modes of nitrate and water (720, 1050, 1250-1450, and 2800-3750 cm-1). These frequencies span the metal-water mode, nitrate in-plane deformation, nitrate symmetric and asymmetric modes, and the OH stretch of condensed phase water molecules. Comparison to NaNO3, and in some cases KNO3, is also shown, providing insight. Splitting and frequency shifts are observed and discussed for both the solid state and solution phase. The Lewis acidity of Fe3+ and Al3+ ions plays a significant role in the observed spectra, in particular for the nitrate asymmetric band splitting and frequency shift. The spectral response from water solvation for iron and aluminum nitrates is nonlinear as compared to linear for sodium nitrate, suggesting significantly different solvation environments that are limited by water hydration capacity at higher concentrations. Moreover, a non-hydrogen bonded OH, dangling OH, from hydrating water molecules is observed spectroscopically for Al and Fe nitrate solutions. Furthermore, aluminum nitrate perturbs the surface water structure more than iron nitrate despite aluminum being a weaker Lewis acid. The surface water structure is thus found to be unique for the Al(NO3)3 solutions as compared to both Fe(NO3)3 and NaNO3, such that surface solvation is more pronounced. This observation exemplifies the nature of the Fe(III) and Al(III) ions and their substantial influence on the surface water structure.

Effect of Cr content on the high temperature oxidation behavior of FeCoNiMnCrx porous high-entropy alloys

FeCoNiMnCr porous high-entropy alloys were prepared using the activation reaction sintering method with Fe, Co, Ni, Mn, and Cr as raw materials. The oxidation behaviors of FeCoNiMnCrx porous high-entropy alloys with different Cr contents, such as pore structure, the surface oxide film phase composition, structure, and morphology, were characterized by X-ray diffraction (XRD), electron probe micro analysis (EPMA), energy dispersive X-ray spectroscopy (EDS), and pore tester after high-temperature oxidation at 800–1000 °C. The results indicate that the initial porous high-entropy alloy comprises a single FCC solid solution phase. With the increase in Cr content, the average pore diameter, average porosity, and air permeability of the porous high-entropy alloy also increase. The oxidation kinetics of the porous high-entropy alloy after exposure to temperatures between 800 °C and 1000 °C follows a single-stage parabolic evolution law. At the same oxidation temperature, With the increase of Cr content, the oxidation gains gradually increased, at the same Cr content at different temperatures, the antioxidant performance of 1000 °C was the weakest, followed by 800 °C, and 900 °C showed excellent antioxidant performance. The oxidation products are mainly Mn2O3, Mn3O4, (Mn, Cr)3O4, Cr2O3and Fe2O3.

The effect of annealing on the microstructure and wear performance of laser-clad high-entropy alloy composite coatings for monorail crane braking systems

Laser cladding was utilized to fabricate WC ceramic particle-reinforced CoCrFeMnNi high-entropy alloy (HEA) composite coatings, with an investigation into the influence of annealing heat treatment on the microstructure and wear behavior of the composite coatings. The HEA composite coatings with a WC particle content of 30 wt% primarily consist of a face-centered cubic (FCC) solid solution phase, various M6C carbides with blocky, fishbone, and dendritic morphologies, and incompletely melted WC ceramic particles. The microstructure of the composite coatings remains stable up to a temperature of 570°C. After annealing at 600°C, the microstructure transforms into a typical dendritic morphology with rod-like carbides precipitating from the solid solution and discontinuously distributed in the interdendritic regions. Due to the annealing softening effect, the microhardness of the coating decreases from 488.1 HV0.3 to 443.1 HV0.3. Following annealing at a high temperature of 800°C, recrystallization leads to a refined equiaxed grain microstructure, with precipitated carbides continuously distributed along the grain boundaries, forming a network. The combined effects of precipitation hardening and fine grain strengthening result in an increase in the microhardness of the coating to 568.6 HV0.3 after annealing at 800°C. As the annealing temperature increases, the wear rate of the WC particle-reinforced CoCrFeMnNi HEA composite coatings also increase. The wear mechanism for the unannealed coating is oxidative wear, and the reduction in hardness leads to adhesive phenomena in the coating after annealing at 600°C. The network of carbides reduces the ductility of the HEA and also the toughness of the oxide film, resulting in the highest wear rate for the coating annealed at 800°C, reaching 38.636×10−6 mm3/(N·m). This study provides valuable insights for the fabrication of advanced wear-resistant coatings.

Effect of order-disorder transition and lattice distortion on the mechanical properties of W-X (X = V, Nb, Ta) solid solutions

With the prosperity of high entropy alloys, short-range ordering is getting more and more attentions and regarded as the deciding role in the hardening or softening of solid solutions. In this work, the phase stability and mechanical properties of short-range ordered and disordered body-centered cubic (BCC) structures of W-X solid solutions (X = V, Nb, and Ta) are systematically investigated through a combination of first-principles calculation, cluster expansion and quasi-harmonic Debye formula. Based on the calculated heat of formation (ΔHf), W-X solid solutions show a strong short-range ordering tendency, as those ordered structures have a lower ΔHf than the disordered ones. Generally, short-range ordering results in the decrease of the shear modulus to bulk modulus ratio (G/B) and hardness for W-V and W-Ta systems, while an increase for W-Nb system, manifesting solid-solution softening and hardening effect, respectively. The short-ranged ordered C11b W2X phase exhibits a singularity in mechanical properties characterized by a higher G/B than solid solution phases compared to other ordered phases. The lattice distortion breaks the symmetric W-W bonds and leads to partial covalency in the W2X phases. Besides the increased brittleness, this distortion also causes the increase of ideal strength and the reduction of maximum tensile elongation of W2X. The effect of short-range ordering and lattice distortion on the hardening or softening of the W-X systems disappears after the order-disorder transition. The W-V and W-Ta phases have higher order-disorder transition temperature than W-Nb phase. Nevertheless, the transition temperature is relatively low in comparison to their melting points, signifying the important role in controlling the solute concentration at lower temperature.

Microstructure and wear behavior of WC-reinforced AlCoCrFeNiSi high entropy alloy coatings prepared by high-velocity arc spraying

In this study, AlCoCrFeNiSi/WC (WC from 0 to 40 wt%) high entropy alloys (HEAs) coatings were deposited on Q235 steel substrates using high-velocity arc spraying technique. The coatings' phases, microstructure, microhardness, nano-hardness, wear properties, and the mechanisms of wear were examined. The results have shown that the WC reinforced HEA had faced-centered cubic, body-centered cubic solid solution and carbide phases, while faced-centered cubic solution and Cr3Si, Al2O3 phase were observed in AlCoCrFeNiSi coating. The coatings possess a dense, lamellar structure and strong adhesion to the substrates. With the addition of reinforced particles, the porosity of the coatings initially decreases and then increases. The average microhardness of the coatings is significantly improved as WC content increased, reaching a maximum of 530 HV0.1. The ratio of nano-hardness to reduced elastic modulus rises as more WC is introduced. The coatings with the WC particles exhibit good wear resistance with the optimum wear rate at WC content of 40 wt%. Under the same conditions, the coating with 40 wt% of WC displayed the lowest wear rate, which decreased by 60.5 % compared to the AlCoCrFeNiSi coating. The AlCoCrFeNiSi coating experienced a mix of adhesive, abrasive, oxidative, and fatigue wear mechanisms. The wear mechanism changed to more abrasive, adhesive, and oxidative in the reinforced coatings. The load-bearing capacity and secondary phase strengthening effects of WC reduce the wear rate of the coatings.

In situ construction of one-dimensional structures induced by Ba doping in Al2O3-TiO2 ceramics derived from quenched powders

In this work, we propose a strategy for in situ construction of rod-like grains in Al2O3-TiO2 ceramics through Ba doping. Ba-doped Al2O3-13 wt% TiO2 composite powder was initially synthesized using combustion synthesis-air atomization, where feedstocks were melted by the Al-O2 combustion reaction and subsequently atomized and rapidly cooled in air, producing quenched powders rich in metastable phases. Upon heat treatment at 1100℃, the metastable phases transformed into stable forms, accompanied by phase separation and solid solution precipitation. Notably, Ba doping induced the formation of rod-like hollandite grains with preferential growth along the [001] direction. Bulk ceramics were prepared through pressureless sintering, and the sample sintered at 1350℃ exhibited a hardness of 14.14±0.61GPa and a fracture toughness of 5.17±0.49MPa∙m1/2. The toughening behavior of rod-like grains, including crack deflection and pull-out/bridging effects, was observed. This study provides insights into the evolution of quenched oxides and the design of ceramic microstructures.

Synergistic Impact of Alloying with Ni on Cu Cathode Interfaces for Fluoride Batteries.

All-solid-state fluoride batteries have the potential to achieve energy densities significantly higher than those of lithium-ion batteries. A common cathode material for fluoride batteries is Cu. Cu has a low polarization, but its rapid capacity degradation due to grain growth and subsequent delamination from the solid-state electrolyte are critical issues. To enhance the performance of Cu-based cathodes in all-solid-state fluoride batteries, we explore alloying of Cu with Ni to create metastable solid solution phases (CuxNi1-x with x = 0, 0.32, 0.52, 0.72, 0.89, and 1.0). Compared to Cu, Ni has a higher polarization but exhibits superior capacity retention. The Cu0.72Ni0.28 alloy demonstrates a polarization as low as Cu, but it has a significantly improved capacity retention, which is comparable to Ni. Transmission electron microscopy observations demonstrate that the thin Ni-rich region formed near the interface inhibits Cu grain growth and delamination from the LaF3 electrolyte. By incorporating an appropriate amount of Ni into Cu, Cu-Ni alloy films combine the advantages of both metals, improving the performance of fluoride batteries.

Effect of an Ultrasonic Vibration on the Microstructure and Properties of Al Alloy/Steel Laser Welding-Brazing Joints

This study analyzes the influence of different ultrasonic amplitudes on the microstructure composition, microhardness, tensile strength, and corrosion resistance of Al alloy/steel laser welding-brazing joints assisted by ultrasonic vibration. The application of ultrasonic vibration did not change the microstructure composition of the joints but refined them. The joints were all composed of θ-Fe(Al, Si)3 and τ5-Al7.2Fe1.8Si formed at the interface reaction zone, as well as an α-Al solid solution and Al-Si eutectic phase generated in the weld seam zone. Meanwhile, the thickness of the IMCs at the interface decreased with an increase in the ultrasonic amplitude. When the ultrasonic amplitude was 8 μm, the IMCs thickness was a minimum of 1.62 μm. In this condition, the reduction of the IMCs thickness and the refined grain of joints made the microhardness and tensile strength reach the maximum. The fracture of joints with ultrasonic amplitudes of 0 and 4.8 μm began at the weld seam and extended to the interface reaction zone at the steel side, while the fracture of joints was located in the heat-affected zone (HAZ) of the Al alloy side when the ultrasonic amplitude was 8.0 and 11.2 μm. The fracture mode of the former presented a typical mixed fracture with cleavage steps and tearing edges, and that of the latter showed ductile fracture with uniform and fine ductile dimples. The corrosion resistance of the joints was improved by adding ultrasonic vibration. When the ultrasonic amplitude was 8 μm, its corrosion resistance was optimum; it was ascribed to a dense oxide film formed on the surface of the metal under the action of ultrasonic vibration.

Research into the Structure and Adhesion of WCCoCr Coatings Plasma-Sprayed onto Castings of AlSi Alloy Plates

The article presents structural investigations and mechanical properties of hard coatings deposited by spraying WCCoCr powder in an argon-hydrogen plasma jet onto the surfaces of AlSi10Mg alloy casting plates. Two variants (A and B) of processing parameters of the powder spraying process onto the surface of silumin plates were applied, resulting in different coating thickness. The coating applied according to variant A was done with 12 passes, and its thickness was approximately 150 μm. The coating applied according to variant B was done with 20 passes, and its thickness was about 320 μm. The microstructures of these coatings are similar, consisting of wavy, alternately deposited phases of solid solutions with varying concentrations of elements, and fine spherical phases, irregularly dispersed carbides. A qualitative analysis of the distribution of microstructure components was performed based on surface mapping. Precipitates differing in their degree of grayness and shape were identified based on microanalysis of their chemical composition. The porosity assessment of coatings performed in five randomly selected areas amounts to an average of 9%. The applied coatings exhibit good adhesion to the substrate, as evidenced by the absence of delamination during scratching tests using a diamond Rockwell indenter loaded with a force of 10 N. The coating hardness averaged 1180HV0.2. The test results indicate the high quality of the WCCoCr coatings, regardless of their thickness.

Optimization of friction stir processing parameters to improve mechanical properties and microstructure of Al5083 aluminum alloy reinforced with AlCoCrFeNiSi high-entropy alloy

Abstract This study explores integrating AlCoCrFeNiSi high-entropy alloy (HEA) particles into the Al5083 aluminum alloy matrix via Friction Stir Processing (FSP) to enhance mechanical characteristics. Microstructural analysis reveals a homogeneous distribution and size reduction of HEA particles, contributing to improved structural strength. X-ray diffraction (XRD) examination confirms the formation of solid solution phases in the HEA particles, validating their role in enhancing material properties. Through the utilization of Design of Experiments (DOE) and Response Surface Methodology (RSM), FSP parameters are systematically optimized, enabling precise predictions of mechanical behavior. Multi-response optimization identifies the optimal combination of FSP parameters, resulting in significant enhancements in Ultimate Tensile Strength (UTS) and Hardness, reaching 314 MPa, 42% elongation, and 75 HV, respectively. Scanning Electron Microscopy (SEM) analysis of tensile test specimens elucidates the impact of varied FSP parameters on microstructural features, emphasizing the importance of optimal mixing for improving interfacial bonding and mechanical properties. This study underscores the effectiveness of integrating HEA particles and optimizing FSP parameters to elevate the mechanical properties of Al5083 aluminum alloy, paving the way for tailored composite materials with enhanced performance for specific applications.

Enhanced mechanical properties of LPSOp/Mg composites using super high pressure treatment

The super high pressure (SHP) technique was employed to fabricate the magnesium matrix composites (MMCs) reinforced with long-period stacking order structure powder (LPSOp) by cubic-anvil large-volume press with six rams. The LPSOp was optimized through high energy ball milling (HEBM) with a chemical composition of Mg85Zn6Y9 (at%). The microstructure and mechanical properties of LPSOp/Mg composite was characterized by X-ray diffraction (XRD), scanning electron microscopy/transmission electron microscopy (SEM/EDS), transmission electron microscopy (TEM), microhardness and compressive tests. The microhardness of LPSOp exhibits a notable increase after HEBM, and the thermal stability of LPSOp is affirmed through elevated annealing. The SHPed LPSOp/Mg consists of Mg and LPSO phase. Upon annealing at 400 °C for 1 h, the LPSO phase precipitates from solid solution of Mg and W phase is also identified. The strength of composites by SHP treatment and subsequently annealing is significantly improved compared with the pure Mg without LPSOp, which demonstrates the maximum compression yield strength (CYS) of 250 MPa and ultimate compression strength (UCS) of 375 MPa with satisfactory ductility. The enhanced mechanical properties are attributed to the synergistic reinforcement effects of the dispersed and 3D skeletal structure of LPSOp with excellent interfacial bonding, the coexistence of nano-scale LPSO and W phase and partial solid solution strengthening.

Microstructure and wear property of (TiN + NbC) double ceramic phase-reinforced in FeCrNiCoAl high-entropy alloy coating fabricated by laser cladding

This study delves into the influence of TiN and NbC ceramic particles on the phase structure, grain organization, microhardness, and wear resistance of FeCoNiCrAl High-Entropy Alloy (HEA) composite coatings produced through laser cladding. The integration of ceramic particles induced a dual BCC solid-solution phase structure (B2+BCC), with the formation of a TiNb phase upon the melting and interaction of TiN and NbC in the melt pool. The ceramic particles significantly modified the grain structure of the HEA coatings, disrupting the Columnar-to-Equiaxed Transition (CET) and favoring the emergence of equiaxed grains. The TiN particles induced a substantial refinement of grain size, albeit unevenly, while NbC had a milder effect. The combined presence of TiN and NbC particles resulted in a more uniform grain refinement, enhancing the mechanical properties of the coatings. Notably, the (TiN + NbC)/HEAs composite coating demonstrated superior mechanical performance under the synergistic effect of both ceramic particles. The average microhardness value increased by 55.80 % compared to 17-4Ph stainless steel, and the wear rate was reduced by 88.38 %, with the wear mechanism primarily involving abrasive and oxidative wear.

Tribological Behavior and In‐Vitro Biocompatibility of a Newly Designed TiZrNbMoTa High‐Entropy Alloy

A novel Ti35Zr15Nb25Mo15Ta10 high‐entropy alloy has been designed, fabricated, and characterized as a viable substitute for the conventional Ti‐6Al‐4V alloy in biomaterial applications. Alloy design is conducted based on various parameters including mixing enthalpy (ΔHmix), omega parameter (Ω), delta parameter (δ), valence electron concentration (VEC), and biocompatibility aspects of its constituent elements with CALPHAD approach. The fabricated Ti35Zr15Nb25Mo15Ta10 alloy demonstrated a body‐centered‐cubic (BCC) solid solution phase with no evidence of intermetallics. Nanoindentation investigations exhibited high hardness of ≈5.1 GPa and a young modulus of ≈140 GPa. The alloy proposed better surface properties and tribological behaviour in comparison with the Ti‐6Al‐4V alloy in dry and wet (under PBS solution) conditions. Furthermore, the newly designed alloy revealed promising behaviour after investigation of in‐vitro biocompatibility compared to the Ti‐6Al‐4V alloy. These initial benefits of the Ti35Zr15Nb25Mo15Ta10 alloy concerning mechanical properties and wear resistance over the conventional Ti‐6Al‐4V alloy present an avenue for exploring novel orthopedic implant alloys.

The effects of refractory elements on the properties of quaternary high entropy carbides—A first-principles and experiment study

In this work, the effects of refractory transition metal elements on the properties of quaternary equimolar ratio high entropy carbides composed of ⅣB, ⅤB and ⅥB transition metals and C element were studied by first-principles calculations and experiments.The calculation results show that all 75 kinds of high entropy carbides were thermodynamically and mechanically stable and can be formed spontaneously. Among them, Hf can promote the synthesis of high entropy carbides, while Cr has the opposite effect. In addition, single phase solid solution structures can be formed for all 73 HECs except (TiZrHfCr)C and (ZrHfVCr)C. Thereafter, the mechanical properties of these 75 quaternary HECs were compared. The calculation results show that W, Mo, and Ta have a positive effect on improving the elastic modulus, fracture toughness, hardness and melting point of high entropy carbides, while Cr has the opposite effect. The calculation results of phonon spectra show that the six high entropy carbides represented by (TiHfNbTa)C, (TiVNbTa)C, (TiZrNbTa)C, (TiZrNbCr)C, (TiZrNbMo)C and (TiZrNbW)C have lattice dynamic stability. (TiHfNbTa)C, (TiVNbTa)C, (TiZrNbTa)C, (TiZrNbMo)C and (TiZrNbW)C face-centered cubic high entropy carbides were prepared by spark plasma sintering and the microstructure and properties were tested. The experimental results are basically consistent with the calculated results.

Kinetics-controlled epitaxial growth and bipolar transport properties of semimetal Bi4Se3

(Bi2)m(Bi2Se3)n (m, n: integers) compounds with an infinitely adaptive superlattice structure exhibit several fascinating topological phases. Here, we study kinetics-controlled epitaxial growth of Bi4Se3 on mica by co-evaporating Bi and Se using molecular beam epitaxy technique, as well as the transport properties of Bi4Se3. By precisely controlling the beam fluxes of Bi and Se and growth temperature, we can tune the growth modes from van der Waals' condensation to spiral growth, thus achieving single-crystalline Bi4Se3 of dislocation-free microplate or mounded thin-film morphologies. This reflects a transition from near-thermodynamic-equilibrium to non-thermodynamic-equilibrium growth processes of single-crystalline Bi4Se3. Thin-film Bi2+xSe3 (1.7 < x < 2) solid-solution phases consisting of randomly stacked Bi2 and Bi2Se3 units are also prepared as comparative samples. Hall and thermopower properties suggest that the as-grown Bi4Se3 films exhibit semimetallic bipolar conduction behaviors while the Bi2+xSe3 films present typical semiconducting transport characteristics with a n-type polarity. Due to semiconductor band structures, the Bi2+xSe3 films show superior thermopower to that of semimetal Bi4Se3.