Epitaxial Films Research Articles

Engineering Carrier Density and Effective Mass of Plasmonic TiN Films by Tailoring Nitrogen Vacancies.

The introduction of nitrogen vacancies has been shown to be an effective way to tune the plasmonic properties of refractory titanium nitrides. However, its underlying mechanism remains debated due to the lack of high-quality single-crystalline samples and a deep understanding of electronic properties. Here, a series of epitaxial titanium nitride films with varying nitrogen vacancy concentrations (TiNx) were synthesized. Spectroscopic ellipsometry measurements revealed that the plasmon energy could be tuned from 2.64 eV in stoichiometric TiN to 3.38 eV in substoichiometric TiNx. Our comprehensive analysis of electrical and plasmonic properties showed that both the increased electronic states around the Fermi level and the decreased carrier effective mass due to the modified electronic band structures are responsible for tuning the plasmonic properties of TiNx. Our findings offer a deeper understanding of the tunable plasmonic properties in epitaxial TiNx films and are beneficial for the development of nitride plasmonic devices.

Correction: Formation of GdAl2 Laves Phase in Gadolinium Zinc Oxide Epitaxy Film

Correction: Formation of GdAl2 Laves Phase in Gadolinium Zinc Oxide Epitaxy Film

Pinning of domain walls in epitaxial garnet film patterned by surface arrays of ferromagnetic metal particles

Rare-earth iron garnet epitaxial films famous for their unique magnetic, microwave and optical properties consistently attract high interest. Domain structure of both bulk and interfaces of garnet films is closely connected with their magnetic properties and magnetization dynamics. In this work, we investigate the magnetic behaviour and domain structure of an epitaxial bismuth-substituted lutetium iron garnet film with a regular array of planar submicron particles made of Co film or Co/Pt multilayer on its surface. Optical polarization microscopy and magnetic force microscopy techniques used for the characterization of these composite structures confirm the mutual influence of the garnet and metal nanostructured layers on each other. On the one hand, dense ordered metal particles provide the pinning of the surface magnetic domains of the garnet film, which further affects the organization of the bulk stripe domains. On the other hand, we observed that the domain structure in the metallic pattern is governed by the domain structure of the garnet placed beneath it.

Controlling Bi/Fe ratio in bismuth iron garnet thin films deposited by confocal magnetron sputtering for enhanced Faraday rotation

We have successfully deposited high-quality bismuth-iron-garnet (BIG; Bi3Fe5O12) epitaxial thin films on single crystal gadolinium-gallium-garnet (GGG; Gd3Ga5O12) (111) substrates through Radio frequency (RF) confocal sputtering, utilizing separate bismuth and iron oxide sputtering targets and optimized thermal treatments. The Bi/Fe ratio in the deposited BIG thin films can be varied by controlling the sputter process parameters. These deposited thin films exhibit homogeneity and surface root mean square (rms) roughness of less than 2 nm. The epitaxial film quality is confirmed by X-ray diffraction (XRD) and Transmission electron microscopy (TEM). Moreover, the films demonstrate low optical loss and a magneto-optical Faraday rotation as high as −34o±1o /μm at a wavelength of 535 nm for a BIG thin film with a Bi/Fe ratio 0.7 and annealing temperature of 510oC. Additionally, the coercivity of the deposited films is lower than that of those deposited via RF sputtering using a single composite target. This co-sputtering approach provides real-time flexibility for the deposition of high-quality BIG films.

Electronic structure and thermoelectric properties of epitaxial Sc1−xVxNy thin films grown on MgO(001)

The electronic structure of Sc1−xVxNy epitaxial films with different alloying concentrations of V are investigated with respect to effects on thermoelectric properties. Band structure calculations on Sc0.75V0.25N indicate that V 3d states lie in the band gap of the parent ScN compound in the vicinity of the Fermi level. Thus, theoretically, the presence of light (dispersive) bands at the Γ point with band multiplicity is expected to lead to lower electrical resistivity, while flat (heavy) bands at X−W−K symmetry points are associated with higher Seebeck coefficients than that of ScN. Hence, to probe the thermoelectric properties experimentally, epitaxial Sc1−xVxNy thin film samples were deposited on MgO(001) substrates. All the samples showed N substoichiometry and pseudocubic crystal structure. The N-vacancy-induced states were visible in the Sc 2p x-ray absorption spectroscopy spectra. The reference ScN and Sc1−xVxNy samples up to x=0.12 were n type, exhibiting carrier concentration of 1021 cm−3, typical for degenerate semiconductors. For the highest V alloying of x=0.15, holes became the majority charge carriers, as indicated by the positive Seebeck coefficient. The underlying electronic structure and bonding mechanisms in Sc1−xVxNy influence the electrical resistivity, Seebeck coefficient, and Hall effect. Thus, this paper contributes to the fundamental understanding to correlate defects and thermoelectric properties to the electronic structure in the Sc-N system with V alloying. Published by the American Physical Society 2024

Combined Electrostatic and Strain Engineering of BiFeO3 Thin Films at the Morphotropic Phase Boundary

AbstractMultiferroic BiFeO3 exhibits a morphotropic phase boundary at large compressive strain that merges metastable phases of tetragonal (T) and rhombohedral (R) character resulting in giant ferroelectric and electromechanical responses. To utilize this functionality in devices, it is essential to understand the response of these ferroelectric phases to the environment of a nanoscale heterostructure. Here, the emergence of ferroelectricity near the morphotropic phase boundary in BiFeO3 is explored directly during thin‐film growth, using optical second harmonic generation. It is found that the epitaxial films form at the growth temperature purely in the T phase with zero critical thickness for the spontaneous polarization. Signatures of monoclinic T‐like and R‐like phases only appear upon sample cooling. The robustness of a single‐domain configuration in the high‐temperature T phase is furthermore demonstrated during growth of capacitor‐like metal | ferroelectric | metal heterostructures. Here, a reduction in tetragonality, rather than multidomain formation, lowers the electrostatic energy in the few‐unit‐cell thickness regime. For this lower tetragonality, density‐functional calculations and scanning transmission electron microscopy point to the stabilization of a novel metastable monoclinic structure upon cooling toward room temperature. The synergistic combination of strain and electrostatic phase stabilization in BiFeO3 heterostructures hence provides a basis for designing new ferroelectric phases and ultrathin ferroelectric devices.

Preparation, wear resistance, and impact toughness of homoepitaxial diamond film deposited on polycrystalline diamond compact by HFCVD method

To minimize the detrimental effects of cobalt binder on the thermal stability of polycrystalline diamond compact (PDC) under high temperature working conditions and enhance the PDC’s properties. Hot filament chemical vapor deposition diamond coated polycrystalline diamond compact (HFCVD-PDC) was prepared by depositing homogeneous epitaxial diamond film on the polycrystalline diamond layer (PCD layer) treated with cobalt binder removal. The effect of deposition pressure on the microstructure of the diamond film was investigated, and the PDC’s wear resistance was assessed using the abrasion ratio test. The drop hammer impact test was utilized to evaluate the impact toughness of the original PDC, cobalt removal PDC, and HFCVD-PDC. The results showed that a continuous and dense nanodiamond film with a cauliflower-like structure was formed on the PDC surface at the deposition pressure of 3 kPa. The abrasion ratio of the HFCVD-PDC increased by 67.44% compared to the original PDC, and by 33.29% compared to the cobalt removal PDC. Furthermore, filling nanodiamonds into the pores of cobalt removal PDC improved its impact toughness. These findings suggest that the application of homogeneous epitaxial diamond on the PCD layer can significantly improve the PDC’s wear resistance and impact toughness.

Negative and persistent photoconductivity in Bi-doped Pb0.5Sn0.5Te epitaxial films

This work presents the investigation of the photoconductivity effect in undoped and doped Pb0.5Sn0.5Te epitaxial films, with bismuth (Bi) atoms, at temperatures of 80 and 300 K. The results indicate that the samples show negative photoconductivity effect (NPC) and persistent photoconductivity (PPC). A detailed study was performed on Pb0.5Sn0.5Te sample doped with 0.15 % Bi, which presented higher photoconductivity amplitude than the other samples, by performing Hall effect and photoconductivity measurements in the temperature range of 80–300 K under dark and illuminated conditions. Using Arrhenius model, trap activation energy was extracted and compared with energies found in literature. From the Hall measurement we found that the NPC effect observed is due to a decrease in the mobility when the sample is illuminated while the carrier concentrations are nearly unaltered. It was also found that Pb0.5Sn0.5Te:Bi presented photoconductivity response for a wide range of wavelengths, indicating that it is potentially interesting for application in optic sensor devices.

Natural width of the superconducting transition in epitaxial TiN films

Abstract We investigate the effect of various fluctuation mechanisms on the dc resistance in superconducting devices based on epitaxial titanium nitride (TiN) films. The samples we studied show a relatively steep resistive transition (RT), with a transition width δT/Tc ~ 0.002-0.025, depending on the film thickness (20 nm, 9 nm, and 5 nm) and device dimensions. This value is significantly broader than expected due to conventional superconducting fluctuations ( δT/Tc < 10-3). The shape and width of the RT can be perfectly described by the well-known effective medium theory, which allows us to understand the origin of the inhomogeneity in the superconducting properties of TiN films. We propose that this inhomogeneity can have both dynamic and static origins. The dynamic mechanism is associated with spontaneous fluctuations in electron temperature (T-fluctuations), while the static mechanism is due to a random spatial distribution of surface magnetic disorder (MD). Our analysis has revealed clear correlations between the transition width and material parameters as well as device size for both proposed mechanisms. While T-fluctuations may contribute significantly to the observed transition width, our findings suggest that the dominant contribution comes from the MD mechanism. Our results provide new insights into the microscopic origin of broadening of the superconducting transition and inhomogeneity in thin superconducting films.

From weak to strong-coupling superconductivity tuned by substrate in TiN films

Abstract The interplay between substrates and superconducting thin films has attracted increasing attention. Here, we report an in-depth investigation on superconducting properties of the epitaxial TiN thin films grown on three different substrates by dc reactive magnetron sputtering. The TiN films grown on (0001) sapphire exhibit (111) crystal orientation, while that grown on (100) Si and MgO substrates exhibit (100) orientation. Moreover, the samples grown on Si reveal a relatively lower level of disorder, accompanied by the higher critical transition temperature Tc and smaller magnitude of upper critical field slope near Tc. Remarkably, we uncovered a rather high value of superconducting gap (with Δ0/kBTc = 3.05) in TiN film on Si indicating a very strong coupling superconductivity, in sharp contrast to the case using sapphires and MgO as the substrate which reveals a weak-coupling feature. The comprehensive analysis considering the scenarios of the three substrate shows that the grain size of the thin films may be an important factor influencing the superconductivity.

Growth Conditions and Interfacial Misfit Array in SnTe (111) Films Grown on InP (111)A Substrates by Molecular Beam Epitaxy.

Tin telluride (SnTe) is an IV-VI semiconductor with a topological crystalline insulator band structure, high thermoelectric performance, and in-plane ferroelectricity. Despite its many applications, there has been little work focused on understanding the growth mechanisms of SnTe thin films. In this manuscript, we investigate the molecular beam epitaxy synthesis of SnTe (111) thin films on InP (111)A substrates. We explore the effect of substrate temperature, Te/Sn flux ratio, and growth rate on the film quality. Using a substrate temperature of 340 °C, a Te/Sn flux ratio of 3, and a growth rate of 0.48 Å/s, fully coalesced and single crystalline SnTe (111) epitaxial layers with X-ray rocking curve full-width-at-half-maxima of 0.09° and root-mean-square surface roughness as low as 0.2 nm have been obtained. Despite the 7.5% lattice mismatch between the SnTe (111) film and the InP (111)A substrate, reciprocal space mapping indicates that the 15 nm SnTe layer is fully relaxed. We show that a periodic interfacial misfit (IMF) dislocation array forms at the SnTe/InP heterointerface, where each IMF dislocation is separated by 14 InP lattice sites/13 SnTe lattice sites, providing rapid strain relaxation and yielding the high quality SnTe layer. This is the first report of an IMF array forming in a rock-salt on zinc-blende material system and at an IV-VI on III-V heterointerface, and highlights the potential for SnTe as a buffer layer for epitaxial telluride film growth. This work represents an important milestone in enabling the heterointegration between IV-VI and III-V semiconductors to create multifunctional devices.

Epitaxial growth of single unit-cell superconducting β-Bi2Pd

Bismuth-based binary alloy β-Bi2Pd has recently been suggested as a connate topological superconductor with immense promise for Majorana zero modes. However, the epitaxial thin films down to the ultimate level of single unit-cell have been challenging. Here, we employed the state-of-the-art molecular beam epitaxy to prepare single unit-cell superconducting β-Bi2Pd films with lateral dimensions of hundreds of nanometers. Utilizing in situ scanning tunneling microscopy/spectroscopy, we uncover evidence of anisotropic superconductivity whose spectra are well fit by anisotropic s-wave gap functions and demonstrate that the epitaxial growth of β-Bi2Pd films relies substantially on the substrate temperature, flux ratio, growth rate, and coverage. The high-quality epitaxial films provide a promising platform to investigate the topological superconductivity at the two-dimensional limit.

Room-Temperature Possible Current-Induced Transition in Ca2RuO4 Thin Films Grown Through Intercalation-Like Cation Diffusion in the A2BO4 Ruddlesden-Popper Structure.

Cation deficiency tuning is a central issue in thin-film epitaxy of functional metal oxides, as it is typically more difficult than anion deficiency tuning, as anions can be readily supplied from gas sources. Here, highly effective internal deficiency compensation of Ru cations is demonstrated for Ca2RuO4 epitaxial films based on diffusive transfer of metal cations in the A2BO4 Ruddlesden-Popper lattice from solid-phase cation sources. Through detailed structural characterization of Ca2RuO4/LaAlO3 (001) thin films grown with external cation sources by solid-phase epitaxy, the occurrence of intercalation-like, interstitial diffusion of La cations (from the substrates) in the A2BO4 structure is revealed, and that of Ru cations is also suggested. Relying on the interstitial-type diffusion, an optimized Ru deficiency compensation method, which does not induce the formation of Can +1RunO3 n +1 Ruddlesden-Popper impurity phases with higher n, is proposed for Ca2RuO4 epitaxial films. In the Ca2RuO4/LaAlO3 (001) thin films grown with Ru deficiency compensation, record-high resistivity values (102-10-1 Ω cm) and a large (more than 200 K) increase in the temperature range of the nonlinear transport properties are demonstrated by transport measurements, demonstrating the possible advantages of this method in the control of the current-induced quantum phase transition of Ca2RuO4.

Producing Freestanding Single-Crystal BaTiO3 Films through Full-Solution Deposition.

Strontium aluminate, with suitable lattice parameters and environmentally friendly water solubility, has been strongly sought for use as a sacrificial layer in the preparation of freestanding perovskite oxide thin films in recent years. However, due to this material's inherent water solubility, the methods used for the preparation of epitaxial films have mainly been limited to high-vacuum techniques, which greatly limits these films' development. In this study, we prepared freestanding single-crystal perovskite oxide thin films on strontium aluminate using a simple, easy-to-develop, and low-cost chemical full-solution deposition technique. We demonstrate that a reasonable choice of solvent molecules can effectively reduce the damage to the strontium aluminate layer, allowing successful epitaxy of perovskite oxide thin films, such as 2-methoxyethanol and acetic acid. Molecular dynamics simulations further demonstrated that this is because of their stronger adsorption capacity on the strontium aluminate surface, which enables them to form an effective protective layer to inhibit the hydration reaction of strontium aluminate. Moreover, the freestanding film can still maintain stable ferroelectricity after release from the substrate, which provides an idea for the development of single-crystal perovskite oxide films and creates an opportunity for their development in the field of flexible electronic devices.

High-Mobility Carriers in Epitaxial IrO2 Films Grown using Hybrid Molecular Beam Epitaxy.

Binary rutile oxides of 5d metals such as IrO2 stand out in comparison to their 3d and 4d counterparts due to limited experimental studies, despite rich predicted quantum phenomena. Here, we investigate the electrical transport properties of IrO2 by engineering epitaxial thin films grown using hybrid molecular beam epitaxy. Our findings reveal phonon-limited carrier transport and thickness-dependent anisotropic in-plane resistance in IrO2 (110) films, the latter suggesting a complex relationship between strain relaxation and orbital hybridization. Magnetotransport measurements reveal a previously unobserved nonlinear Hall effect. A two-carrier analysis of this effect shows the presence of minority carriers with mobility exceeding 3000 cm2/(V s) at 1.8 K. These results point toward emergent properties in 5d metal oxides that can be controlled using dimensionality and epitaxial strain.

Formation of pseudo-morphic domain in Cr2O3(0001) epitaxial film grown on α-Al2O3(0001) and its effect on Néel temperature

To address the issue of the impact of the epitaxial strain on the Néel temperature T N, we investigated the formation of the epitaxial domain in the Cr2O3 layer grown on the α-Al2O3(0001) substrate isostructural to Cr2O3 and determined T N of the fabricated films. We varied the sputtering power for the Cr2O3 growth from 10 W to 40 W to alter the strain condition of the epitaxial film. When the sputtering power is 10 W, the single epitaxial domain is formed, whereas the pseudo-morphic and relaxed domains coexist for the sputtering power above 20 W. T N decreased from about 271 K to below 252 K accompanied by the formation of the two types of epitaxial domains. The lattice parameters of the pseudo-morphic domain are beyond the elastic deformation approximation adopted in the theoretical approaches, suggesting that the correlation between the T N value and the microstructure also goes beyond the existing theoretical framework.

Solid phase epitaxy of SrRuO3 encapsulated by SrTiO3 membranes

Solid phase epitaxy (SPE) has been widely employed for various thin-film materials, making it valuable for industrial applications due to its scalability. In complex oxides, SPE has been limited to a few materials because of the challenges in maintaining stoichiometric control during growth, particularly when volatile phases are present at high temperatures. Here, we investigate the impact of encapsulation layers on the SPE of complex oxides, using SrRuO3 (SRO) as a model system. An amorphous SRO layer was deposited on a SrTiO3 (STO) substrate, followed by the transfer of a single-crystalline STO membrane as an encapsulation layer in order to suppress the evaporation of volatile species (RuO2) during the SPE process. Whereas both encapsulated and unencapsulated SRO layers were successfully crystallized, the unencapsulated films suffered a substantial loss of Ru ions—exceeding 20%—compared to their encapsulated counterparts. This loss of Ru ions led to a loss of metallicity in the unencapsulated SRO layers, whereas the encapsulated layers retained their metallic ferromagnetic properties. This study demonstrates that the encapsulation provided by oxide membranes effectively suppresses stoichiometric loss during SPE, presenting a new strategy in stabilizing a broader class of functional oxides as epitaxial thin films.

Large Rashba spin–orbit coupling in metallic SrTaO3 thin films

We fabricated conductive SrTaO3 epitaxial films on insulator substrates and measured the Rashba parameter using weak anti-localization analysis. The Rashba parameter, reaching up to 9.9 × 10−13 eVm, is the highest among metallic oxides and is comparable to the LaAlO3/SrTiO3 interface, which is widely used in Rashba effect studies. This indicates the potential for oxide-based spintronic devices. To use them as devices, it is important to investigate how film thickness affects the resistivity. Films ranging from 8.6 to 25 nm exhibited metallic conduction, but those thicker than 25 nm showed an unexpected increase in resistivity, suggesting instability of the meta-stable Ta4+ state.

Development of GeSn epitaxial films with strong direct bandgap luminescence in the mid-wave infrared region using a commercial chemical vapor deposition reactor

Germanium tin (GeSn) is a material of interest for electronic and photonic device applications, but its development and commercialization have been limited by material quality issues and lack of availability from epitaxy suppliers. In this paper, we report initial studies in optimizing GeSn films deposited on a Ge buffer layer grown on 200-mm diameter silicon (Si) substrates with an ASM Epsilon 2000 chemical vapor deposition reactor designed for commercial production. Using a single-step growth process, a Sn content up to 22% near the surface of a GeSn film was achieved due to the increase in Sn incorporation via strain relaxation. A two-step growth process resulted in a bilayer structure with a nearly 100% relaxation on the first layer, followed by a higher quality GeSn layer with 18% Sn as evident by a high photoluminescence intensity emitting in the mid-wave infrared region at 3.2 μm at 20 K.

Optimisation of pulsed laser deposited Ba1-xKxBiO3 thin films with tunable superconducting properties by control of K doping level, x

The mid-TC superconductor Ba1-XKXBiO3 (BKBO) exhibits different superconducting mechanisms depending on x, in the range ∼ 0.35–0.65. The optimal doping for the highest TC is reported to be around x = 0.4. To understand more about the dependence of the superconducting mechanism on x, high quality and reproducible epitaxial films with controlled x are needed. This has been challenging owing to the volatility of K and (to a lesser extent) Bi. In this work, we use pulsed laser deposition (PLD) with several novel process steps to achieve high-quality films in a reproducible way. These include a modified method for target preparation, a low NO2 growth pressure, and precise positioning of substrates in the PLD plume. Optimum TC films (32 K onset) were grown from an x = 0.4 target, i.e. with no excess K, as is normally used. Stable, higher K content films (made from an x = 0.45 target), were also grown. These x = 0.45 films had a lower TC (22.5 K onset), as expected for (K) overdoped films, with very high upper critical field, HC2 (0 K), and irreversibility field, Hirr (0 K), values, from linear extrapolation, of ∼ 31.7 T and ∼ 28.8 T, respectively. The growth methodology demonstrated in this work is highly beneficial for fundamental mechanistic studies of this complex superconductor on which there is renewed interest, and where controlled compositions and crystalline quality are currently limited.