Epitaxial Growth Of Thin Films Research Articles

Pulsed-Mode Metalorganic Vapor-Phase Epitaxy of GaN on Graphene-Coated c-Sapphire for Freestanding GaN Thin Films.

We report the growth of high-quality GaN epitaxial thin films on graphene-coated c-sapphire substrates using pulsed-mode metalorganic vapor-phase epitaxy, together with the fabrication of freestanding GaN films by simple mechanical exfoliation for transferable light-emitting diodes (LEDs). High-quality GaN films grown on the graphene-coated sapphire substrates were easily lifted off by using thermal release tape and transferred onto foreign substrates. Furthermore, we revealed that the pulsed operation of ammonia flow during GaN growth was a critical factor for the fabrication of high-quality freestanding GaN films. These films, exhibiting excellent single crystallinity, were utilized to fabricate transferable GaN LEDs by heteroepitaxially growing InxGa1-xN/GaN multiple quantum wells and a p-GaN layer on the GaN films, showing their potential application in advanced optoelectronic devices.

Epitaxial growth of Si thin films with hexagonal close-packed structures on metal substrates.

We have studied the epitaxial growth of Si thin films on the Cd(0001) surface using low-temperature scanning tunneling microscopy. When deposited at low temperatures (100K), Si atoms form dendritic islands with triangular shapes, indicating the existence of anisotropic edge diffusion in the process of Si film growth. After annealing to elevated temperatures, the triangular dendritic Si islands become hexagonal compact islands. Moreover, the 2D Si islands located on two different substrate terraces exhibit different heights due to the influence of quantum-well states in Cd(0001) films. Based on high-resolution scanning tunneling microscopy images, it is observed that the first, second, and third Si layers show the pseudomorphic 1 × 1 structure. In particular, the first and second layer islands reveal the opposite triangles, indicating the hexagonal close-packed stacking of Si atoms. These results provide important information for the growth of pristine Si films on metal substrates and the understanding of Si-metal interaction.

Epitaxial growth of thin films of X-type Sr2Co2Fe28O46 hexaferrite by chemical solution deposition

Epitaxial growth of thin films of X-type Sr2Co2Fe28O46 hexaferrite by chemical solution deposition

Spin Hall Switching Enabled by Uniaxial In-Plane Magnetocrystalline Anisotropy

We present a new method for stabilization of magnetic devices: in-plane uniaxial magnetocrystalline anisotropy, achieved through epitaxial growth of a magnetic thin film on a single-crystal substrate. This paradigm enables the creation of in-plane spin orbit torque magnetic random access memory (SOT-MRAM) devices that function without external fields and exhibit the same scalability as perpendicular SOT-MRAM. Through theoretical derivations and numerical simulations based on the Landau-Lifshitz-Gilbert (LLG) equation with spin transfer torque, we show that switching of such devices can be optimized by varying the angle between the injected spin current and the crystalline easy axis, and contrast this angular dependence with the Stoner-Wohlfarth model. Furthermore, we demonstrate rich and complex magnetization dynamics in this system, including strong and tunable dependence on bulk and interfacial magnetoresistance and boundaries between stochastic and deterministic switching. Finally, we present a concept that couples our in-plane anisotropy layer with an out-of-plane ferromagnet to achieve out-of-plane field-free SOT-MRAM switching. We quantify regions of operation for this new device and link them to simulation results for the in-plane layer alone.

Epitaxial Growth of Cobalt Oxide Thin Films on Sapphire Substrates Using Atmospheric Pressure Mist Chemical Vapor Deposition

This study demonstrated the epitaxial growth of single-phase (111) CoO and (111) Co3O4 thin films on a-plane sapphire substrates using an atmospheric pressure mist chemical vapor deposition (mist-CVD) process. The phase structure of the grown cobalt oxide films was manipulated by controlling the growth temperature and process ambient, confirmed through X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy. Furthermore, the electrical properties of Co3O4 films were significantly improved after thermal annealing in oxygen ambient, exhibiting a stable p-type conductivity with an electrical resistivity of 8.35 Ohm cm and a carrier concentration of 4.19 × 1016 cm−3. While annealing CoO in oxygen atmosphere, the Co3O4 films were found to be most readily formed on the CoO surface due to the oxidation reaction. The orientation of the atomic arrangement of formed Co3O4 was epitaxially constrained by the underlying CoO epitaxial layer. The oxidation of CoO to Co3O4 was largely driven by outward diffusion of cobalt cations, resulting in the formation of pores in the interior of formed Co3O4 films.

Fabrication of highly oriented Mn4N/Pt epitaxial bilayer structure on MgO(001) for spintronics applications

Magnetization control by electric current or spin current is an attractive technology with potential applications in memory and logic devices, and Mn4N has attracted much attention in recent years as a candidate material for current-induced magnetization switching and magnetic domain wall motion, as well as a skyrmion material. For these applications, a bilayer structure of Mn4N and heavy metals must be formed with high crystalline quality. In this study, we have achieved the epitaxial growth of Mn4N thin films on MgO(001) with a Pt underlayer. The reflection high-energy electron diffraction images and x-ray diffraction ω-rocking curves show that the Mn4N films fabricated on the Pt underlayers exhibit higher crystalline quality than the Mn4N films directly formed on the MgO. Furthermore, anomalous Hall effect loops with bump-like structures were observed. This is considered to be due to the topological spin texture. The Mn4N/Pt epitaxial bilayer structure has potential for use in spin–orbit torque applications and is a candidate configuration for topological spin textures.

Large-area epitaxial growth of InAs nanowires and thin films on hexagonal boron nitride by metal organic chemical vapor deposition

Large-area epitaxial growth of III–V nanowires and thin films on van der Waals substrates is key to developing flexible optoelectronic devices. In our study, large-area InAs nanowires and planar structures are grown on hexagonal boron nitride templates using metal organic chemical vapor deposition method without any catalyst or pre-treatments. The effect of basic growth parameters on nanowire yield and thin film morphology is investigated. Under optimised growth conditions, a high nanowire density of 2.1 109 cm−2 is achieved. A novel growth strategy to achieve uniform InAs thin film on h-BN/SiO2/Si substrate is introduced. The approach involves controlling the growth process to suppress the nucleation and growth of InAs nanowires, while promoting the radial growth of nano-islands formed on the h-BN surface. A uniform polycrystalline InAs thin film is thus obtained over a large area with a dominant zinc-blende phase. The film exhibits near-band-edge emission at room temperature and a relatively high Hall mobility of 399 cm−2/(Vs). This work suggests a promising path for the direct growth of large-area, low-temperature III–V thin films on van der Waals substrates.

Phase transition from SrRuO3 to Sr3Ru2O7 by tuning oxygen pressure at low processing temperature

The epitaxial growth of Sr3Ru2O7 thin films in the Ruddlesden-Popper type remains a challenge as the growth temperature required for a typical pulsed laser deposition (PLD) process can be as high as 1100 °C. In this study, high quality Sr3Ru2O7 epitaxial thin films were obtained using PLD with a single SrRuO3 target. By adjusting the oxygen partial pressure, the structure underwent a phase transition from SrRuO3 to Sr3Ru2O7 facilitated by the formation and development of oxygen and ruthenium vacancies. Remarkably, for the first time, high-quality Sr3Ru2O7 thin films with good crystalline quality were successfully grown at a low temperature of 680 °C on SrTiO3 substrates.

Low temperature epitaxial growth of Cantor-nitride thin films by magnetic field assisted magnetron sputtering

Low-temperature epitaxial growth of multicomponent alloy-based thin films remains an outstanding challenge in materials science and is important for established fundamental properties of these complex materials. Here, Cantor nitride (CrMnFeCoNi)N thin films were epitaxially grown on MgO(100) substrates at low deposition temperature by magnetic-field-assisted dc-magnetron sputtering, a technique where a magnetic field is applied to steer the dense plasma to the substrate thereby influencing the flux of Ar-ions bombarding the film during growth. Without ion bombardment, the film displayed textured growth. As the ion flux was increased, the films exhibited epitaxial growth. The epitaxial relationship between film and substrate was found to be cube on cube (001)film||(001)MgO, [100]film||[100]MgO. The epitaxy was retained up to a thickness of approximately ∼100 nm after which the growth becomes textured with a 002 out-of-plane orientation. The elastic constants determined by Brillouin inelastic light scattering were found to be C11 = 320 GPa, C12 = 125 GPa, and C44 = 66 GPa, from which the polycrystalline Young’s modulus was calculated as 204 GPa and Poisson's ratio = 0.32, whereas available elastic properties still remained very scarce.

Expanding the Perovskite Periodic Table to Include Chalcogenide Alloys with Tunable Band Gap Spanning 1.5–1.9 eV

AbstractOptoelectronic technologies are based on families of semiconductor alloys. It is rare that a new semiconductor alloy family is developed to the point where epitaxial growth is possible; since the 1950s, this has happened approximately once per decade. Herein, this work demonstrates epitaxial thin film growth of semiconducting chalcogenide perovskite alloys in the Ba‐Zr‐S‐Se system by gas‐source molecular beam epitaxy (MBE). This work stabilizes the full range y = 0 − 3 of compositions BaZrS(3‐y)Sey in the perovskite structure. The resulting films are environmentally stable and the direct band gap (Eg) varies strongly with Se content, as predicted by theory, with Eg = 1.9 − 1.5 eV for y = 0 − 3. This creates possibilities for visible and near‐infrared (VIS–NIR) optoelectronics, solid‐state lighting, and solar cells using chalcogenide perovskites.

Band gap energy and near infrared to ultraviolet complex optical properties of single crystal TbScO3

TbScO3 is a wide bandgap semiconductor with potential applications in charge trap memory devices and acts as an alternate gate dielectric in fully depleted transistors and also a substrate for epitaxial thin film growth. TbScO3 has an orthorhombic crystal structure, which gives rise to optical anisotropy. Generalized ellipsometric spectra are measured for multiple in-plane rotations of (110) and (001) oriented TbScO3 single crystals over a photon energy range of 0.7–8.5 eV to determine the complex dielectric function (ε = ε1 + iε2) spectra for electric fields oscillating along each axis. A direct bandgap is identified at 6.50 eV, and above gap critical point transitions are found at 6.99, 7.14, 7.16, 7.21, and 7.42 eV.

Li iontronics in single-crystalline T-Nb2O5 thin films with vertical ionic transport channels.

The niobium oxide polymorph T-Nb2O5 has been extensively investigated in its bulk form especially for applications in fast-charging batteries and electrochemical (pseudo)capacitors. Its crystal structure, which has two-dimensional (2D) layers with very low steric hindrance, allows for fast Li-ion migration. However, since its discovery in 1941, the growth of single-crystalline thin films and its electronic applications have not yet been realized, probably due to its large orthorhombic unit cell along with the existence of many polymorphs. Here we demonstrate the epitaxial growth of single-crystalline T-Nb2O5 thin films, critically with the ionic transport channels oriented perpendicular to the film's surface. These vertical 2D channels enable fast Li-ion migration, which we show gives rise to a colossal insulator-metal transition, where the resistivity drops by 11 orders of magnitude due to the population of the initially empty Nb 4d0 states by electrons. Moreover, we reveal multiple unexplored phase transitions with distinct crystal and electronic structures over a wide range of Li-ion concentrations by comprehensive in situ experiments and theoretical calculations, which allow for the reversible and repeatable manipulation of these phases and their distinct electronic properties. This work paves the way for the exploration of novel thin films with ionic channels and their potential applications.

Epitaxial growth of crystalline thin-films of perfluorinated copper phthalocyanine on the single-crystal copper phthalocyanine

Understanding and controlling the growth structures of molecular heterojunctions are important for the pursuit of highly efficient organic semiconductor devices. In this study, a well-defined molecular heterojunction was constructed by the deposition of an n-type organic semiconductor molecule, perfluorinated copper phthalocyanine (F16CuPc), on single-crystals of a typical p-type material, copper phthalocyanine (CuPc). The heterojunction was characterized using synchrotron radiation surface X-ray diffraction techniques to unveil the epitaxial growth of crystalline thin-films of F16CuPc on the CuPc surface. The inter-lattice relationships between F16CuPc and CuPc deduced from the present results imply that the in-plane orientation of the F16CuPc crystal lattice was predominantly governed by the molecular-level alignments of the π-backbones of the F16CuPc and CuPc molecules at the nucleation center for crystal growth at the interface.

Effect of oxygen pressure during the growth of ZnSnO3 epitaxial thin films on LiNbO3 substrates

High-quality ZnSnO3 epitaxial films are grown on LiNbO3(0001) substrates by pulsed laser deposition in an oxygen pressure range of 0.1–10 Pa. The crystalline quality, composition, surface topography, structure, defect formation energy and photovoltaic properties of the epitaxial films are found to be highly sensitive to change in the oxygen pressure by experiments and first-principles density functional theory (DFT). The epitaxial relationship between the film and the substrate is identified as ZnSnO3(0001) || LiNbO3(0001) with ZnSnO3 [2¯ 110] || LiNbO3[2¯ 110]. The film grown atPO2 = 10 Pa has the highest crystal quality, but the photodetector based on the film obtained atPO2 = 0.1 Pa presents the highest responsivity (2.24 A/W at 1 V) and light/dark current ratio (∼105 at 1 V) under the 254-nm-light irradiation. Our results indicate that the as-grown ZnSnO3 epitaxial film should be a potential material for fabricating high-performance UV photodetectors.

Co2Fe(Ti0.5Al0.5) epitaxial thin films: Structural and magnetic properties of a Heusler alloy with Z-site transition metal substitution

We investigate the structural, static, and dynamic magnetic properties of epitaxial Heusler Co2Fe(Ti0.5Al0.5) (CFTA) alloy thin films with thickness varying from 6 nm to 80 nm grown by sputter beam epitaxy on cubic MgO(001), MgAl2O4(001), and hexagonal Al2O3(112̄0) substrates. X-ray diffraction measurements indicate epitaxial growth of CFTA thin films with B2 chemical ordering, with cubic [001] and [220] CFTA axes normal to the cubic and hexagonal substrates, respectively. Microstructure analysis of films grown on MgO substrates reveals a uniformly oriented epitaxial crystal with small variations consistent with strain distortions, providing an explanation for the relatively large X-ray rocking curve values found. Meanwhile, films on Al2O3(112̄0) substrates reveal columnar growth with frequent in-plane grain rotations. A pronounced four-fold magnetocrystalline anisotropy is observed in epitaxial thin films grown on cubic substrates. A pronounced uniaxial anisotropy for films grown on Al2O3(112̄0) substrates is observed. A saturation magnetization of ∼5.0μB/f.u. (where f.u. represents formula unit) is obtained at room temperature, slightly smaller compared to the expected value based on the Slater-Pauling rule. Ferromagnetic resonance spectroscopy finds an effective damping parameter and inhomogeneous linewidth broadening comparable to those found in parent compound Co2FeAl, which suggests that Ti substitution can be achieved without negatively affecting the magnetic properties of the system.

Epitaxial growth of NbN thin films for electrodes using atomic layer deposition

The epitaxial growth of NbN thin film was accomplished via atomic layer deposition (ALD) for the first time using NbCl5 and NH3 as the Nb precursor and nitrogen source at a deposition temperature of 450 ℃. The cubic NbN thin film was grown epitaxially on a cubic MgO crystal through the coherent lattice matching between NbN and MgO with a small lattice mismatch (∼2.8%). A high concentration of Cl impurity of 4–5% remained in NbN thin films grown on a SiO2 substrate using ALD. However, the Cl impurity concentration decreased to ∼ 2% in the epitaxially grown NbN thin films, which facilitated the epitaxial growth of NbN thin films on the MgO substrate. The origin was attributed to a residual strain at the NbN/MgO interface, which induced a bond length change in Nb-N-Cl. The bond length change may promote Cl desorption during NbN ALD because an in-plane compressive strain in the NbN film and an in-plane tensile strain in the MgO surface were observed. Finally, the epitaxially grown NbN thin film exhibited a 50% lower resistivity than that grown with a polycrystalline phase based on the enhanced carrier mobility owing to the improved crystallinity of epitaxial NbN thin films.

Thermal-strain driving sharp metal-to-insulate transition and island-grain growth of solution-derived NdNiO3 epitaxial thin films

An ultra-sharp metal-to-insulate transition (MIT) of 1.24 K−1 in the epitaxial perovskite NdNiO3 thin films was derived by the chemical solution deposition on the LaAlO3 substrates. The thermal strains from shrink, grain growth, and thermal expansion coefficient misfit play a key role in the film microstructure and electrical properties. The originally theoretical in-plane compressive epitaxial strain changes into a tensile one caused by the thermal driving force. It relaxes with improved grain growth via decreased oxygen vacancies with increasing annealing temperature, while the concurrently enhanced tensile strain from the thermal expansion coefficient misfit between the films and the substrate leads to the destabilization of Ni3+ and the higher MIT temperature. Nevertheless, too much higher tensile strain gives rise to island-grain growth in the films, leading to the weak and even disappeared MIT.

Tutorial: Metalorganic chemical vapor deposition of β-Ga2O3 thin films, alloys, and heterostructures

β-phase gallium oxide (Ga2O3) is an emerging ultrawide bandgap (UWBG) semiconductor with a bandgap energy of ∼ 4.8 eV and a predicted high critical electric field strength of ∼8 MV/cm, enabling promising applications in next generation high power electronics and deep ultraviolet optoelectronics. The advantages of Ga2O3 also stem from its availability of single crystal bulk native substrates synthesized from melt, and its well-controllable n-type doping from both bulk growth and thin film epitaxy. Among several thin film growth methods, metalorganic chemical vapor deposition (MOCVD) has been demonstrated as an enabling technology for developing high-quality epitaxy of Ga2O3 thin films, (AlxGa1−x)2O3 alloys, and heterostructures along various crystal orientations and with different phases. This tutorial summarizes the recent progresses in the epitaxial growth of β-Ga2O3 thin films via different growth methods, with a focus on the growth of Ga2O3 and its compositional alloys by MOCVD. The challenges for the epitaxial development of β-Ga2O3 are discussed, along with the opportunities of future works to enhance the state-of-the-art device performance based on this emerging UWBG semiconductor material system.

Epitaxial growth of gadolinium and samarium thin films and their subsequent facile nitridation at ambient temperatures

Lanthanide nitride species have recently been shown to be easily formed at ambient temperatures and low pressures via the reaction of clean lanthanide surfaces with molecular nitrogen. However, understanding and predicting the nature and efficiency of this process is still in its infancy. In this work we report on the nitridation of the surface of two lanthanide metals, gadolinium (Gd) and samarium (Sm). To that end, epitaxial gadolinium and samarium thin layers are grown on AlN(0001) by molecular beam epitaxy and exposed to molecular nitrogen in high vacuum conditions and ambient temperature. In situ reflection high-energy electron diffraction is used to monitor the growth of Gd in real time, as well as the subsequent exposure to nitrogen, showing a clear transition from a pure Gd surface to a gadolinium nitride (GdN) surface layer. The formation of a nitride layer is further reinforced by magnetic measurements showing clear contributions from the Gd metal and GdN surface layers. Formation of SmN is investigated using synchrotron X-ray photoelectron spectroscopy to probe the surface of Sm pre- and post-nitrogen exposure, showing a change in the surface valence from divalent to trivalent samarium, and confirming the nitridation of the pure Sm surface layer.

Epitaxial growth of (Ba0.7Sr0.3)TiO3 thin films on GdScO3 substrates by magnetron sputtering

Epitaxial growth of Ba0.7Sr0.3TiO3 (BST70) thin films on GdScO3 (GSO) substrates had been realized using the radio frequency magnetron sputtering system with the epitaxial alignment [001]BST70||[110]GSO and [010]BST70||[001]GSO. Reciprocal space mapping and transmission electron microscope results confirm the epitaxial growth without an impurity phase at the interface. The Fourier-filtered image shows that the BST70 thin film grew well with few dislocations. The out-of-plane parameter of the as-deposited film was elongated due to strain, which was induced by the differences in the thermal expansion coefficients between the film and the substrate, and oxygen vacancies. The highly strained as-deposited BST70 films could be relaxed by the post-annealing procedure at 800 °C in an O2-rich atmosphere for better epitaxial quality.