Single Crystal Films Research Articles

Laser patterning of large-scale perovskite single-crystal-based arrays for single-mode laser displays

Lead halide perovskites have attracted considerable attention as potential candidates for high-performance nano/microlasers, owing to their outstanding optical properties. However, the further development of perovskite microlaser arrays (especially based on polycrystalline thin films) produced by the conventional processing techniques is hindered by the chemical instability and surface roughness of the perovskite structures. Herein, we demonstrate a laser patterning of large-scale, highly crystalline perovskite single-crystal films to fabricate reproducible perovskite single-crystal-based microlaser arrays. Perovskite thin films were directly ablated by femtosecond-laser in multiple low-power cycles at a minimum machining line width of approximately 300 nm to realize high-precision, chemically clean, and repeatable fabrication of microdisk arrays. The surface impurities generated during the process can be washed away to avoid external optical loss due to the robustness of the single-crystal film. Moreover, the high-quality, large-sized perovskite single-crystal films can significantly improve the quality of microcavities, thereby realizing a perovskite microdisk laser with narrow linewidth (0.09 nm) and low threshold (5.1 μJ/cm2). Benefiting from the novel laser patterning method and the large-sized perovskite single-crystal films, a high power and high color purity laser display with single-mode microlasers as pixels was successfully fabricated. Thus, this study may offer a potential platform for mass-scale and reproducible fabrication of microlaser arrays, and further facilitate the development of highly integrated applications based on perovskite materials.

Impact of Sn incorporation on sputter epitaxy of GeSn

Epitaxial growth of high-quality low tin content germanium (GeSn) alloy is demonstrated by sputter deposition. Adding several percent of Sn during simultaneous sputter deposition significantly improved the crystallographic structure of the GeSn alloy, leading to intense photoluminescence even at room temperature. Dislocation-free single-crystal GeSn films were formed on a Ge(100) substrate under tuned growth conditions, that is, an Sn/Ge flux ratio of 6.2% and deposition temperature of 500 °C, in which compositional gradation of the Sn content in the film thickness direction spontaneously formed. The growth mechanisms are discussed based on growth kinetics and Sn diffusion on the growing surface.

Structural characterization of Zn2SnO4 epitaxial single crystal films prepared on c-cut α-Al2O3 films by magnetron sputtering

Amorphous zinc stannate (Zn2SnO4) films were deposited on α-Al2O3 (0006) substrate by magnetron sputtering. And single crystal Zn2SnO4 films were obtained after thermal-annealing. The structural and optical properties of Zn2SnO4 films at different annealing temperatures were systematically studied. The structural analyses revealed that the sample annealed at 900 °C exhibited the best crystallization quality with an inverse spinel structure. The heteroepitaxy mechanisms were further elucidated by XRD and HETEM. The epitaxial relationship between thin film and substrate can be concluded as Zn2SnO4 (111)//α-Al2O3 (0006) with Zn2SnO4 [0 11‾]//α-Al2O3 <1‾ 100>. The obtained Zn2SnO4 films showed excellent transparency with an average transmittance of 88.8% in the visible region. The optical band gaps of Zn2SnO4 films annealed at temperatures ranging from 600 to 1100 °C was found to be within the range of 3.7–4.2 eV.

Growth and Photoelectrochemical Characterization of Epitaxial ZnTe Photocathodes for Carbon Dioxide Reduction

Harnessing solar energy to drive photocatalytic carbon dioxide reduction reactions (CO2RR) provides an appealing pathway to generate hydrocarbon and oxygenated fuels without an external power source. Zinc telluride (ZnTe) is a II-VI semiconductor which has been identified as a promising photocathode material due to its suitable band gap alignments to CO2 reduction reaction potentials, chemical stability, and strong p-type character. Using molecular beam epitaxy (MBE), single crystal and epitaxial layers are synthesized to gain a deeper understanding of fundamental charge transport and reactivity mechanisms between the single crystal ZnTe thin film and the CO2-saturated electrolyte. These findings are of fundamental interest and are also critical to the design of efficient tandem solar fuels generators for unassisted photoelectrochemical CO2R. Epitaxy allows for highly controlled doping of the thin films over a large range of carrier concentrations. This work focuses largely on the synthesis and characterization of nitrogen doped p-type ZnTe via MBE. Films grown in the temperature range of 340–360ºC on GaAs of (100) orientation with a 200 nm undoped ZnTe buffer layer and a 100 nm doped ZnTe layer have been characterized by RHEED, XRD, AFM, and Hall effect measurements. Doping concentrations between 1020 cm-3 and 1018 cm-3 have been achieved. Dark current-voltage measurements have been used to indicate stability of the electrode in aqueous conditions in less than -0.5 V vs RHE. Future work will include further investigations into carrier dynamics via transient absorption spectroscopy and continual development of a tandem, ZnTe-based photocathode.

(Invited, Digital Presentation) Wafer-Scale Epitaxial Growth of Transition Metal Dichalcogenide Monolayers on Sapphire for Large Area Device Applications

Wafer-scale epitaxial growth of semiconducting transition metal dichalcogenide (TMD) monolayers such as MoS2, WS2 and WSe2 is of significant interest for device applications to circumvent size limitations associated with the use of exfoliated flakes. Epitaxy is required to achieve single crystal films over large areas via coalescence of TMD domains. Our research has focused on epitaxial growth of 2D semiconducting TMDs on c-plane sapphire substrates using metalorganic chemical vapor deposition (MOCVD). Steps on the miscut sapphire surface serve as preferential sites for nucleation and can be used to induce a preferred crystallographic direction to the TMD domains which enables a reduction in twin boundaries in coalesced films. The step-directed growth is dependent on the surface termination of the sapphire which can be altered through pre-growth annealing in H2 and chalcogen-rich environments. Uniform growth of TMD monolayers with significantly reduced inversion domains is demonstrated on 2” diameter c-plane sapphire substrates enabling large area transfer of monolayers for characterization and device fabrication and testing. Applications for wafer-scale TMD monolayers in nanoelectronics, sensing and photonics will be discussed.

Compact magneto-optical isolator by µ-transfer printing of magneto-optical single-crystal film on silicon waveguides.

Optical isolators provide one-way propagation and are necessary to protect laser diodes from damage and unstable operation caused by reflected light. Although magneto-optical (MO) devices can operate as isolators, achieving high-density integration using conventional direct bonding methods is difficult because a large and thick growth substrate remains on the circuits. We experimentally demonstrated a compact Mach-Zehnder interferometer-based MO isolator with Si waveguides by the µ-transfer printing of a Ce:YIG/SGGG coupon. The isolator has a footprint of 0.25 mm2 with a Ce:YIG/SGGG coupon of 50 × 800 µm2 and ∼ 1-µm thickness and achieved a maximum isolation ratio of 14 dB in telecom bands.

Determination of the preferred epitaxy for III-nitride semiconductors on wet-transferred graphene.

Transferred graphene provides a promising III-nitride semiconductor epitaxial platform for fabricating multifunctional devices beyond the limitation of conventional substrates. Despite its tremendous fundamental and technological importance, it remains an open question on which kind of epitaxy is preferred for single-crystal III-nitrides. Popular answers to this include the remote epitaxy where the III-nitride/graphene interface is coupled by nonchemical bonds, and the quasi-van der Waals epitaxy (quasi-vdWe) where the interface is mainly coupled by covalent bonds. Here, we show the preferred one on wet-transferred graphene is quasi-vdWe. Using aluminum nitride (AlN), a strong polar III-nitride, as an example, we demonstrate that the remote interaction from the graphene/AlN template can inhibit out-of-plane lattice inversion other than in-plane lattice twist of the nuclei, resulting in a polycrystalline AlN film. In contrast, quasi-vdWe always leads to single-crystal film. By answering this long-standing controversy, this work could facilitate the development of III-nitride semiconductor devices on two-dimensional materials such as graphene.

Structure and Properties of Thin Magnetron Films of Cadmium Arsenide on Various Substrates

Purpose of the study. Synthesis of cadmium arsenide magnetron films on various substrates and study of their structure, composition, optical and electrical properties.Methods. The deposition of thin films of cadmium arsenide was carried out by the method of non-reactive highfrequency magnetron sputtering in an argon atmosphere. The structure and composition of the films were studied using X-ray phase analysis, scanning electron microscopy, energy dispersive analysis, and small-angle X-ray diffractometry. Optical studies were performed using Raman spectroscopy. The results of a study of the electrical properties of thin films of cadmium arsenide are presented.Results. On silicon, sapphire, and strontium titanate substrates, thin films of the Dirac semimetal, cadmium arsenide, were obtained with a thickness of about 40 nm. A study of their structure and composition showed a significant effect of annealing in an argon atmosphere following deposition on the crystallinity of the film. After annealing, regardless of the crystal structure of the substrate, partial orientation of the film with the (112) texture axis. The films closest to the stoichiometric composition were obtained by deposition followed by annealing onto an oriented strontium titanate substrate, and to the crystal structure of cadmium arsenide single crystals of a film on a sapphire substrate. Annealing also leads to a smoothing of the film surface, a decrease in structural defects, and the transition of the fractal dimension of its topology to two-dimensional from close to three-dimensional immediately after deposition. The optical properties after annealing also change, which indicates their transition from a polycrystalline (amorphous) state to a single-crystal (textured).Conclusion. Experimental studies of the structure and properties performed by various methods made it possible to establish that single-crystal or textured cadmium arsenide films suitable for studying the manifestation of topological properties can be obtained by controlled annealing.

Hydrogen-modulation method for wafer-scale few-layer single-crystal graphene growth

Single-crystal few-layer graphene films have potential applications in microelectronic and optoelectronic devices. Considerable efforts have been taken to prepare large-area bilayer graphene through chemical vapor deposition, but the growth of uniform graphene films with increased layers remains challenging. Herein, a hydrogen-modulation method for growing wafer-scale few-layer single-crystal graphene through chemical vapor deposition was proposed. By controlling the hydrogen flow rate at different stages, the dissolution amount and segregation process of carbon atoms in a CuNi substrate can be regulated separately. The hydrogen-modulation method fully exploits the effect of the dissolution–segregation mechanism, and the number of graphene layers can be controlled by modulating the hydrogen flow rate. Through the proposed method, the coverages of bilayer and trilayer graphene can reach more than 99% and 95%, respectively. The stacking and uniformity of few-layer graphene were evaluated by Raman and microstructure characterization, and bilayer and trilayer graphene were confirmed as AB and ABA stacks, respectively. Transmission line test structure and field effect transistor were prepared to verify the electrical properties of bilayer graphene. Results show that the square resistance of bilayer graphene is significantly lower than that of single-layer graphene, and it can also achieve high on-state current on field effect transistor.

Magnetic Phase Transitions in Ultrathin YFeO3 Films According to Synchrotron Mössbauer Reflectometry Data

The magnetic properties of ultrathin single-crystal Y57FeO3 orthoferrite films have been studied by Mössbauer reflectometry. Mössbauer spectra were measured using the ESRF synchrotron in the reflection geometry. As the temperature changes from 3.6 K to about 773 K, the splitting of the Zeeman sextet in the spectra successively decreases and, simultaneously, a quadrupole doublet appears in them, which indicates the development of a magnetic phase transition. From the temperature dependences of the magnetic hyperfine field Bhf for the main orthorhombic Y57FeO3 phase, Néel temperatures equal to TN ≈ 593 K, 562 K, and 567 K and the critical parameter values equal to β ≈ (0.28–0.3) ± 0.02 are determined in films with thicknesses of 28, 6.5, and 4 nm, respectively. An analysis of changing the ratio of the line intensities in the Zeeman sextet with temperature makes it possible to trace the successive rotation of the direction of the antiferromagnetic axes in Y57FeO3 toward the surface plane with an increase in the temperature and a decrease in the film thickness.

Large magnetostriction in γʹ-Fe4N single-crystal thin film

An Fe4N(110) single-crystal film of 50 nm thickness with γʹ phase is prepared through hetero-epitaxial growth on an MgO(110) single-crystal substrate at 400 °C by reactive sputtering. The out-of-plane and in-plane lattice constants agree with those of bulk within small differences less than 0.2% and the orientation dispersions are about 1.2°. The degree of N site ordering in Fe4N structure is estimated to be 0.995. The arithmetical mean surface roughness is as small as 0.3 nm. These data show that a high-quality Fe4N single-crystal film is successfully formed. The Fe4N film shows in-plane magnetic anisotropy with the easy magnetization direction parallel to [001] and with the hard direction parallel to [1_11], which is reflecting the positive magnetocrystalline anisotropy, K1. A large negative λ100 value of –40 × 10–6 and a fairly-large positive λ111 value of +150 × 10–6 are observed. The present study has shown that γʹ-Fe4N compound is one of the strong candidates for rare-metal-free magnetostrictive materials.

Pseudo-dielectric functions, band-to-band transitions, and dielectric-related factors in a single-crystal LiTi2O4 thin film

This article is devoted to studying the optical properties of a novel single-crystal LiTi2O4 thin film. A high-quality (011)-oriented LiTi2O4 single-crystal thin film was prepared on a MgAl2O4 (011) substrate by pulsed laser deposition. The weak in-plane optical anisotropy is discovered by Mueller-matrix spectroscopic ellipsometry, which can be attributed to the cooperative Jahn-Teller distortion in the Ti–O octahedrons. The pseudo-dielectric functions were determined in the photon energy of 1.24–5.06 eV using the ellipsometric spectra. The optical conductivity, plasma frequency, effective mass, scattering time and other dielectric-related factors are also discussed. The critical points obtained in the pseudo-dielectric functions are originated from the charge-transfer transitions of the Ti related pairs. The results demonstrate that the enhanced effective mass is responsible for the high optical transparency of LiTi2O4 rather than the large high frequency dielectric constant ε∞.

Structure and spectroscopic properties of Er3+ doped LiNbO3 thin film grown by e-beam evaporation

Er3+ doped LiNbO3 (Er: LN) single crystal films with varied doping levels of Er3+ were grown on z-cut LiTaO3 bulk single crystals by using e-beam evaporation method. The crystallographic orientation, fluorescence properties, ions valence states, Er3+ concentration and Li2O content of films were studied. The main phase of the obtained films is determined to be LN from X-ray diffraction and Raman scattering studies, and the films are found to be orienting along (006). Enhancement in the visible and near-infrared luminescence is observed as the doping concentration of Er3+ is increased. The Li2O content of films is determined using the optical birefringence method and found to be at a constant value of 48.8 mol%, which is consistent with the Raman results. XPS results show that the Er concentration in the films is lower than that in the polycrystalline powder since e-beam evaporation has a low efficiency for heavier Er3+. Fluorescence intensity ratios estimated at different measurement temperatures suggest that the Er: LN films have excellent temperature sensitivity, which shows the potential of the films for optical thermometry applications.

Secondary electron emission of B-doped/undoped double-layer heteroepitaxial single crystal diamond film

A B-doped/undoped double-layer single crystal diamond structure was proposed to enhance secondary electron emission (SEE), and the double-layer single crystal diamond film was heteroepitaxially grown on MgO substrate by microwave plasma chemical vapor deposition. The crystal quality, surface morphology and conductivity of the film were studied. It is found that the film has high crystal quality, the full width at half maximum of X-ray diffraction rocking curve is 0.14°, and the surface roughness is small. For these reasons, the B-doped/undoped double-layer single crystal diamond film has better SEE performance than the B-doped/undoped double-layer polycrystalline diamond film. At the incident electron energy of 2 keV, the SEE yield of B-doped/undoped double-layer single crystal diamond reached 22.4. The physical model calculation results indicate that at a low B doping concentration, less sp2 carbon and smaller surface roughness are beneficial to improve the SEE yield.

On the Role of the Sr3−xCaxAl2O6 Sacrificial Layer Composition in Epitaxial La0.7Sr0.3MnO3 Membranes

AbstractThe possibility to fabricate freestanding single crystal complex oxide films has raised enormous interest to be integrated in next‐generation electronic devices envisaging distinct and novel properties that can deliver unprecedented performance improvement compared to traditional semiconductors. The use of the water‐soluble Sr3Al2O6 (SAO) sacrificial layer to detach the complex oxide film from the growth substrate has significantly expanded the complex oxide perovskite membranes library. Nonetheless, the extreme water sensitivity of SAO hinders its manipulation in ambient conditions and restricts the deposition approaches to those using high vacuum. This study presents a pioneering study on the role of Ca‐substitution in solution processed SAO (Sr3−xCaxAl2O6 with x ⩽ 3) identifying a noticeable improvement on surface film crystallinity preserving a smooth surface morphology while favoring the manipulation in a less‐restricted ambient conditions. Then, the study focuses on the effect of the sacrificial composition on the subsequent ex situ deposition of La0.7Sr0.3MnO3 (LSMO) by pulsed laser deposition, to obtain epitaxial films with a variable degree of strain. Finally, epitaxial and strain‐free LSMO membranes with metal‐insulator transition at 290 K are delivered. This study offers a hybrid and versatile approach to prepare and easily manipulate crystalline perovskite oxide membranes by facilitating ex situ growth on SAO‐based sacrificial layer.

Preparation and electrical properties of ultra-thin Bi2212 films by sol-gel method

In order to achieve flexible applications of superconducting thin film materials in devices, the surface quality of the film is critical. The thickness of the film is one of the important factors affecting its surface quality. In this paper, Bi2212 superconducting thin films of different thicknesses were prepared on LaAlO3(100) and SrTiO3(100) single crystal substrates by sol-gel method and the effects of film thickness and different heterogeneous structures on their crystallographic, morphological and superconducting properties were investigated. The results showed that the roughness gradually increased with increasing Bi2212 thickness at the initial stage of film growth and stabilized after reaching a certain thickness, while the superconducting properties were destroyed at very small sample thickness, which was consistent in both single-crystal substrate films. In the Bi2212/LaAlO3 structure, the surface quality of the sample was excellent with a roughness of 5.4 nm at a thickness of about 18 nm for Bi2212, and the growth of the precipitated phase was inhibited to a greater extent. The film also had good superconductivity. This work provided a further research basis for the preparation of high quality Bi2212 films and offers further possibilities for their practical application.

Energy Harvesting of Deionized Water Droplet Flow over an Epitaxial Graphene Film on a SiC Substrate.

This study investigates energy harvesting by a deionized (DI) water droplet flow on an epitaxial graphene film on a SiC substrate. We obtain an epitaxial single-crystal graphene film by annealing a 4H-SiC substrate. Energy harvesting of the solution droplet flow on the graphene surface has been investigated by using NaCl or HCl solutions. This study validates the voltage generated from the DI water flow on the epitaxial graphene film. The maximum generated voltage was as high as 100 mV, which was a quite large value compared with the previous reports. Furthermore, we measure the dependence of flow direction on electrode configuration. The generated voltages are independent of the electrode configuration, indicating that the DI water flow direction is not influenced by the voltage generation for the single-crystal epitaxial graphene film. Based on these results, the origin of the voltage generation on the epitaxial graphene film is not only an outcome of the fluctuation of the electrical-double layer, resulting in the breaking of the uniform balance of the surface charges, but also other factors such as the charges in the DI water or frictional electrification. In addition, the buffer layer has no effect on the epitaxial graphene film on the SiC substrate.

Strain investigation of PECVD passivation layer for ferroelectric domain wall random access memory

Ferroelectric domain-wall random access memory (DWRAM), based on the utilization of highly conductive domain walls in insulating ferroelectric LiNbO3 (LNO) single-crystal thin films, holds great promise for the future of memory storage. The ability to scale this technology up in a crossbar architecture means that it has the otential to surpass the storage density capabilities of commercial ferroelectric random access memory devices. Nevertheless, the passivation layer in the vertically integrated structure (VIS) architecture is critical because it affects many vital parameters of the memory such as retention, on/off current ratio, reliability, etc. Therefore, a detailed strain investigation of silicon nitride and silicon dioxide fabricated by plasma-enhanced chemical vapor deposition (PECVD) is presented. Furthermore, the effect of residual strain on the electrical properties of LNO DW cells was investigated. The results indicated that a monolayer of SiO2 or Si3N4 is not a good choice for the insulating layer because of the undesirable passivation caused by defects and residual strain. Hence, a Si3N4/SiO2 composite passivation layer is proposed, which not only solves the residual strain problem but also ensures good insulation performance. Finally, a crossbar array of DW memory cells with an on/off current ratio greater than 104 was fabricated using the Si3N4/SiO2 composite dielectric layer, demonstrating good uniformity and retention. This work validates the feasibility of high-density integration of LNO domain wall memories and provides a foundation for selecting passivation layers in the VIS architecture.

Crystallization of Copper Films on Sapphire Substrate for Large-Area Single-Crystal Graphene Growth.

Chemical vapor deposition synthesis of graphene on polycrystalline copper substrates from methane is a promising technique for industrial production and application. However, the quality of grown graphene can be improved by using single-crystal copper (111). In this paper, we propose to synthesize graphene on epitaxial single-crystal Cu film deposited and recrystallized on a basal-plane sapphire substrate. The effect of film thickness, temperature, and time of annealing on the size of copper grains and their orientation is demonstrated. Under optimized conditions, the copper grains with the (111) orientation and a record size of several millimeters are obtained, and the single-crystal graphene is grown over their entire area. The high quality of synthesized graphene has been confirmed by Raman spectroscopy, scanning electron microscopy, and the sheet resistance measurements by the four point probe method.

Direct Observation of Magnetic Skyrmions and Their Current-Induced Dynamics in Epitaxial Single-Crystal Oxide Films.

Magnetic skyrmions are scarcely investigated for single-crystal quality films, for which skyrmions may have a remarkable performance. Even in the limited studies in this aspect, the skyrmions are usually probed by the topological Hall effect, missing important information on dynamic properties. Here, we present a comprehensive investigation on the generation/manipulation of magnetic skyrmions in La0.67Ba0.33MnO3 single-crystal films. Using the technique of magnetic force microscopy, the current-driven skyrmion dynamics are directly observed. Unlike isolated skyrmions produced by magnetic field alone, closely packed skyrmions can be generated by electric pulses in a magnetic background, with a high density (∼60/μm2) and a small size (dozens of nanometers). The threshold current moving skyrmions is ∼2.3 × 104 A/cm2, 2-3 orders of magnitude lower than that required by metallic multilayers or van der Waals ferromagnetic heterostructures. Our work demonstrates the great potential of single-crystal oxide films in developing skyrmion-based devices.