Liquid Phase Epitaxy Method Research Articles

Nanoscale Ga/Al substituted yttrium iron garnet films by liquid phase epitaxy

Yttrium iron garnet (YIG) has minimum damping factor and low ferromagnetic resonance (FMR) linewidth, making it a preferred material for low loss microwave and spintronic devices. The saturation magnetization of YIG is 1750 Gauss, and for low-frequency devices, a lower saturation magnetization is more suitable. Ga3+ and Al3+ are with smaller radii and non-magnetic moment, so the substitution of Ga3+ and Al3+ can decrease saturation magnetization. Here, 4.8–193.7 nm ultra-thin Y3(GaAlFe)5O12 garnet (GaAl-YIG) monocrystalline films are prepared on gadolinium gallium garnet (GGG) substrates by using the liquid-phase epitaxy (LPE) method. As expected, these films exhibit a low saturation magnetization of almost less than 100 Gauss, while their FMR linewidth remains at levels close to that of YIG. The films show a (111) orientation and in a state of tension, and the diffraction intensity of the films get stronger as films thickness increases. The free energy and density of states are calculated for different Ga/Al substitution position by density functional theory simulations. The elements show a different diffusion distance in the GaAl-YIG/GGG interface, and the variation of magnetization properties with interface width are analyzed. The surface roughness of the films is only a few angstroms. The damping factor of these ultra-thin films are on an order of 10−4 except the 4.8 nm film, which suggests that the minimum thickness of the garnet film with good performance by using the LPE method is about 10 nm. According to the analysis of structure and magnetization properties, it demonstrates that the LPE method has potential to provide nanoscale garnet films for low loss microwave and spintronic devices.

Photoluminescence and Raman spectroscopy of Ce3+ doped Y3Al5O12 single crystalline films grown onto Y3Al5O12 and Lu3Al5O12 substrates

Raman spectroscopy, high spectral resolution luminescence, and X-ray diffraction techniques were employed to study two Ce3+ doped Y3Al5O12 single crystalline films grown by liquid phase epitaxy method onto Y3Al5O12 and Lu3Al5O12 single crystal substrates. Optical spectra were obtained with a micrometer step along the cross-sections of epitaxial structures, allowing excellent differentiation of the film, the transition layer, and the substrate of each sample. X-ray measurements demonstrate the mismatch between the lattice constants of the Y3Al5O12:Ce3+ film and its Lu3Al5O12 substrate, an effect related to different compositions. Consequently, the film grown onto Lu3Al5O12 exhibits higher residual stresses than its counterpart grown onto Y3Al5O12. This was confirmed by a mutual comparison of the Raman bands positions of the films. The luminescence spectra of both samples consist mainly of cerium 5d-4f emission, the intensity of which allows for additional study of epitaxial cross section and estimation of the size of transition layer.

Nanometer-thick Ga/Al substituted yttrium iron garnet ultra-thin films by liquid phase epitaxial method

Abstract In microwave and spintronic applications, the Gilbert damping coefficient and ferromagnetic resonance (FMR) line width play a decisive role in the component losses. Yttrium iron garnet (YIG) film is a good candidate due to the extremely small damping factor. 4.8 and 51.3 nm ultra-thin Y3(GaAlFe)5O12 (GaAl-YIG) films are grown on gadolinium gallium garnet (GGG) substrate using liquid phase epitaxial (LPE) technology. The films show a (111) orientation and tensile strain, and the roughness of the film surface is small. The films show a low saturation magnetization because of Ga and Al substituted, and the comparison of magnetization properties with film thickness is analyzed. The FMR line width is tested, and the calculated damping constant of the 51.3 nm film is on the order of 10−4. The structural and magnetization properties analysis demonstrates that LPE technology has the potential to provide nanometer-thick garnet films for low-loss spintronic devices.

Three-Layered Composite Scintillator Based on the Epitaxial Structures of YAG and LuAG Garnets Doped with Ce3+ and Sc3+ Impurities.

In this study, we propose novel three-layer composite scintillators designed for the simultaneous detection of different ionizing radiation components. These scintillators are based on epitaxial structures of LuAG and YAG garnets, doped with Ce3+ and Sc3+ ions. Samples of these composite scintillators, containing YAG:Ce and LuAG:Ce single crystalline films with different thicknesses and LuAG:Sc single crystal substrates, were grown using the liquid phase epitaxy method from melt solutions based on PbO-B2O3 fluxes. The scintillation properties of the proposed composites, YAG:Ce film/LuAG:Sc film/LuAG:Ce crystal and YAG:Ce film/LuAG:Ce film/LuAG:Sc crystal, were investigated under excitation by radiation with α-particles from a 239Pu source, β-particles from 90Sr sources and γ-rays from a 137Cs source. Considering the properties of the mentioned composite scintillators, special attention was paid to the ability of simultaneous separation of the different components of mixed ionizing radiation containing the mentioned particles and quanta using scintillation decay kinetics. The differences in scintillation decay curves under α- and β-particle and γ-ray excitations were characterized using figure of merit (FOM) values at various scintillation decay intensity levels (1/e, 0.1, 0.05, 0.01).

MOF-Derived Zn/N-Doped Porous Carbon Film on a Carbon Nanotube for High-Performance Supercapacitors.

Designing high-performance binder-free electrochemical electrodes is crucially important toward supercapacitors. In this paper, a Zn/N-doped porous carbon film coating on flexible carbon nanotubes (ZIF-8@CT-800) derived from the epitaxial Zn-MOF film growth on cotton textile was successfully fabricated via a combination of the liquid-phase epitaxial (LPE) method and calcination treatments. The ZIF-8@CT-800 serves directly as a self-supported electrode for supercapacitors and exhibits a high areal capacitance of 930 mF·cm-2 at a current density of 1 mA·cm-2 and a good recyclability of 86% after 2000 cycles. The excellent supercapacitor property is ascribed to the unique structural design of ZIF-8@CT-800, which provides appropriate channels for enhanced electronic and ionic transport as well as increased surface area for accessing more electrolyte ions. This work will provide significant guidance for designing MOF-derived porous carbon to construct flexible binder-free electrode materials with high electrochemical performance.

PA2PbBr4/MAPbBr3 Heterojunction X‐Ray Detector with Enhanced Sensitivity and Excellent Self‐Powered Functionality

AbstractHeterojunctions combining 2D and 3D perovskites have caused a surge in the research on X‐ray detectors. The enhanced charge transport facilitated by the built‐in electric field further amplifies the potential of this material system, paving the way for highly sensitive and efficient X‐ray detectors. In this study, PA2PbBr4 single‐crystal film with a thickness of 10 µm is successfully grown on the surface of MAPbBr3 substrate via liquid phase epitaxial method, forming a 2D/3D heterojunction. This innovative detector exhibits a dramatically enhanced sensitivity of 3.81 × 104 µC Gy−1 cm−2 at an X‐ray tube voltage of 70 keV and a bias of 50 V mm−1, along with an ultra‐low detection limit of 11.84 nGy s−1, surpassing the performance of the conventional MAPbBr3 X‐ray detectors by a factor of four and 2 × 103 times higher than that of commercialized α‐Se detectors. Furthermore, the 2D/3D heterojunction exhibits exceptional self‐powered X‐ray detection capabilities, achieving a remarkable sensitivity of 3562.26 µC Gy−1 cm−2 at 70 keV X‐ray tube voltage. This superior performance implies reduced energy consumption, high portability, decreased ion migration, and provides inspiration for the next generation of high‐performance X‐ray detectors.

Study on the Faraday rotation angle of La-substituted barium hexaferrite in the terahertz band.

M-type barium hexaferrites (Ba1-xLaxFe12O19) were prepared by the liquid phase epitaxial (LPE) method, in which Ba2+ was substituted by La3+. The Faraday rotation effect of materials in the frequency range of 0.5-0.8 terahertz (THz) is studied by THz time-domain spectroscopy (THz-TDS). It was demonstrated that the M-type barium hexaferrites have a large Faraday rotation angle, and the Faraday rotation angle can be further enhanced by the substitution of La3+. For 500 µm thick film samples, the Faraday rotation angle exceeded 20° under the maximum measuring magnetic field of 400 mT. Moreover, the Faraday rotation angle is not saturated, and it will further increase with the increase of the magnetic field. At 0.8 THz, the Faraday rotation angle of the sample with x = 0 is 21.48°, for x = 0.05 which is 21.62°, and for x = 0.19 which is 28.38°. The Faraday rotation angle is enhanced by about 32%. By measuring the magnetic properties of the material, we found that the fundamental cause of the enhancement in the Faraday rotation angle lies in the increased saturation magnetization of the material after La3+ substitution. In the experiment, it was also found that the transmittance of the material to the THz wave decreased sharply with the increase of La substitution. For sample x = 0, the transmittance is as high as 60%. When the substitution amount of La is only x = 0.05, the transmittance decreases to about 55%. When the maximum substitution amount of La is x = 0.24, the transmittance of the material is only about 2%.

Temperature dependence of photoluminescence kinetics and scintillation properties of LuY2(Al5-xScx)O12:Ce (x = 1, 1.5, 2) garnet single-crystalline films

The temperature dependence of photoluminescence (PL) kinetics and scintillation properties were investigated in LuY2(Al5-xScx)O12:Ce (x = 1, 1.5, 2) garnet single-crystalline films grown by the isothermal liquid phase epitaxy method. With the increase of Sc content, the Ce3+ 5d1 level was shifted to higher energy while the Ce3+ 5d2 level was shifted to lower energy due to the decrease in crystal field splitting of the 5d levels. Activation energy of thermal quenching, determined from temperature-dependent PL decay times, decreased with increasing Sc content. At room temperature, the decrease of light yield (LY) value with increasing Sc content is caused by the thermal ionization process. LuY2(Al4Sc)O12:Ce showed a LY value of 510 photons/MeV when excited by 5.5 MeV α-particles, which is ∼21 % larger than that of Lu2Y(Al4Sc)O12:Ce due to a smaller bandgap Eg of the former.

Giant reduced magnetic anisotropy in magneto-optical garnet

Magneto-optical garnet shows great potential in integrated optical isolators due to its highly efficient non-reciprocity. In this work, we prepared magneto-optical lithium-modified terbium bismuth iron garnet films using the liquid phase epitaxy method and systemically investigated the effect of lithium modification on magnetic properties. We found a trace amount of lithium modification induced in-plane magnetization and a minimum in-plane driving field around 2 Oe. Meanwhile, high remanence over 70% was obtained in tensile-strain samples. Most importantly, in comparison to unmodified samples, the calculation of anisotropy demonstrated the giant reduction of growth-induced anisotropy in the Li: TbBiIG up to 105erg/cm3. It reveals a new rule of ions’ preferred occupation in dodecahedral sublattices indirectly. Furthermore, enhanced Faraday rotation in the near-infrared band was confirmed in the samples about 1 micrometer, up to 48% higher than unmodified samples. Our work shows Li:TbBiIGs enable a prime candidate material with substantial potential for integrated optical isolation applications.

Analysis of GaN crystal growth mechanism in liquid-phase epitaxial Na-flux method

Analysis of GaN crystal growth mechanism in liquid-phase epitaxial Na-flux method

In-plane magnetic properties and anisotropy of scandium substituted thulium iron garnet thin films for fluxgate magnetometer

In-plane easily magnetized scandium substituted thulium iron garnet films(Tm3Fe5-xScxO12) with soft magnetic properties have recently attracted attention for fluxgate magnetometer applications. In this paper, thin Tm3Fe5-xScxO12 films were prepared on gadolinium gallium garnet substrates by liquid phase epitaxial(LPE) method. Microstructural properties, composition, magnetic properties and the in-plane anisotropy of the films were discussed. We found that the films turned from tensile stress to compressive stress as the Sc3+ substitution decreased, and the in-plane anisotropy was mainly caused by stress reducing as Sc3+ declined. By analyzing the in-plane magnetic hysteresis loops, the magnetic performance was the best when x = 0.75. Tm3Fe4.25Sc0.75O12 film had the lowest in-plane coercive field(0.006 Oe) and the highest initial magnetic permeability(378), which was more beneficial to realize fluxgate magnetometers.

Growth and microwave properties of layered ferrogarnet structures

The ferrogarnet structures consisting from one- to three- layers of monocrystalline yttrium-iron garnet Y3Fe5O12 (YIG) films, two- layered YIG - La,Ga:YIG and two- layered {Y,Sm,Lu}3(Fe,Ga)5O12 -YIG structures were grown by liquid-phase epitaxy (LPE) method on gadolinium - gallium garnet Gd3Ga5O12 (GGG) substrates of (111) orientation. The obtained layered ferrogarnet structures were studied by the methods of ferromagnetic resonance (FMR) and magnetostatic wave (MSW) interference. The two- and three- layered YIG structures have a wide FMR line width (∆H). For the three- layered YIG structures with the total thickness of 68-102 μm ∆H = 5,7- 11,5 Oe. The line width ∆H = 0,34 – 1,22 Oe correspond to the two- layered (Y,Sm,La)3(Fe,Ga)5O12 – YIG structures with thicknesses from 3 to 65 μm. Individual layers in all structures are characterized by similar or different saturation magnetizations (4πMs).The frequency MSW separation in the YIG - La,Ga:YIG layered structure was observed. It was shown that the propagation losses of MSW in one- and two- layered structures increase with decreasing wavelength of MSW and transition to a two- layered structure.

Color converters for white LEDs using liquid phase epitaxy growth method

The development of innovative high-power lighting sources is urgently required to design and investigate the new high structural quality and high-temperature stable converters in the form of single crystals and single crystalline films. This research deals with the growth and investigation of structural, luminescence, and photoconversion properties (color coordinates, color temperature and color rendering index) of the single crystalline films of Ce3+ doped (Lu, Y, Tb, Gd)3Al5O12 garnets, grown using the Liquid Phase Epitaxy method onto undoped Y3Al5O12 substrates. The combination of Ce3+ doped Lu3Al5O12, Y3Al5O12, Tb3Al5O12, Gd2.9Lu0.1Al5O12 film converter with respective thickness with commercial blue LED allows for obtaining green-yellow-orange-emitting pc-WLEDs. The application of the mentioned film converters results in the formation of four basic trends on the color diagram depending on the thickness of the converter.

Regularities of Manganese Charge State Formation and Luminescent Properties of Mn-Doped Al2O3, YAlO3, and Y3Al5O12 Single Crystalline Films

In this work, three sets of single crystalline films (SCF) of Al2O3:Mn sapphire, YAlO3:Mn perovskite (YAP:Mn), and Y3Al5O12:Mn garnet (YAG:Mn), with a nominal Mn content of 0.1%, 1%, and 10 atomic percent (at.%) in the melt-solutions, were crystallized by the liquid phase epitaxy (LPE) method onto sapphire, YAP and YAG substrates, respectively. We have also calculated the average segregation coefficient of Mn ions for Al2O3:Mn, YAP:Mn and YAG:Mn SCFs with Mn content in the melt-solution in the 0.1–10% concentration range, which was equal to 0.1, 0.14 and 0.2, respectively. The main goal of the conducted research was the spectroscopic determination of the preferable valence states of manganese ions which were realized in the SCFs of sapphire, perovskite and garnet depending on the Mn content. For this purpose, the absorption, cathodoluminescence (CL), photoluminescence (PL) emission/excitation spectra and PL decay kinetics of Al2O3:Mn, YAP:Mn and YAG:Mn SCFs with different Mn concentrations were studied. Based on the CL and PL spectra, we showed that Mn ions, depending on the Mn content in the melt-solution, are incorporated in Al2O3:Mn, YAP:Mn and YAG:Mn SCFs in the different charged states and are located in the different crystallographic positions of the mentioned oxide lattices. We have observed the presence of the luminescence of Mn4+, Mn3+ and Mn2+ valence states of manganese ions in CL spectra in all SCFs under study with 0.1 and 1% Mn concentrations. Namely, the Mn4+ ion valence state with the main sharp emission bands peaked at 642 and 672 nm, related to the 2E → 4A2 transitions, was found in the luminescence spectra of the all studied Al2O3:Mn SCFs. The luminescence of the Mn2+ valence state was found only in YAP:Mn and YAG:Mn SCFs, grown from melt solution with 1% Mn content, in the emission bands peaked at 525 and 560 nm, respectively, related to the 4T1 → 6A1 transitions. The PL and CL spectra of YAP:Mn and YAG:Mn SCFs with the Mn content in the 0.1–1% range show that the main valence state of manganese ions in these films is Mn3+ with the main emission bands peaking at 655 and 608 nm, respectively, related to the 1T2 → 5E transitions. Meanwhile, higher than 1% Mn content in the melt solution causes a strong concentration quenching of luminescence of all Mn centers in Al2O3:Mn, YAP:Mn and YAG:Mn SCFs.

Enhanced terahertz magneto-optical performance in substrate-free ultra-thick TbErBi:RIG crystal films

A wafer-scale single crystal thick film of rare-earth iron garnet (RIG) has been successfully produced on a 3-in. gadolinium gallium garnet (GGG) substrate using the liquid phase epitaxy method. The RIG crystal's thickness measures ∼550 μm. By removing the GGG substrate through polishing, we improved the terahertz (THz) transmittance of the RIG crystal. In the frequency range of 0.1–1.0 THz, the RIG material exhibits a large refractive index of around 4.50, with a transmittance of ∼60% and an absorption rate of only 10–50 cm−1. Furthermore, we investigated the THz magneto-optical effect in the RIG material through THz time-domain spectroscopy. The observed results demonstrate the presence and significance of the magneto-optical effect in the RIG crystal. To provide further insights, we measured the THz Faraday rotation angle of the 550 μm-thick RIG crystal using the THz-TDS system under an external magnetic field of 0.17 T. The measured Faraday rotation angle reached 22°, and the calculated Verdet constant for the RIG sample was ∼120°/mm/T. Considering these findings, our study highlights the unique properties of this wafer-scale single crystal thick film of RIG, including its low loss, high transmission, and strong magneto-optical effect in the THz range. These characteristics make it a promising candidate for various applications, such as THz magnetic polarization conversion, non-reciprocal phase shifters, and isolators.

Improved Optical Efficiency of 850-nm Infrared Light-Emitting Diode with Reflective Transparent Structure.

This study investigated a reflective transparent structure to improve the optical efficiency of 850 nm infrared light-emitting diodes (IR-LEDs), by effectively enhancing the number of extracted photons emitted from the active region. The reflective transparent structure was fabricated by combining transparent epitaxial and reflective bonding structures. The transparent epitaxial structure was grown by the liquid-phase epitaxy method, which efficiently extracted photons emitted from the active area in IR-LEDs, both in the vertical and horizontal directions. Furthermore, a reflective bonding structure was fabricated using an omnidirectional reflector and a eutectic metal, which efficiently reflected the photons emitted downwards from the active area in an upward direction. To evaluate reflective transparent IR-LED efficiency, a conventional absorbing substrate infrared light-emitting diode (AS IR-LED) and a transparent substrate infrared light-emitting diode (TS IR-LED) were fabricated, and their characteristics were analyzed. Based on the power-current (L-I) evaluation results, the output power (212 mW) of the 850 nm IR-LED with the reflective transparent structure increased by 76% and 26%, relative to those of the AS IR-LED (121 mW) and TS IR-LED (169 mW), respectively. Furthermore, the reflective transparent structure possesses both transparent and reflective properties, as confirmed by photometric and radial theta measurements. Therefore, light photons emitted from the active area of the 850 nm IR-LED were efficiently extracted upward and sideways, because of the reflective transparent structure.

Liquid phase epitaxy growth and visible emission of Tb3+,Gd3+:LiYF4 layers

Single-crystalline layers of 12 at.% Tb3+, 5 at.% Gd3+:LiYF4 were grown by the liquid phase epitaxy method on (001) oriented bulk undoped LiYF4 substrates using LiF as a solvent. The growth temperature was 737–740 °C, the growth duration was 15 - 25 min, and the layer thickness was 40–90 µm. The structural, morphological, vibronic and spectroscopic properties of the layers were studied. Tb3+ ions were uniformly distributed in the layers with no diffusion into the substrate. Polarized Raman spectroscopy confirmed the orientation of the layers (growth along the [001] direction). Under excitation in the blue, the layers exhibited intense green emission. For the 5D4 → 7F5 Tb3+ transition, the peak stimulated-emission cross-section is 1.28 × 10−21 cm2 at 542.0 nm for π-polarization. The luminescence lifetime of the 5D4 Tb3+ state is 5.05 ms at room temperature. The crystal-field splitting of Tb3+ multiplets was determined at low temperature. The developed epitaxies are promising for green and yellow waveguide lasers.

The epitaxial iron-yttrium garnet films with homogeneous properties and narrow FMR line width

The growth of iron-yttrium garnet Y3Fe5O12 (YIG) films with of 1...15 μm thicknesses on single-crystal substrates of gallium-gadolinium garnet Gd3Ga5O12 (GGG) was carried out using the method of liquid phase epitaxy (LPE). The influence of the composition and mass of the charge, the temperature regimes, the rates of movement and the substrate rotation on the films parameters were studied. The layered structure caused by the heterogeneity of the chemical composition in the film thickness was determined and studied The dependence of the degree impurity of Pb2+ and Pt4+ ions in YIG films and their influence on the ferromagnetic resonance (FMR) line width ∆H on the films growth conditions was investigated. It’s shown that in order to obtain by the LPE method the series of defect-free films with low magnetic losses and reproducible parameters, it’s necessary to use melt-solutions of large mass (6...12 kg) and apply their additional mixing during the growth process.

Studies of the crystal structure of solid solutions (Sn2)1−x−y(GaAs)x(ZnSe)y, (GaAs)1−x(ZnSe)x grown from liquid phase

The possibility of growing (Sn2)1−x−y(GaAs)x(ZnSe)y, (GaAs)1−x(ZnSe)x solid solutions on a GaAs(100) substrate is shown at the temperature of the beginning of crystallization, respectively, TOC = 570 °C and TOC = 750 °C by the method of liquid-phase epitaxy from a limited tin solution-melt in the cooling rate range of 0.5–3 K/min. The content of the chemical composition and the perfection of the substrate-film boundary of epitaxial layers of solid solutions (Sn2)1−x−y(GaAs)x(ZnSe)y, (GaAs)1−x(ZnSe)x were studied using a scanning electron microscope (SEM).X-ray diffraction studies have shown that the resulting films are single-crystal with (100) orientation and have a sphalerite structure. Using a transmission electron microscope (TEM), we obtained HR TEM images of (GaAs)1−x(ZnSe)x poly- and single-crystal samples grown at a crystallization onset temperature TOC = 750 °C with forced cooling at a rate of 3 deg/min. and 1 deg/min. Some electrophysical and photoelectric properties of the samples have been studied.

Development of Three-Layered Composite Color Converters for White LEDs Based on the Epitaxial Structures of YAG:Ce, TbAG:Ce and LuAG:Ce Garnets

This work was dedicated to the development of novel types of composite phosphor converters of white LED, based on the epitaxial structures containing Y3Al5O12:Ce (YAG:Ce) and Tb3Al5O12:Ce (TbAG:Ce) single crystalline films, steeply grown, using the liquid-phase epitaxy method, onto LuAG:Ce single crystal substrates. The influence of Ce3+ concentration in the LuAG:Ce substrate, as well as the thickness of the subsequent YAG:Ce and TbAG:Ce films, on the luminescence and photoconversion properties of the three-layered composite converters were investigated. Compared to its traditional YAG:Ce counterpart, the developed composite converter demonstrates broadened emission bands, due to the compensation of the cyan-green dip by the additional LuAG:Ce substrate luminescence, along with yellow-orange luminescence from the YAG:Ce and TbAG:Ce films. Such a combination of emission bands from various crystalline garnet compounds allows the production of a wide emission spectrum of WLEDs. In turn, the variation in the thickness and activator concentration in each part of the composite converter allows the production of almost any shade from green to orange emission on the chromaticity diagram.