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At least 19 records

Molecular Beam Epitaxy (MBE) Growth of Model Cathodes to Study Interfacial Ion Diffusion

Lithium-ion batteries (LIBs) have been the focus of research for decades owing to their superior energy storage potential and wide range of applications. However, long-term stability issues still persist in LIB cathodes as the result of the formation of a solid electrolyte interface (SEI), structural transformations, or the loss of active cathode materials. In nanoscale cathodes, it is often impossible to isolate, let alone mitigate the causes of the observed capacity loss. Herein, a novel approach is presented to synthesizing LIB cathode model systems using thin-film molecular beam epitaxy (MBE). Specifically, 100 nm thick LiMn 2 O 4 (LMO) thin-film cathodes are grown on SrRuO 3 /SrTiO 3 (100) single-crystal substrates and characterized in their pristine and cycled states. The pristine thin films exhibit the electro-chemical cycling behavior and structural evolution previously seen in bulk LMO cathodes. The formation of surface-layer rocksalt MnO and spinel Mn 3 O 4 along with the mass-loss associated with the corrosion of active Mn ions is also reported. It is, therefore, demonstrated that these MBE-grown model systems can be used for detailed studies of their surface structures and the electrode/electrolyte interfacial evolution in LIB cathodes, leading to the development of materials for rechargeable batteries with higher capacity and better stability.

25 ENERGY STORAGE↗

Molecular Beam Epitaxy of Monocrystalline GaAs on Water-Soluble NaCl Thin Films

The goal of this project was to demonstrate the feasibility of employing an epitaxial NaCl thin film as a water-soluble release layer for III-V photovoltaic devices and GaAs substrate reuse. Over the course of this project efforts were focused on: 1) achieving crystalline NaCl thin films on GaAs (100) substrate, 2) exploring the growth parameters for subsequent GaAs on NaCl thin films in effort to improve crystallinity of the semiconductor layer, 3) deposition and removal of single crystalline solar cell devices from the parent substrate, and 4) improving morphology and reducing large scale defects in the removed layers to fabricate a working a solar cell device. There was no previous work on direct integration of GaAs/NaCl/GaAs heterostructures at the time of this study. We used molecular beam epitaxy (MBE) to deposit both the alkali halide salt and subsequent III-V material in the same chamber, with no vacuum break. Single crystalline GaAs films were achieved on NaCl layers through careful tuning of the growth parameters and exposure to the reflection high energy electron diffraction (RHEED) beam. Dissolution of the NaCl layer in water provided rapid release of the semiconductor layer from the substrate. Monocrystalline solar cells were grown on the III-V templates using MBE and dynamic hydride vapor phase epitaxy (HVPE). However, the extended time at elevated temperatures required for the cell growth resulted in large area defects from fusion of the semiconductor overlayer to the substrate, causing shorts in fabricated devices. By changing the way that the template layer was grown, the density of these defects could be reduced. Unfortunately, the defects were not reduced to a level allowing for fabrication of a working device.

14 SOLAR ENERGY↗

Applying CLIPS to control of molecular beam epitaxy processing

A key element of U.S. industrial competitiveness in the 1990's will be the exploitation of advanced technologies which involve low-volume, high-profit manufacturing. The demands of such manufacture limit participation to a few major entities in the U.S. and elsewhere, and offset the lower manufacturing costs of other countries which have, for example, captured much of the consumer electronics market. One such technology is thin-film epitaxy, a technology which encompasses several techniques such as Molecular Beam Epitaxy (MBE), Chemical Beam Epitaxy (CBE), and Vapor-Phase Epitaxy (VPE). Molecular Beam Epitaxy (MBE) is a technology for creating a variety of electronic and electro-optical materials. Compared to standard microelectronic production techniques (including gaseous diffusion, ion implantation, and chemical vapor deposition), MBE is much more exact, though much slower. Although newer than the standard technologies, MBE is the technology of choice for fabrication of ultraprecise materials for cutting-edge microelectronic devices and for research into the properties of new materials.

Rabeau, Arthur A.↗

Hybrid MBE Route to Adsorption-Controlled Growth of BaTiO 3 Membranes with Robust Polarization Switching

Freestanding ferroelectric membranes are promising for flexible electronics, nonvolatile memory, photonics, and spintronics, but their synthesis is challenged by the need for reproducibility with precise stoichiometric control. Here, we demonstrate the adsorption-controlled growth of single-crystalline, epitaxial BaTiO 3 films by hybrid molecular beam epitaxy (MBE) on a binary oxide sacrificial layer. Using a simple water-droplet lift-off method, we obtained submillimeter- to millimeter-sized membranes that retained crystallinity, as confirmed by high-resolution X-ray diffraction, and exhibited robust tetragonal symmetry, as verified by Raman spectroscopy. Impedance spectroscopy confirmed a high dielectric constant of ∼1340, reflecting the robust dielectric response of the membranes. Ferroelectric functionality was revealed by piezoresponse force microscopy (PFM) and further verified by polarization-electric field (P-E) loop measurements with Positive-Up-Negative-Down (PUND). The P-E loops exhibited a remnant polarization of ∼5 μC cm –2 and a coercive field of ∼63 kV cm –1 . Furthermore, these results were interpreted in relation to c- and a-domain configurations.

Raman spectroscopy↗

High Throughput, High Yield Fabrication of High Quantum Efficiency Back-Illuminated Photon Counting, Far UV, UV, and Visible Detector Arrays

In this paper we discuss the high throughput end-to-end post fabrication processing of high performance delta-doped and superlattice-doped silicon imagers for UV, visible, and NIR applications. As an example, we present our results on far ultraviolet and ultraviolet quantum efficiency (QE) in a photon counting, detector array. We have improved the QE by nearly an order of magnitude over microchannel plates (MCPs) that are the state-of-the-art UV detectors for many NASA space missions as well as defense applications. These achievements are made possible by precision interface band engineering of Molecular Beam Epitaxy (MBE) and Atomic Layer Deposition (ALD).

spectroscopy↗

Polymer-assisted transfer of MBE-grown van der Waals materials

Molecular beam epitaxy (MBE) has been used to create high-quality, large-scale two-dimensional van der Waals (2D vdW) materials. However, due to the strong adhesion between the substrate and deposited materials, the peel-off and dry transfer of MBE-grown vdW films onto other substrates has been challenging. This limits the study and use of MBE films for heterogeneous integration including stacked and twisted heterostructures. In this work, we develop a polymer-assisted dry transfer method and successfully perform full-film transfer of various MBE-grown 2D vdW materials including transition metal dichalcogenides (TMD), topological insulators (TI) and 2D magnets. In particular, we transfer air-sensitive 2D magnets, characterize their magnetic properties, and compare them with as-grown materials. The results show that the transfer technique does not degrade the magnetic properties, with the Curie temperature and hysteresis loops exhibiting similar behaviors after the transfer. Our results enable further development of heterogeneous integration of 2D vdW materials based on MBE growth.

Li, Ziling [The Ohio State University]↗

Full-film dry transfer of MBE-grown van der Waals materials

Abstract Molecular beam epitaxy (MBE) has been used to create high-quality, large-scale two-dimensional van der Waals (2D vdW) materials. However, due to the strong adhesion between the substrate and deposited materials, the peel-off and dry transfer of MBE-grown vdW films onto other substrates has been challenging. This limits the study and use of MBE films for heterogeneous integration including stacked and twisted heterostructures. In this work, we develop a polymer-assisted dry transfer method and successfully perform full-film transfer of various MBE-grown 2D vdW materials including transition metal dichalcogenides, topological insulators and 2D magnets. In particular, we transfer air-sensitive 2D magnets, characterize their magnetic properties, and compare them with as-grown materials. The results show that the transfer technique does not degrade the magnetic properties, with the Curie temperature and hysteresis loops exhibiting similar behaviors after the transfer. Our results enable further development of heterogeneous integration of 2D vdW materials based on MBE growth.

Li, Ziling (ORCID:0000000203537036)↗

High polarization InAlGaAs/AlGaAs photocathodes grown using MBE

Strained superlattices of GaAs/GaAsP grown using molecular beam epitaxy (MBE) have been used for more than 20 years to generate high polarization electron beams for nuclear physics. GaAs/GaAsP superlattices have several manufacturing challenges, including the thick graded layer required for the virtual GaAsP substrate, the significant difference in optimal growth temperatures for GaAs and GaAsP, and the scarcity of MBE systems using phosphorus. InAlGaAs/AlGaAs strained superlattice photocathode are an alternative structure that eliminates many of hurdles to growing GaAs/GaAsP in MBE systems. Measurements of quantum efficiency and polarization from InAlGaAs/AlGaAs will be presented. These include studies on a variety of growth parameters to optimize performance, including digital alloys, growth temperature variations, and variation in structure.

Stutzman, Marcy L↗

Fabrication of photovoltaic laser energy converterby MBE

A laser-energy converter, fabricated by molecular beam epitaxy (MBE), was developed. This converter is a stack of vertical p-n junctions connected in series by low-resistivity, lattice matched CoSi2 layers to achieve a high conversion efficiency. Special high-temperature electron-beam (e-beam) sources were developed especially for the MBE growth of the junctions and CoSi2 layers. Making use of the small (greater than 1.2 percent) lattice mismatch between CoSi2 and Si layers, high-quality and pinhole-free epilayers were achieved, providing a capability of fabricating all the junctions and connecting layers as a single growth process with one pumpdown. Well-defined multiple p-n junctions connected by CoSi2 layers were accomplished by employing a low growth temperature (greater than 700 C) and a low growth rate (less than 0.5 microns/hour). Producing negligible interdiffusion, the low growth temperature and rate also produced negligible pinholes in the CoSi2 layers. For the first time, a stack of three p-n junctions connected by two 10(exp -5) Ohm-cm CoSi2 layers was achieved, meeting the high conversion efficiency requirement. This process can now be optimized for high growth rate to form a practical converter with 10 p-n junctions in the stack.

Lu, Hamilton↗

Enhanced quantum efficiency of high-purity silicon imaging detectors by ultralow temperature surface modification using Sb doping

A low temperature process for Sb doping of silicon has been developed as a backsurface treatment for high-purity n-type imaging detectors. Molecular beam epitaxy (MBE) is used to achieve very high dopant incorporation in a thin, surface-confined layer. The growth temperature is kept below 450 (deg)C for compatibility with Al-metallized devices. Imaging with MBE-modified 1kx1k charge coupled devices (CCDs) operated in full depletion has been demonstrated. Dark current is comparable to the state-of-the-art process, which requires a high temperature step. Quantum efficiency is improved, especially in the UV, for thin doped layers placed closer to the backsurface. Near 100% internal quantum efficiency has been demonstrated in the ultraviolet for a CCD with a 1.5 nm silicon cap layer.

charged coupled devices (CCDs)↗

Influence of Growth Parameters and Annealing on Properties of MBE Grown GaAsSbN SQWs

In this paper we report the growth of GaAsSbN/GaAs single quantum well (SQW) heterostructures by molecular beam epitaxy (MBE) and their properties. A systematic study has been carried out to determine the effect of growth conditions, such as the source shutter opening sequence and substrate temperature, on the structural and optical properties of the layers. The substrate temperatures in the range of 450-470 C were found to be optimal. Simultaneous opening of the source shutters (SS) resulted in N incorporation almost independent of substrate temperature and Sb incorporation higher at lower substrate temperatures. The effects of ex-situ annealing in nitrogen ambient and in-situ annealing under As ovepressure on the optical properties of the layers have also been investigated. A significant increase in photoluminescence (PL) intensity with reduced full width at half maxima (FWHM) in conjunction with a blue shift in the emission energy was observed on 10 annealing the samples. In in-situ annealed samples, the PL line shapes were more symmetric and the temperature dependence of the PL peak energy indicated significant decrease in the exciton localization energy as exhibited by a less pronounced S-shaped curve. The inverted S-shaped curve observed in the temperature dependence of PL FWHM is also discussed. 1.61 micrometer emission with FWHM of 25 meV at 20K has been obtained in in-situ annealed GaAsSbN/GaAs SQW grown at 470 C by SS.

Wu, Liangjin↗

Epitaxial Regrowth and Hole Shape Engineering for Photonic Crystal Surface Emitting Lasers (PCSELs)

In the present research, epitaxial regrowth by molecular beam epitaxy (MBE) is investigated as a fabrication process for void-semiconductor photonic crystal (PhC) surface emitting lasers (PCSELs). The PhC is patterned by electron beam lithography (EBL) and inductively coupled plasma (ICP) etch and is subsequently regrown by molecular beam epitaxy to embed a series of voids in bulk semiconductor. Experiments are conducted to investigate the effects of regrowth on air-hole morphology. The resulting voids have a distinct teardrop shape with the radius and depth of the etched hole playing a very critical role in the final regrown void’s dimensions. We demonstrate that specific hole diameters can encourage deposition to the bottom of the voids or to their sidewalls, allowing us to engineer the shape of the void more precisely as is required by the PCSEL design. A 980 nm InGaAs quantum well laser structure is optimized for low threshold lasing at the design wavelength and full device structures are patterned and regrown. An optically pumped PCSEL is demonstrated from this process.

36 MATERIALS SCIENCE↗

A method of producing high quality oxide and related films on surfaces

Aluminum oxide or aluminum nitride films were deposited on molecular beam epitaxy (MBE) grown GaAS(100) using a novel cryogenic-based reactive thin film deposition technique. The process involves the condensation of molecular oxygen, ammonia, or other gases normally used for reactive thin film deposition on the substrate before the metal is deposited. The metal vapor is deposited into this layer and reacts with the molecular solid to form the desired compound or a precursor that can be thermally decomposed to generate the desired compound. The films produced by this method are free of impurities, and the low temperatures can be used to control the film and interfacial structure. The process can be easily integrated with existing MBE systems. Ongoing research using the same apparatus suggests that photon or electron irradiation could be used to promote the reactions needed to produce the intended material.

Ruckman, Mark W.↗

Possibilities for LWIR detectors using MBE-grown Si(/Si(1-x)Ge(x) structures

Traditionally, long wavelength infrared (LWIR) detection in Si-based structures has involved either extrinsic Si or Si/metal Schottky barrier devices. Molecular beam epitaxially (MBE) grown Si and Si/Si(1-x)Ge(x) heterostructures offer new possibilities for LWIR detection, including sensors based on intersubband transitions as well as improved conventional devices. The improvement in doping profile control of MBE in comparison with conventional chemical vapor deposited (CVD) Si films has resulted in the successful growth of extrinsic Si:Ga, blocked impurity-band conduction detectors. These structures exhibit a highly abrupt step change in dopant profile between detecting and blocking layers which is extremely difficult or impossible to achieve through conventional epitaxial growth techniques. Through alloying Si with Ge, Schottky barrier infrared detectors are possible, with barrier height values between those involving pure Si or Ge semiconducting materials alone. For both n-type and p-type structures, strain effects can split the band edges, thereby splitting the Schottky threshold and altering the spectral response. Measurements of photoresponse of n-type Au/Si(1-x)Ge(x) Schottky barriers demonstrate this effect. For intersubband multiquntum well (MQW) LWIR detection, Si(1-x)Ge(x)/Si detectors grown on Si substrates promise comparable absorption coefficients to that of the Ga(Al)As system while in addition offering the fundamental advantage of response to normally incident light as well as the practical advantage of Si-compatibility. Researchers grew Si(1-x)Ge(x)/Si MQW structures aimed at sensitivity to IR in the 8 to 12 micron region and longer, guided by recent theoretical work. Preliminary measurements of n- and p-type Si(1-x)Ge(x)/Si MQW structures are given.

Hauenstein, Robert J.↗

Incorporation of Ti in epitaxial Fe2TiO4 thin films

The titanomagnetites (Fe2-xTixO4, x = 1) are a family of reducible spinel-structure oxides of interest for their favorable magnetic, catalytic, and electrical transport properties. To understand the stability of the system during low temperature deposition, epitaxial thin films of Fe2TiO4 were deposited by molecular beam epitaxy on MgO(001) at 250 – 375°C. The homogeneous incorporation of Ti, Fe valence, and film morphology were all found to be strongly dependent on the oxidation conditions at the low substrate temperatures employed. More oxidizing conditions led to phase separation into epitaxial, faceted Fe3O4 and rutile TiO2. Less oxidizing conditions resulted in polycrystalline films that exhibited Ti segregation to the film surface, as well as mixed Fe valence (Fe3+, Fe2+, Fe0). A narrow window of intermediate oxygen partial pressure during deposition yielded nearly homogeneous Ti incorporation and a large fraction of Fe2+. However, these films were poorly crystallized, and no occupation of tetrahedral sites in the spinel lattice by Fe2+ was detected by x-ray magnetic circular dichroism at the Fe L-edge. After vacuum annealing, a small fraction of Fe2+ was found to occupy tetrahedral sites. Comparison of these results with previous work suggests that the restriction of the deposition conditions to low temperature by the MgO substrate limits the incorporation of Ti into the spinel lattice. This work suggests a path towards obtaining stoichiometric, well-crystallized Fe2TiO4 by MBE by utilizing high substrate temperature and low oxygen partial pressure during deposition on temperature-stable substrates.

Kaspar, Tiffany C.↗

Growth of III-V films by control of MBE growth front stoichiometry

For the growth of strain-layer materials and high quality single and multiple quantum wells, the instantaneous control of growth front stoichiometry is critical. The process of the invention adjusts the offset or phase of molecular beam epitaxy (MBE) control shutters to program the instantaneous arrival or flux rate of In and As4 reactants to grow InAs. The interrupted growth of first In, then As4, is also a key feature.

Grunthaner, Frank J.↗

Investigation of spin and magnetism in two dimensional materials with atomic-scale spatial resolution (Final Technical Report)

Spintronics is an approach to energy-efficient electronics beyond silicon CMOS that utilizes the electron’s spin degree of freedom for memory and logic. The record spin diffusion length in graphene has generated considerable interest in two dimensional (2D) materials (i.e. graphene and beyond) as a platform for spintronics. Magnetism in 2D van der Waals materials may offer additional opportunities for tunability via strain, external fields, and layer-dependent quantum effects. The inherently atomic-scale nature of exchange interactions and the inherently all-surface nature of 2D sheets motivate an integrated approach combining atomic-scale magnetic characterization, epitaxial growth, and nanodevice fabrication. The mission of the research is to develop and utilize atomic-scale imaging of spin and magnetism via spin-polarized scanning tunneling microscopy (STM) in conjunction with atom-by-atom materials growth via molecular beam epitaxy (MBE) and nanoscale device fabrication to explore new frontiers of spintronics and quantum science in 2D materials. The PIs are particularly motivated by understanding how the magnetic and spin-dependent properties at the atomic scale lead to interesting and potentially useful phenomena in spintronic devices at the macroscopic scale.

36 MATERIALS SCIENCE↗