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At least 109 records · Page 6

Toward understanding the dimensional crossover of canonical spin-glass thin films

Spin-glass thin films exhibit many features different from the bulk. The freezing temperatures of spin-glass films are suppressed for reduced thickness and follow the Kenning relation. The dynamics are altered near the vacuum interface. These phenomena are closely related to the lower critical dimension of spin glasses, the spin-glass correlation length, and the dimensional crossover from d = 3 to d = 2. In this article, we review the experimental facts and theoretical perspectives for spin-glass thin films. We focus on canonical spin-glass systems with the Ruderman–Kittel–Kasuya–Yosida (RKKY) interaction between magnetic impurities in a nonmagnetic host. Open questions to be addressed are emphasized.

interfacial effects↗

Ionic-liquid-Assisted Fabrication of Lignocellulosic Thin Films with Tunable Hydrophobicity

Thin films with enhanced water repellency and mechanical strength can be fabricated from renewable lignocellulosic feedstock as a replacement for petrochemical-derived synthetic polymers, such that it minimizes life cycle impact on the environment and human health. In this work, hybrid poplar wood, either untreated (control) or pretreated with hot water at 160 °C for 20 min (HWE-20), 60 min (HWE-60), and 90 min (HWE-90), was dissolved in 1-ethyl-3-methylimidazolium acetate and regenerated to fabricate thin films. The HWE-90 films were enriched in lignin by 74%, specifically on the surface, which along with hemicellulose depletion imparted hydrophobicity (108° water contact angle) when compared to the control (56°), HWE-20 (77°), and HWE-60 (84°) films. They also exhibited 86% reduced water vapor sorption hysteresis and 75% improved storage modulus compared to the control. Thus, we demonstrate how to tune the lignocellulosic film properties via a combination of hot water pretreatment and ionic liquid dissolution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Picosecond magneto-optic thermometry measurements of nanoscale thermal transport in AlN thin films

The thermal conductivity Λ of wide bandgap semiconductor thin films, such as AlN, affects the performance of high-frequency devices, power devices, and optoelectronics. However, accurate measurements of Λ in thin films with sub-micrometer thicknesses and Λ > 100 W m -1 K -1 is challenging. Widely used pump/probe metrologies, such as time–domain thermoreflectance (TDTR) and frequency–domain thermoreflectance, lack the spatiotemporal resolution necessary to accurately quantify thermal properties of sub-micrometer thin films with high Λ. In this work, we use a combination of magneto-optic thermometry and TiN interfacial layers to significantly enhance the spatiotemporal resolution of pump/probe thermal transport measurements. We use our approach to measure Λ of 100, 400, and 1000 nm AlN thin films. We coat AlN thin films with a ferromagnetic thin-film transducer with the geometry of (1 nm-Pt/0.4 nm-Co) x3 /(2 nm-TiN). This PtCo/TiN transducer has a fast thermal response time of <50 ps, which allows us to differentiate between the thermal response of the transducer, AlN thin film, and substrate. For the 100, 400, and 1000 nm thick AlN films, we determine Λ to be 200 ± 80, 165 ± 35, and 300 ± 70 W m -1 K -1 , respectively. We conclude with an uncertainty analysis that quantifies the errors associated with pump/probe measurements of thermal conductivity, as a function of transducer type, thin-film thermal conductivity, and thin-film thickness. Time resolved magneto-optic Kerr effect experiments can measure films that are three to five times thinner than is possible with standard pump/probe metrologies, such as TDTR. This advance in metrology will enable better characterization of nanoscale heat transfer in high thermal conductivity material systems like wide bandgap semiconductor heterostructures and devices.

36 MATERIALS SCIENCE↗

Effects of film thickness on electrochemical properties of nanoscale polyethylenedioxythiophene (PEDOT) thin films grown by oxidative molecular layer deposition (oMLD)

Poly(3,4-ethylene dioxythiophene) (PEDOT) has a high theoretical charge storage capacity, making it of interest for electrochemical applications including energy storage and water desalination. Nanoscale thin films of PEDOT are particularly attractive for these applications to enable faster charging. Recent work has demonstrated that nanoscale thin films of PEDOT can be formed using sequential gas-phase exposures via oxidative molecular layer deposition, or oMLD, which provides advantages in conformality and uniformity on high aspect ratio substrates over other deposition techniques. But to date, the electrochemical properties of these oMLD PEDOT thin films have not been well-characterized. In this work, we examine the electrochemical properties of 5–100 nm thick PEDOT films formed using 20–175 oMLD deposition cycles. We find that film thickness of oMLD PEDOT films affects the orientation of ordered domains leading to a substantial change in charge storage capacity. Interestingly, we observe a minimum in charge storage capacity for an oMLD PEDOT film thickness of ~30 nm (60 oMLD cycles at 150 °C), coinciding with the highest degree of face-on oriented PEDOT domains as measured using grazing incidence wide angle X-ray scattering (GIWAXS). Thinner and thicker oMLD PEDOT films exhibit higher fractions of oblique (off-angle) orientations and corresponding increases in charge capacity of up to 120 mA h g -1 . Electrochemical measurements suggest that higher charge capacity in films with mixed domain orientation arise from the facile transport of ions from the liquid electrolyte into the PEDOT layer. Greater exposure of the electrolyte to PEDOT domain edges is posited to facilitate faster ion transport in these mixed domain films. In conclusion, these insights will inform future design of PEDOT coated high-aspect ratio structures for electrochemical energy storage and water treatment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mitigating photorefractive effect in thin-film lithium niobate microring resonators

Thin-film lithium niobate is an attractive integrated photonics platform due to its low optical loss and favorable optical nonlinear and electro-optic properties. However, in applications such as second harmonic generation, frequency comb generation, and microwave-to-optics conversion, the device performance is strongly impeded by the photorefractive effect inherent in thin-film lithium niobate. In this paper, we show that the dielectric cladding on a lithium niobate microring resonator has a significant influence on the photorefractive effect. By removing the dielectric cladding layer, the photorefractive effect in lithium niobate ring resonators can be effectively mitigated. Our work presents a reliable approach to control the photorefractive effect on thin-film lithium niobate and will further advance the performance of integrated classical and quantum photonic devices based on thin-film lithium niobate.

42 ENGINEERING↗

Synthesis and Mechanical Properties of sub 5‐μm PolyUiO‐66 Thin Films on Gold Surfaces

Abstract Metal‐organic framework (MOF) thin films currently lack the mechanical stability needed for electronic device applications. Polymer‐based metal‐organic frameworks (polyMOFs) have been suggested to provide mechanical advantages over MOFs, however, the mechanical properties of polyMOFs have not yet been characterized. In this work, we developed a method to synthesize continuous sub‐5 μm polyUiO‐66(Zr) films on Au substrates, which allowed us to undertake initial mechanical property investigations. Comparisons between polyUiO‐66 and UiO‐66 thin films determined polyUiO‐66 thin films exhibit a lower modulus but similar hardness to UiO‐66 thin films. The initial mechanical characterization indicates that further development is needed to leverage the mechanical property advantages of polyMOFs over MOFs. Additionally, the demonstration in this work of a continuous surface‐supported polyUiO‐66 thin film enables utilization of this emerging class of polyMOF materials in sensors and devices applications.

Frederick, Esther↗

Non-Contact Mass Density and Thermal Conductivity Measurements of Organic Thin Films Using Frequency–Domain Thermoreflectance

Thin-film organic materials are broadly used to study amorphous stabilization of active pharmaceuticals, control explosive detonation phenomena, and introduce insulation in novel thermal barriers. Their synthesis, however, introduces defects and thickness variations that warrant careful characterization of local thermophysical properties such as thermal conductivity and mass density. In this study, wide bandwidth (200 Hz to 20 MHz) frequency–domain thermoreflectance (FDTR) is demonstrated to simultaneously extract the thermal conductivity and mass density of 1 μm physical vapor-deposited indomethacin films on Si and SiO 2 substrates, as well as 10 and 100 μm films on Si. By assuming a bulk specific heat capacity, mass densities are determined with FDTR measurements of volumetric heat capacity and are in good agreement with the literature, as well as models based upon a dependence on porosity and the kinetic theory for phonons. Lastly, it is found that for broad-band FDTR measurements, insulating substrates provide improved fidelity for the extraction of thermal conductivity and volumetric heat capacity in organic thin films. Overall, this work demonstrates the potential for FDTR as a non-contact method to determine microscale mass density variations across the surface and thickness of organic thin films.

36 MATERIALS SCIENCE↗

Thermal Conductivity of β-Phase Ga 2 O 3 and (Al x Ga 1– x ) 2 O 3 Heteroepitaxial Thin Films

Heteroepitaxy of β-phase gallium oxide (β-Ga 2 O 3 ) thin films on foreign substrates shows promise for the development of next-generation deep ultraviolet solar blind photodetectors and power electronic devices. In this work, the influences of the film thickness and crystallinity on the thermal conductivity of ($\bar{2}01$)-oriented β-Ga 2 O 3 heteroepitaxial thin films were investigated. Unintentionally doped β-Ga 2 O 3 thin films were grown on c-plane sapphire substrates with off-axis angles of 0° and 6° toward $\langle$$11\bar{2}0$$\rangle$ via metal–organic vapor phase epitaxy (MOVPE) and low-pressure chemical vapor deposition. The surface morphology and crystal quality of the β-Ga 2 O 3 thin films were characterized using scanning electron microscopy, X-ray diffraction, and Raman spectroscopy. The thermal conductivities of the β-Ga 2 O 3 films were measured via time-domain thermoreflectance. The interface quality was studied using scanning transmission electron microscopy. The measured thermal conductivities of the submicron-thick β-Ga 2 O 3 thin films were relatively low as compared to the intrinsic bulk value. The measured thin film thermal conductivities were compared with the Debye–Callaway model incorporating phononic parameters derived from first-principles calculations. The comparison suggests that the reduction in the thin film thermal conductivity can be partially attributed to the enhanced phonon-boundary scattering when the film thickness decreases. They were found to be a strong function of not only the layer thickness but also the film quality, resulting from growth on substrates with different offcut angles. Growth of β-Ga 2 O 3 films on 6° offcut sapphire substrates was found to result in higher crystallinity and thermal conductivity than films grown on on-axis c-plane sapphire. However, the β-Ga 2 O 3 films grown on 6° offcut sapphire exhibit a lower thermal boundary conductance at the β-Ga 2 O 3 /sapphire heterointerface. In addition, the thermal conductivity of MOVPE-grown ($\bar{2}01$)-oriented β-(Al x Ga 1–x ) 2 O 3 thin films with Al compositions ranging from 2% to 43% was characterized. Because of phonon-alloy disorder scattering, the β-(Al x Ga 1–x ) 2 O 3 films exhibit lower thermal conductivities (2.8–4.7 W/m∙K) than the β-Ga 2 O 3 thin films. The dominance of the alloy disorder scattering in β-(Al x Ga 1–x ) 2 O 3 is further evidenced by the weak temperature dependence of the thermal conductivity. This work provides fundamental insight into the physical interactions that govern phonon transport within heteroepitaxially grown β-phase Ga 2 O 3 and (Al x Ga 1–x ) 2 O 3 thin films and lays the groundwork for the thermal modeling and design of β-Ga 2 O 3 electronic and optoelectronic devices.

36 MATERIALS SCIENCE↗

Electronic properties of epitaxial La 1- x Sr x RhO 3 thin films

Here, we report on the synthesis and electronic properties of epitaxial perovskite La 1- x Sr x RhO 3 thin films. Thin films with a Sr content ranging from $\textit{x}$ = 0 to 0.5 have been grown using molecular beam epitaxy. Transport and x-ray photoemission spectroscopy data reveal an insulator-metal-insulator transition, accompanied by a $\textit{p-}$ to $\textit{n}-$ type carrier change observed in Hall measurements. Combined with theoretical calculations, we find that the addition of Sr does not directly dope carriers into the conduction band, but rather induces localized Rh 4$\textit{d}$ states within the LaRhO 3 band gap. The bandwidth of the impurity band increases with Sr content, eventually causing the valence band (VB) and the localized Rh 4$\textit{d}$ band to overlap, which explains the first insulator-to-metal transition occurring at $\textit{x}$ = 0.35. For Sr content $\textit{x}$ > 0.4, possible cation ordering results in an increase of the gap between the VB and the Rh 4$\textit{d}$ band, leading to the second metal-to-insulator transition. We map out the electronic phase diagram of the Sr-doped LaRhO 3 system and suggest strategies to engineer the electronic states in rhodate systems via delocalizing the Rh 3+ states.

36 MATERIALS SCIENCE↗

Facile healing of cracks in organic–inorganic halide perovskite thin films

Organic-inorganic halide perovskite (OIHP) thin films at the heart of the burgeoning thin-film perovskite solar cells (PSCs) technology possess poor mechanical properties, which is likely to limit the long-term reliability of PSCs as they are poised for commercialization. In an effort to address this issue, in this work we demonstrate that through-thickness cracks induced by bending-tension in thin films of the two prototypical OlHPs, methylammonium lead triiodide (MAPbl(3)) and formamidinium lead triiodide (FAPbl(3)), can be healed easily. This is through the application of either a moderate compressive stress (bending-compression) at room temperature or a simple heat-treatment at modest temperatures. The crack-healing process is found to be time-dependent, which indicates that facile mass-transport in OlHPs plays a key role in this phenomenon. An explanation for this phenomenon is provided, one based on the fundamentals of brittle fracture. This discovery has broad implications for the prevention and/or restoration of the overall performance, environmental stability, and mechanical reliability of PSCs, and other devices.

36 MATERIALS SCIENCE↗

Au and Pt Diffusion in Electrodeposited Amorphous Sb 2 Te 3 Thin Films

Amorphous Sb 2 Te 3 thin films are synthesized using electrodeposition in different thicknesses to explore their solid electrolytic nature with respect to some noble metals. Au and Pt are used as the substrate materials and thermally diffused into the Sb 2 Te 3 films under passivated and nonpassivated conditions. Rutherford backscattering spectrometry is used to study the Au and Pt diffusion into the films as a function of depth. It is found that Au diffuses into the Sb 2 Te 3 thin films even at room temperature. In contrast, there is no observable diffusion of Pt at room temperature. At a higher temperature (i.e., 200 °C), both Au and Pt diffuse into the Sb 2 Te 3 thin films and Au diffusion is more significant than Pt. Overall, the findings suggest that amorphous Sb 2 Te 3 can be used as a good solid electrolyte to permit the diffusion of some noble metals such as Au and Pt.

36 MATERIALS SCIENCE↗

A Thermodynamic Investigation of Ni on Thin-Film Titanates (ATiO3)

Thin, ~1-nm films of CaTiO3, SrTiO3, and BaTiO3 were deposited onto MgAl2O4 by Atomic Layer Deposition (ALD) and then studied as catalyst supports for ~5 wt % of Ni that was added to the perovskite thin films by Atomic Layer Deposition. Scanning Transmission Electron Microscopy demonstrated that both the Ni and the perovskites uniformly covered the surface of the support following oxidation at 1073 K, even after redox cycling, but large Ni particles formed following a reduction at 1073 K. When compared to Ni/MgAl2O4, the perovskite-containing catalysts required significantly higher temperatures for Ni reduction. Equilibrium constants for Ni oxidation, as determined from Coulometric Titration, indicated that the oxidation of Ni shifted to lower PO2 on the perovskite-containing materials. Based on Ni equilibrium constants, Ni interactions are strongest with CaTiO3, followed by SrTiO3 and BaTiO3. The shift in the equilibrium constant was shown to cause reversible deactivation of the Ni/CaTiO3/MgAl2O4 catalyst for CO2 reforming of CH4 at high CO2 pressures, due to the oxidation of the Ni.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of Oxygen Modification on the Structural and Magnetic Properties of Highly Epitaxial La0.7Sr0.3MnO3 (LSMO) thin films

Abstract La 0.7 Sr 0.3 MnO 3 , a strong semi-metallic ferromagnet having robust spin polarization and magnetic transition temperature ( T C ) well above 300 K, has attracted significant attention as a possible candidate for a wide range of memory, spintronic, and multifunctional devices. Since varying the oxygen partial pressure during growth is likely to change the structural and other physical functionalities of La 0.7 Sr 0.3 MnO 3 (LSMO) films, here we report detailed investigations on structure, along with magnetic behavior of LSMO films with same thickness (~30 nm) but synthesized at various oxygen partial pressures: 10, 30, 50, 100, 150, 200 and 250 mTorr. The observation of only ( 00 l ) reflections without any secondary peaks in the XRD patterns confirms the high-quality synthesis of the above-mentioned films. Surface morphology of the films reveals that these films are very smooth with low roughness, the thin films synthesized at 150 mTorr having the lowest average roughness. The increasing of magnetic T C and sharpness of the magnetic phase transitions with increasing oxygen growth pressure suggests that by decreasing the oxygen growth pressure leads to oxygen deficiencies in grown films which induce oxygen inhomogeneity. Thin films grown at 150 mTorr exhibits the highest magnetization with T C = 340 K as these thin films possess the lowest roughness and might exhibit lowest oxygen vacancies and defects. Interpretation and significance of these results in the 30 nm LSMO thin films prepared at different oxygen growth pressures are also presented, along with the existence and growth pressure dependence of negative remanent magnetization (NRM) of the above-mentioned thin films.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

In Situ X-ray Measurements to Follow the Crystallization of BaTiO 3 Thin Films during RF-Magnetron Sputter Deposition

Here, we report on adding an important dimension to the fundamental understanding of the evolution of the thin film micro structure evolution. Thin films have gained broad attention in their applications for electro-optical devices, solar-cell technology, as well storage devices. Deep insights into fundamental functionalities can be realized via studying crystallization microstructure and formation processes of polycrystalline or epitaxial thin films. Besides the fundamental aspects, it is industrially important to minimize cost which intrinsically requires lower energy consumption at increasing performance which requires new approaches to thin film growth in general. Here, we present a state of the art sputtering technique that allows for time-resolved in situ studies of such thin film growth with a special focus on the crystallization via small angle scattering and X-ray diffraction. Focusing on the crystallization of the example material of BaTiO 3 , we demonstrate how a prototypical thin film forms and how detailed all phases of the structural evolution can be identified. The technique is shaped to enable a versatile approach for understanding and ultimately controlling a broad variety of growth processes, and more over it demonstrate how to in situ investigate the influence of single high temperature sputtering parameters on the film quality. It is shown that the whole evolution from nucleation, diffusion adsorption and grain growth to the crystallization can be observed during all stages of thin film growth as well as quantitatively as qualitatively. This can be used to optimize thin-film quality, efficiency and performance.

36 MATERIALS SCIENCE↗