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At least 91 records · Page 5

Combining Spectroscopic Techniques to Determine the Optical Constants of Powdered Lactose

A method for deriving the optical constants (n/k) of organic powdered materials using pressed pellets in the mid-infrared spectral range is introduced that combines variable angle spectroscopic ellipsometry and transmission spectroscopy. The approach is applied to lactose, in which three different forms of pellets were pressed and measured: A pure lactose pellet and a mixed lactose/KBr pellet with a large analyte percentage were used for ellipsometric measurements, and a KBr transmission pellet with only a small analyte percentage were used for transmission measurements. The transmission data provide an initial set of oscillators and improve the spectral fitting of weak absorption features (k<0.01). Ellipsometric data for the pure and mixed pellets are then fit simultaneously to derive the final n/k values for lactose from 6000-400 cm-1. An alternative method just using the ellipsometric data from the mixed pellet and the transmission data is also presented and shows good agreement with the multi-sample analysis, providing a simpler method for powders that do not press easily into pure pellets. Finally, the derived optical constants are used to model the reflectance data, demonstrating a good match with the measured reflectance spectra if non-idealities are included.

Yokosuk, Michael O.↗

Defect passivation in nanostructured silica for stable birefringence in polarization optics

Nanostructured materials with anisotropic microstructure exhibit direction-dependent refractive index, known as form birefringence. One of the main advantages of these nanostructured materials is that the ease of fabrication significantly reduces the cost of production. However, their birefringence is affected by humidity as well as time. The hypothesis is that defects, particularly silanols, are responsible. Here, in this work, we present the use of hexamethyldisilazane (HMDS) vapor as a passivation strategy. Using spectroscopic ellipsometry and Raman scattering, the data show that HMDS successfully passivates silanol groups and promotes O-Si-O bond formation, resulting in improved stability. The results demonstrate a simple method to enhance the reliability of all-silica polarization optics offering potential advancements for high-power laser components.

Mireles, Marcela [Univ. of Rochester, NY (United S↗

Self-assembled multifunctional nanostructures for surface passivation and photon management in silicon photovoltaics

This work reports the fabrication and characterization of multifunctional, nanostructured passivation layers formed using a self-assembly process that provide both surface passivation and improved light trapping in crystalline silicon photovoltaic (PV) cells. Scalable block copolymer self-assembly and vapor phase infiltration processes are used to form arrays of aluminum oxide nanostructures (Al 2 O 3 ) on crystalline silicon without substrate etching. The Al 2 O 3 nanostructures are characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and spectroscopic ellipsometry. Injection-level dependent photoconductance measurements are used to determine the effective carrier lifetime of the samples to confirm the nanostructures successfully passivate the Si surface. Finite element method simulations and reflectance measurement show that the nanostructures increase the internal rear reflectance of the PV cell by suppressing the parasitic optical losses in the metal contact. An optimized morphology of the structures is identified for their potential use in PV cells as multifunctional materials providing surface passivation, photon management, and carrier transport pathways.

14 SOLAR ENERGY↗

Surface Analysis and Hydrogen Permation Measurements for Super-Permeating Membrane Materials

In this report, we summarize preliminary surface characterization results for Nb surfaces, using low energy ion scattering, direct recoil spectrometry, and Auger electron spectroscopy. While most surface analysis tools cannot detect hydrogen, the low energy ion beam techniques described here are among the few techniques that are directly sensitive to it. For this study, we examined chemisorption using both molecular and atomic hydrogen (using an heated tungsten capillary to dissociate the hydrogen.) To complement these results, we have been performing ex-situ spectroscopic ellipsometry as a means of detecting the surface oxide.

36 MATERIALS SCIENCE↗

Investigation of Ga 2 O 3 as a new transparent conductive oxide for photovoltaics applications

This small innovation project intended to leverage recent activity and advances in ultrawide-bandgap oxide power electronics toward the investigation of Ga 2 O 3 as a transparent conductive oxide (TCO) for use in photovoltaics (PV). Ga 2 O 3 ’s theoretical advantage over incumbent TCOs is its very large bandgap of 4.8 eV, ensuring optical transparency of photons with λ ≥ 260 nm, effectively the full terrestrial solar spectrum. At the time of proposal writing, literature on Ga 2 O 3 as a TCO/optical material was relatively sparse — what little existed was focused on for UV sensors and/or emitters, with none related to PV. As such, this project was intended to help determine the potential of Ga 2 O 3 as a PV-oriented TCO by investigating its deposition using tools common to the PV and electronics industries — atomic layer deposition (ALD) and RF sputtering (RS), both of which are already used in PV manufacturing — and its resultant optical and electronic properties. Final project goals were to test its application to Si and III-V solar cells. Controllable film thickness and excellent uniformity was established for both methods deposition methods, with ALD providing higher precision for thinner films and RS more effective for growing thicker films. The as-deposited films were found to be amorphous in nature. Spectroscopic ellipsometry (SE) confirmed bandgaps of at least 4.8 eV and non-parasitic absorption across both AM0 and AM1.5G spectra; a refractive index approaching the expected value of 1.8 was also observed, with some degree of tunability based on process parameters. Using this initial optical data, a transfer matrix model, which interfaces with in-house EQE and LIV models, was developed to simulate Ga 2 O 3 optical effects on various solar cells, included potential in antireflection coatings (ARCs). Despite promising optical properties, the resultant resistivity / conductivity metrics did not meet expectations, regardless of deposition process. Although thick RS-deposited films, using both undoped and 1 at% Ge (n-type) doped sintered targets — demonstrated high net carrier concentrations (via C-V), and low specific resistance Ohmic contacts were demonstrated, transmission line measurements (TLM) showed very high resistivity. Further analysis indicated high vertical film conductivity, but very low lateral conductivity. Deeper characterization revealed a relatively high density of nano/microcrystalline inclusions that were ostensibly the source of the vertical conductivity, with the amorphous matrix serving as an effective insulator (likely due to high concentrations of electronic trap states). Despite extensive work to increase film polycrystallinity — demonstrated via high temperature annealing — sufficient lateral conductivity for TCO use was not achieved. The final phase of the project shifted focus toward investigation of ALD-deposited Ga 2 O 3 ’s potential as a passivant and/or passivating contact for both Si and III-V solar cells, with expectation of performance similar to Al 2 O 3 . However, initial rounds of testing using our baseline ALD process yielded minimal (but not quite zero) passivation of both GaInP and Si surfaces. Dielectric passivation is well-known to be highly process sensitive; given the unoptimized nature of the process used, this work was deemed inconclusive. The final outlook with respect to feasibility of Ga 2 O 3 as a PV-oriented TCO is, ultimately, still uncertain. The work performed in this project confirmed the optical properties and deposition methods, but the achieved electrical properties do not meet technological needs; literature reports in recent years are somewhat inconsistent and potentially untrustworthy, but generally appear to be in line with our results. At the very least it is clear that, should Ga 2 O 3 still be under consideration for PV TCO and/or selective contact applications, a significant amount of optimization and study is still needed.

14 SOLAR ENERGY↗

Ab initio study of the structure and properties of amorphous silicon hydride from accelerated molecular dynamics simulations

This paper presents a large-scale ab initio simulation study of amorphous silicon hydride (a-Si 1-x H x ) with an emphasis on the structure and properties of the material across a range of hydrogen concentration by combining accelerated molecular dynamics (MD) simulations with first-principles density-functional calculations. The accelerated MD scheme relied on classical metadynamics, which enabled the development of 2600+ high-quality structural models of a-Si 1-x H x , with system sizes ranging from 150 to 6,000 atoms and hydrogen concentrations vary from 6 to 20 at. %. The resulting amorphous networks were found to be completely free from any coordination defects and that they all exhibited a pristine band-gap in their electronic spectrum. The microstructural properties of hydrogen distributions were examined with great emphasis on the presence of isolated and clustered environments of hydrogen atoms. The results were compared with a suite of experimental data obtained from x-ray diffraction, infrared spectroscopy, spectroscopic ellipsometry and nuclear magnetic resonance studies.

36 MATERIALS SCIENCE↗

Structural, Optical and Mechanical Properties of Nanocrystalline Molybdenum Thin Films Deposited under Variable Substrate Temperature

Molybdenum (Mo), which is one among the refractory metals, is a promising material with a wide variety of technological applications in microelectronics, optoelectronics, and energy conversion and storage. However, understanding the structure–property correlation and optimization at the nanoscale dimension is quite important to meet the requirements of the emerging nanoelectronics and nanophotonics. In this context, we focused our efforts to derive a comprehensive understanding of the nanoscale structure, phase, and electronic properties of nanocrystalline Mo films with variable microstructure and grain size. Molybdenum films were deposited under varying temperature (25–500 °C), which resulted in Mo films with variable grain size of 9–22 nm. The grazing incidence X-ray diffraction analyses indicate the (110) preferred growth behavior the Mo films, though there is a marked decrease in hardness and elastic modulus values. In particular, there is a sizable difference in maximum and minimum elastic modulus values; the elastic modulus decreased from ~460 to 260–280 GPa with increasing substrate temperature from 25–500 °C. The plasticity index and wear resistance index values show a dramatic change with substrate temperature and grain size. Additionally, the optical properties of the nanocrystalline Mo films evaluated by spectroscopic ellipsometry indicate a marked dependence on the growth temperature and grain size. This dependence on grain size variation was particularly notable for the refractive index where Mo films with lower grain size fell in a range between ~2.75–3.75 across the measured wavelength as opposed to the range of 1.5–2.5 for samples deposited at temperatures of 400–500 °C, where the grain size is relatively higher. The conductive atomic force microscopy (AFM) studies indicate a direct correlation with grain size variation and grain versus grain boundary conduction; the trend noted was improved electrical conductivity of the Mo films in correlation with increasing grain size. The combined ellipsometry and conductive AFM studies allowed us to optimize the structure–property correlation in nanocrystalline Mo films for application in electronics and optoelectronics.

36 MATERIALS SCIENCE↗

Synthesis of epitaxial TaO$_2$ thin films on Al$_2$O$_3$ by suboxide molecular-beam epitaxy and thermal laser epitaxy

Tantalum dioxide (TaO2) is a metastable tantalum compound. Here, we report the epitaxial stabilization of TaO2 on Al2O3 (1-102) (r-plane sapphire) substrates using suboxide molecular-beam epitaxy (MBE) and thermal laser epitaxy (TLE), demonstrating single-oriented, monodomain growth of anisotropically strained thin films. Microstructural investigation is performed using synchrotron X-ray diffraction and scanning transmission electron microscopy. The tetravalent oxidation state of tantalum is confirmed using X-ray absorption and photoemission spectroscopy as well as electron energy-loss spectroscopy. Optical properties are investigated via spectroscopic ellipsometry and reveal a 0.3 eV Mott gap of the tantalum 5d electrons. Density-functional theory and group theoretical arguments are used to evaluate the limited stability of the rutile phase and reveal the potential to unlock a hidden metal-insulator transition concomitant with a structural phase transition to a distorted rutile phase, akin to NbO2. Our work expands the understanding of tantalum oxides and paves the way for their integration into next-generation electronic and photonic devices.

FOS: Physical sciences↗

Elastomeric reflection suppressor

Various embodiments of the present technology generally relate to reflection suppressors. More specifically, some embodiments use elastomeric materials doped with optical absorbers for temporary suppression of Fresnel reflections for multiple substrates spanning wide spectral and angular bandwidth. The refractive index of the elastomer can be tuned to match a substrate and thereby minimize reflection. Some embodiments can use the addition of different absorptive dopants to allow for either broadband or wavelength-selective reflection suppression. As performance is limited only by index mismatch, both spectral and angular performance significantly exceed that of anti-reflection coatings. After use, these light traps may be removed and reused without damaging the substrate. These films have uses in spectroscopic ellipsometry, holography, and lithography.

Miller, David↗

Advances in Molecular Beam Epitaxy Growth of Ultra-Wide Bandgap Ga2O3 Based Alloys

Gallium oxide (Ga2O3) is an emerging ultra-wide bandgap semiconductor material that has attracted attention for its potential to outperform existing SiC and GaN based devices operating at high breakdown voltages and high temperature. Isovalent alloying of In and Al in Ga2O3 provides the ability to engineer bandgap energy and strain of the material. Alloying with Al increases the bandgap energy and the theoretically achievable Baliga's figure of merit, a key measure of a material's ultimate performance limits for high power switching devices. Alloying with In introduces compressive strain and can be used to counteract the tensile strain of Al incorporation. The resulting (AlxGa1-x-yIny)2O3 alloy can be lattice-matched to commercially available Ga2O3 wafers and has a tunable bandgap energy greater than that of Ga2O3, 4.76 eV. Such lattice-matched material can be grown arbitrarily thick without the detrimental effects of elastic strain and relaxation, making it suitable for high voltage diodes and transistors. However, efforts to synthesize isovalent alloys are complicated by their tendency to phase separate into corundum Al2O3 or bixbyite In2O3. Literature reports of the quaternary (AlxGa1-x-yIny)2O3 are limited to <1% unintentional indium incorporation in In-catalyzed (AlxGa1-x)2O3. The primary limitation to quaternary growth is the limited incorporation of indium at elevated growth temperatures. This limited incorporation is due to both the volatility of indium oxide and Al and Ga cation exchange reactions which replace indium in In2O3. We report on the development of a novel high-throughput molecular beam epitaxy (MBE) technique to screen the growth conditions for the ternary alloy (InyGa1-y)2O3, and the application of these findings to the first successful synthesis of phase pure monoclinic (AlxGa1-x-yIny)2O3 by MBE. By leveraging the unique sub-oxide chemistry of Ga2O3 and in-situ monitoring of crystal properties by reflection high-energy electron diffraction (RHEED), a cyclical growth and etch-back method is developed and applied to rapidly characterize the (InyGa1-y)2O3 growth space. This cyclical method provides approximately 10x increase in experimental throughput and up to 46x improvement in Ga2O3 substrate utilization. Appropriate growth conditions for monoclinic (InyGa1- y)2O3 are identified by machine learning analysis of RHEED patterns and targeted growths are characterized ex-situ to confirm improved In incorporation. These growth conditions are then combined with established (AlxGa1-x)2O3 growth conditions to grow quaternary (AlxGa1-x-yIny)2O3 with Al mole fractions ranging from 1.4% - 24.4% and In mole fractions ranging from 3.1% to 15.5%. The chemical and optical properties of the alloys are investigated by XRD, XPS, and spectroscopic ellipsometry. A lattice-matched (AlxGa1-x-yIny)2O3 alloy is examined by 4D-STEM and the chemical and physical uniformity of Al and In incorporation are discussed.

alloy↗

Method to derive the infrared complex refractive indices n(λ) and k(λ) for organic solids from KBr pellet absorption measurements

Obtaining the complex refractive index vectors $n($$\tilde{v})$ and $k($$\tilde{v})$ allows calculation of the (infrared) reflectance spectrum that is obtained from a solid in any of its many morphological forms. Here, we report an adaptation to the KBr pellet technique using two gravimetric dilutions to derive quantitative $n($$\tilde{v})$/$k($$\tilde{v})$ for dozens of powders with greater repeatability. The optical constants of bisphenol A and sucrose are compared to those derived by other methods, particularly for powdered materials. The variability of the $k$ values for bisphenol A was examined by 10 individual measurements, showing an average coefficient of variation for $k$ peak heights of 5.6%. Though no established standards exist, the pellet-derived $k$ peak values of bisphenol A differ by 11% and 31% from their single-angle- and ellipsometry-derived values, respectively. These values provide an initial estimate of the precision and accuracy of complex refractive indices that can be derived using this method. Limitations and advantages of the method are discussed, the salient advantage being a more rapid method to derive $n$/$k$ for those species that do not readily form crystals or specular pellets.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Inferring relative dose-dependent color center populations in proton irradiated thoria single crystals using optical spectroscopy

In this work, we have utilized photoluminescence spectroscopy and optical ellipsometry to characterize the dose-dependence of the photoluminescence emission intensity and changes in optical absorption of thoria single crystals subject to irradiation with energetic protons at room- and elevated-temperatures. The photoluminescence peaks and the optical absorption bands are attributed to creation of new electronic states emerging from defects resulting from displacement damage. These bands are most likely associated with electrons trapped at the oxygen vacancy sites similar to color centers formed in other irradiated oxides and halides. Our experimental observations are supported by a standard density functional theory calculation of the electronic structure in pristine and oxygen vacancy-bearing thoria crystals. The dose-dependence of the intensity of the photoluminescence peaks is used to parameterize a rate theory model that estimates the concentration of color centers in the irradiated crystals. This parameterization provides optimized migration barrier parameters for oxygen interstitials and vacancies that simultaneously capture the optical response of the crystals irradiated at room- and elevated-temperature. These optical spectroscopy techniques offer a promising pathway to characterize the population of color centers formed at the sites of oxygen anion vacancies, particularly in irradiated nuclear fuels, where atomic-level defects cannot be readily imaged using electron microscopy. When combined with other direct and indirect characterization tools, our approach can provide new insight into defect formation and accumulation in energy materials over single atomic to extended length scales.

36 MATERIALS SCIENCE↗

Controlling Nanoscale Pore Size and Wall Composition in Polycarbonate Membranes via Atomic Layer Deposition and Sequential Infiltration Synthesis: Implications for High Water Permeance

Polymer membranes have a wide variety of applications, ranging from water treatment to energy storage. Many of these applications require precise control over the membrane porosity and surface chemistry. In this study, we explore the modification of isoporous polycarbonate (PC) track-etched membranes (PCTEs) by atomic layer deposition (ALD) and sequential infiltration synthesis (SIS) to tune the pore size and the pore wall surface chemistry. We first performed a detailed study of Al 2 O 3 ALD and SIS in PCTE using a variety of in situ and ex situ measurements. We discovered that short precursor exposure times are critical to achieve conformal Al 2 O 3 ALD in the PCTE nanopores, while longer precursor exposure times resulted in Al 2 O 3 SIS within the bulk of the PC leaving the membranes brittle. Next, we tuned the PCTE pore size via Al 2 O 3 ALD and studied its effect on the water contact angle and the water permeance. Here, we found that the membranes became more hydrophilic, and the permeance decreased with increasing ALD Al 2 O 3 cycles. Finally, we studied the effect of hydrophilic (SnO 2 )/hydrophobic (In 2 O 3 ) ALD metal oxide coatings on membrane properties. We found that the most hydrophilic SnO 2 showed the highest water flux and the least hydrophilic In 2 O 3 showed the lowest water flux through the PCTE membranes. Our results demonstrate that ALD is an effective method to tune the surface and transport properties of PCTE membranes, but care must be exercised to avoid SIS and bulk modification of the polymer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Uncovering an Interfacial Band Resulting from Orbital Hybridization in Nickelate Heterostructures

The interaction of atomic orbitals at the interface of perovskite oxide heterostructures has been investigated for its profound impact on the band structures and electronic properties, giving rise to unique electronic states and a variety of tunable functionalities. In this study, we conducted an extensive investigation of the optical and electronic properties of epitaxial NdNiO 3 thin films grown on a series of single crystal substrates. Unlike films synthesized on other substrates, NdNiO 3 on SrTiO 3 (NNO/STO) gives rise to a unique band structure which features an additional unoccupied band situated above the Fermi level. Our comprehensive investigation, which incorporated a wide array of experimental techniques and density functional theory calculations, revealed that the emergence of the interfacial band structure is primarily driven by the orbital hybridization between Ti 3d orbitals of the STO substrate and O 2p orbitals of the NNO thin film. Furthermore, exciton peaks have been detected in the optical spectra of the NNO/STO film, attributable to the pronounced electron-electron (e-e) and electron-hole (e-h) interactions propagating from the STO substrate into the NNO film. Further, these findings underscore the substantial influence of interfacial orbital hybridization on the electronic structure of oxide thin-films, thereby offering key insights into tuning their interfacial properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Characterization of Tunnel Oxides in TOPCon Solar Cells

The 1.12 nm thickness for the tunnel oxide layer is near the optimal range described by Choi et al. This thickness should be effective at enabling quantum tunneling; however, it is slightly lower than the reported optimal range which could negatively impact the passivation of the poly-Si interface. An appropriate balance between the two functions must be met to optimize efficiency. Follow up work could focus on testing the optimal range for tunnel oxide thickness in TOPCon solar cells, as well as improving the manufacturing process to produce better control of film thickness. This work could be extended into more advanced TOPCon solar cells including double or triple stack structures, as well as experimental pinhole designs.

SOLAR ENERGY↗

Optical contrast analysis of α -RuCl 3 nanoflakes on oxidized silicon wafers

α-RuCl 3 , a narrow-band Mott insulator with a large work function, offers intriguing potential as a quantum material or as a charge acceptor for electrical contacts in van der Waals devices. In this work, we perform a systematic study of the optical reflection contrast of α-RuCl 3 nanoflakes on oxidized silicon wafers and estimate the accuracy of this imaging technique to assess the crystal thickness. Via spectroscopic micro-ellipsometry measurements, we characterize the wavelength-dependent complex refractive index of α-RuCl 3 nanoflakes of varying thickness in the visible and near-infrared. Building on these results, we simulate the optical contrast of α-RuCl 3 nanoflakes with thicknesses below 100 nm on SiO 2 /Si substrates under different illumination conditions. We compare the simulated optical contrast with experimental values extracted from optical microscopy images and obtain good agreement. Finally, we show that optical contrast imaging allows us to retrieve the thickness of the RuCl 3 nanoflakes exfoliated on an oxidized silicon substrate with a mean deviation of –0.2 nm for thicknesses below 100 nm with a standard deviation of only 1 nm. Our results demonstrate that optical contrast can be used as a non-invasive, fast, and reliable technique to estimate the α-RuCl 3 thickness.

2D materials↗

Second-harmonic and linear spectroscopy of $\textit{α}$-In 2 Se 3

We report spectroscopic measurements of optical transmission, ellipsometry, and second-harmonic generation (SHG) from as-grown vapor-deposited $\textit{α}$-In 2 Se 3 nanoflakes ranging in thickness from a single quintuple layer (QL) to bulk material. In this work, we compare these measurements with ab initio calculations of structural and optical properties. Linear optical measurements yield thickness-dependent band gaps and dielectric functions, while SHG diagnoses microscopic film structure and ferroelectric polarization. The rotational anisotropy of SHG for s-polarized incident photons of energy 1.4 eV reveals crystalline symmetry and orientation of individual QLs. Peak SHG intensity increases from one to three QLs, then decreases for larger numbers, tracking thickness-dependent trends in the second-order susceptibility components $χ^{xxx}$ and $χ^{zxx}$. Comparison of measured and calculated SHG spectra for s-polarized photons of energies between 1.2 and 1.7 eV incident upon two QL samples discriminates among candidate stacking arrangements, and favors an arrangement with electric polarization vectors of the two QLs pointing outward in opposite directions.

36 MATERIALS SCIENCE↗

Optical functions of uniaxial rutile and anatase (TiO 2 ) revisited

In this study, the optical functions of uniaxial rutile and anatase (TiO2) were determined from 200 to 850 nm (6.2 to 1.46 eV) using several of four optical techniques: (1) standard spectroscopic two-modulator generalized ellipsometry (2-MGE), (2) near-normal-incidence two-modulator generalized ellipsometry microscopy (2-MGEM), (3) Mueller matrix transmission of rutile, and (4) polarized transmission of rutile. The 2-MGE measurements yielded highly accurate values of the dielectric functions and error estimates from 1.46 to 6.2 eV, whereas the polarization-dependent transmission yielded more accurate values of the absorption coefficient below the band edge of rutile. The 2-MGEM also measured the diattenuation, which is related to the birefringence, and other parameters but at near-normal incidence at a single wavelength (577 nm).

36 MATERIALS SCIENCE↗