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At least 325 records · Page 18

Thin-film chemical expansion of ceria based solid solutions: laser vibrometry study

The chemical expansion of Pr 0.1 Ce 0.9 O 2-δ (PCO) and CeO 2-δ thin films is investigated in the temperature range between 600 °C and 800 °C by laser Doppler vibrometry (LDV). It enables non-contact determination of nanometer scale changes in film thickness at high temperatures. The present study is the first systematic and detailed investigation of chemical expansion of doped and undoped ceria thin films at temperatures above 650 °C. The thin films were deposited on yttria stabilized zirconia substrates (YSZ), operated as an electrochemical oxygen pump, to periodically adjust the oxygen activity in the films, leading to reversible expansion and contraction of the film. This further leads to stresses in the underlying YSZ substrates, accompanied by bending of the overall devices. Film thickness changes and sample bending are found to reach up to 10 and several hundred nanometers, respectively, at excitation frequencies from 0.1 to 10 Hz and applied voltages from 0–0.75 V for PCO and 0–1 V for ceria. At low frequencies, equilibrium conditions are approached. As a consequence maximum thin-film expansion of PCO is expected due to full reduction of the Pr ions. The lower detection limit for displacements is found to be in the subnanometer range. At 800 °C and an excitation frequency of 1 Hz, the LDV shows a remarkable resolution of 0.3 nm which allows, for example, the characterization of materials with small levels of expansion, such as undoped ceria at high oxygen partial pressure. As the correlation between film expansion and sample bending is obtained through this study, a dimensional change of a free body consisting of the same material can be calculated using the high resolution characteristics of this system. A minimum detectable dimensional change of 5 pm is estimated even under challenging high-temperature conditions at 800 °C opening up opportunities to investigate electro-chemo-mechanical phenomena heretofore impossible to investigate. The expansion data are correlated with previous results on the oxygen nonstoichiometry of PCO thin films, and a defect model for bulk ceria solid solutions is adopted to calculate the cation and anion radii changes in the constrained films during chemical expansion. The constrained films exhibit anisotropic volume expansion with displacements perpendicular to the substrate plane nearly double that of bulk samples. The PCO films used here generate high total displacements of several 100 nm’s with high reproducibility. Consequently, PCO films are identified to be a potential core component of high-temperature actuators. They benefit not only from high displacements at temperatures where most piezoelectric materials no longer operate while exhibiting, low voltage operation and low energy consumption.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Are Contact Angle Measurements Useful for Oxide-Coated Liquid Metals?

This work establishes that static contact angles for gallium-based liquid metals have no utility despite the continued and common use of such angles in the literature. In the presence of oxygen, these metals rapidly form a thin (~1–3 nm) surface oxide “skin” that adheres to many surfaces and mechanically impedes its flow. This property is problematic for contact angle measurements, which presume the ability of liquids to flow freely to adopt shapes that minimize the interfacial energy. We show here that advancing angles for a metal are always high (>140°)—even on substrates to which it adheres—because the solid native oxide must rupture in tension to advance the contact line. The advancing angle for the metal depends subtly on the substrate surface chemistry but does not vary strongly with hydrophobicity of the substrate. During receding measurements, the metal droplet initially sags as the liquid withdraws from the “sac” formed by the skin and thus the contact area with the substrate initially increases despite its volumetric recession. Furthermore, the oxide pins at the perimeter of the deflated “sac” on all the surfaces are tested, except for certain rough surfaces. With additional withdrawal of the liquid metal, the pinned angle gets smaller until eventually the oxide “sac” collapses. Thus, static contact angles can be manipulated mechanically from 0° to >140° due to hysteresis and are therefore uninformative. We also provide recommendations and best practices for wetting experiments, which may find use in applications that use these alloys such as soft electronics, composites, and microfluidics.

36 MATERIALS SCIENCE↗

Increasing the mobility and power-electronics figure of merit of AlGaN with atomically thin AlN/GaN digital-alloy superlattices

Alloy scattering in random AlGaN alloys drastically reduces the electron mobility and, therefore, the power-electronics figure of merit. As a result, Al compositions greater than 75% are required to obtain even a twofold increase in the Baliga figure of merit compared to GaN. However, beyond approximately 80% Al composition, donors in AlGaN undergo the DX transition, which makes impurity doping increasingly more difficult. Moreover, the contact resistance increases exponentially with the increase in Al content, and integration with dielectrics becomes difficult due to the upward shift of the conduction band. Atomically thin superlattices of AlN and GaN, also known as digital alloys, are known to grow experimentally under appropriate growth conditions. These chemically ordered nanostructures could offer significantly enhanced figure of merit compared to their random alloy counterparts due to the absence of alloy scattering, as well as better integration with contact metals and dielectrics. In this work, we investigate the electronic structure and phonon-limited electron mobility of atomically thin AlN/GaN digital-alloy superlattices using first-principles calculations based on density-functional and many-body perturbation theory. The bandgap of the atomically thin superlattices reaches 4.8 eV, and the in-plane (out-of-plane) mobility is 369 (452) cm 2 V -1 s -1 . Using the modified Baliga figure of merit that accounts for the dopant ionization energy, here we demonstrate that atomically thin AlN/GaN superlattices with a monolayer sublattice periodicity have the highest modified Baliga figure of merit among several technologically relevant ultra-wide bandgap materials, including random AlGaN, β-Ga 2 O 3 , cBN, and diamond.

36 MATERIALS SCIENCE↗

Cooled thin metal liner

A first metal sheet (34) has openings (46) in registration with depressions (40) in a second contacting metal sheet (36). Each depression has a downstream wall (42) at an angle of 24.degree. from the plane of the sheets. A metering hole (56) in the depression amidst cooling air in a direction to first impinge against an overlaying portion (48) of the first plate, before it diffuses along the downstream wall.

Liang, George P.↗

In Situ Li Seed Formation Enables Uniform Plating in Anode-Free Solid-State Batteries

Anode-free solid-state batteries (AFSSBs) are a promising route toward achieving high energy density. In these cells, the anode contains no pre-stored lithium (Li). Instead, all Li inventory originates from the cathode and is freshly deposited onto a bare current collector during charging. However, achieving uniform and defect-free Li plating on this bare current collector remains a major challenging, often resulting in low Li plating/stripping efficiency and rapid capacity decay. Here, for the first time, operando neutron imaging is employed to visualize Li plating/stripping behavior in an anode-free full cell with LiNi 0.82 Mn 0.07 Co 0.11 O 2 (NMC) as the cathode. Operando measurements reveal that complete stripping of Li leaves isolated Li residues on the current collector, which degrades interfacial contact between the current collector and solid-state electrolyte. To mitigate this interfacial issue and promote more uniform Li deposition, we implement a discharge cutoff voltage strategy that intentionally retains a thin residual Li layer after stripping. This thin Li layer, serving as an in situ–formed seed layer, not only enables more homogeneous subsequent Li plating but also improves interfacial contact. As a result, the anode-free cell with a controlled discharge voltage of 3.5 V exhibits excellent long-term cycling stability, maintaining a discharge capacity of 116 mAh g -1 with a retention rate of 83.4% and an average Coulombic efficiency of approximately 99.9% after 430 cycles at 0.25 C. In contrast, the cell with a conventional discharge cutoff voltage of 2.8 V exhibits rapid capacity decay, retaining only 59.7 mAh g -1 after 50 cycles with a capacity retention of 40.7%. This work offers a practical strategy to unlock the long-term viability of anode-free solid-state batteries.

25 ENERGY STORAGE↗

Defect-mediated metastability and carrier lifetimes in polycrystalline (Ag,Cu)(In,Ga)Se 2 absorber materials

Using a combination of optical and electrical measurements, we develop a model for metastable defects in Ag-alloyed Cu(In,Ga)Se 2 , one of the leading thin film photovoltaic materials. By controlling the pre-selenization conditions of the back contact prior to the growth of polycrystalline (Ag,Cu)(In,Ga)Se 2 absorbers and subsequently exposing them to various stresses (light soaking and dark-heat), we explore in this paper the nature and role of metastable defects on the electro-optical and photovoltaic performance of high-efficiency solar cell materials and devices. Positron annihilation spectroscopy indicates that dark-heat exposure results in an increase in the concentration of the selenium–copper divacancy complex (V Se –V Cu ), attributed to depassivation of donor defects. Deep-level optical spectroscopy finds a corresponding increase of a defect at Ev+0.98 eV, and deep-level transient spectroscopy suggests that this increase is accompanied by a decrease in the concentration of mid-bandgap recombination centers. Time-resolved photoluminescence excitation spectroscopy data are consistent with the presence of the V Se –V Cu divacancy complex, which may act as a shallow trap for the minority carriers. Light-soaking experiments are consistent with the V Se –V Cu optical cycle proposed by Lany and Zunger, resulting in the conversion of shallow traps into recombination states that limit the effective minority carrier recombination time (and the associated carrier diffusion length) and an increase in the doping density that limits carrier extraction in photovoltaic devices.

14 SOLAR ENERGY↗

Apparatus for electrical measurements of thin films from 77 to 1000 K

A novel method of mounting thin samples for electrical measurements is described. A vacuum chuck holds a mounting plate, which, in turn, holds the sample. Contacts on the mounting plate establish electrical connection to the sample. The attachment of wires directly to the samples is unnecessary. Measurements can be made at temperatures from 77 to 1000 K. As an application of the apparatus, resistivity and Hall measurements of a thin silicon carbide sample are presented.

Matus, L. G.↗

Controlled exposure of CuO thin films through corrosion-protecting, ALD-deposited TiO 2 overlayers

Ultra-thin film coatings are used to protect semiconductor photoelectrodes from the harsh chemical environments common to photoelectrochemical energy conversion. These layers add contact transfer resistance to the interface that can result in a reduction of photoelectrochemical energy conversion efficiency of the photoelectrode. Here, we describe the concept of a partial protection layer, which allows for direct chemical access to a small fraction of the semiconductor underlayer for further functionalization by an electrocatalyst. The rest of the interface remains protected by a stable, inert protection layer. CuO is used as a model system for this scheme. Atomic layer deposition (ALD)-prepared TiO 2 layers on CuO thin films prepared from electrodeposited Cu 2 O allow for the control of interfacial morphology to intentionally expose the CuO underlayer. The ALD-TiO 2 overlayer shrinks during crystallization, while Cu 2 O in the underlayer expands during oxidation. As a result, the TiO 2 protection layer cracks to expose the oxidized underlying CuO layer, which can be controlled by preceding thermal oxidation. Furthermore, this work demonstrates a potentially promising strategy for the parallel optimization of photoelectrochemical interfaces for chemical stability and high performance.

14 SOLAR ENERGY↗

Development of ~25% Efficient Double Side Screen Printed Poly-Si/SiO x Passivated Contact Solar Cells

This program aims to overcome these challenges and develop high-efficiency (24-25%) double-side (DS) TOPCon solar cells by maximizing passivation on both sides while mitigating light absorption losses. To achieve this, the program will implement either thin (≤ 20 nm) homogeneous n-TOPCon on the entire front surface or selective area thick (≥ 100 nm) n-TOPCon only underneath the front metal contact with ~90% field region composed of dielectric passivated textured n-Si in between the poly-Si/metal grid. The rear side will feature ~250 nm-thick full-area planar p-TOPCon, which functions as the rear junction. Recombination and parasitic absorption losses in the front and rear TOPCon layers will be minimized by tailoring their doping profiles and thickness. Additionally, the device performance will be further enhanced through the optimization of bulk parameters, including the carrier lifetime, resistivity, and thickness of the n-type Si absorber. Finally, advanced metallization techniques, such as fine-line printing, and floating busbar or busbar-less designs, will be employed to reduce recombination, resistive, and optical losses. The program started with the development of a technology roadmap for DS-TOPCon cells to achieve target efficiency.

14 SOLAR ENERGY↗

Carbon-Nanotube Conductive Layers for Thin-Film Solar Cells

Thin, transparent layers comprising mats of carbon nanotubes have been proposed for providing lateral (that is, inplane) electrical conductivities for collecting electric currents from the front surfaces of the emitter layers of thin-film solar photovoltaic cells. Traditionally, thin, semitransparent films of other electrically conductive materials (usually, indium tin oxide, zinc oxide, or cadmium sulfide) have been used for this purpose. As in the cases of the traditional semitransparent conductive films, the currents collected by the nanotube layers would, in turn, be further collected by front metal contact stripes. Depending on details of a specific solar-cell design, the layer of carbon nanotubes would be deposited in addition to, or instead of, a semitransparent layer of one of these traditional conductive materials (see figure). The proposal is expected to afford the following advantages: The electrical conductivity of the carbon- nanotube layer would exceed that of the corresponding semitransparent layer of traditional electrically conductive material. The greater electrical conductivity of the carbon-nanotube layer would make it possible to retain adequate lateral electrical conductivity while reducing the thickness of, or eliminating entirely, the traditional semitransparent conductive layer. As a consequence of thinning or elimination of the traditional semitransparent conductive layer, less light would be absorbed, so that more of the incident light would be available for photovoltaic conversion. The greater electrical conductivity of the carbon-nanotube layer would make it possible to increase the distance between front metal contact stripes, in addition to (or instead of) thinning or eliminating the layer of traditional semitransparent conductive material. Consequently, the fraction of solar-cell area shadowed by front metal contact stripes would be reduced again, making more of the incident light available for photovoltaic conversion. The electrical conductivities of individual carbon nanotubes can be so high that the mat of carbon nanotubes could be made sparse enough to be adequately transparent while affording adequate lateral electrical conductivity of the mat as a whole. The thickness of the nanotube layer would be chosen so that the layer would contribute significant lateral electrical conductivity, yet would be as nearly transparent as possible to incident light. A typical thickness for satisfying these competing requirements is expected to lie between 50 and 100 nm. The optimum thickness must be calculated by comparing the lateral electrical conductivity, the distance between front metal stripes, and the amount of light lost by absorption in the nanotube layer.

Landis, Geoffrey A.↗

Use of non-contact voltmeter to quantify potential induced degradation in CdTe modules

Potential induced degradation (PID) is a significant reliability issue for photovoltaic modules in the field. Conventionally, to detect the PID-affected modules, all the modules in a string are individually disconnected and measured using I-V (current–voltage) tracers. It is extremely time-consuming, expensive and unsafe (if the module connectors are field aged) approach. In our approach, we aim detecting the PID-affected modules quickly, inexpensively and safely without disconnecting individual modules in the string. In this study, contactless electrostatic voltmeter’s (ESV) strength was explored to detect the PID-affected cadmium telluride (CdTe) modules in a string. These contactless measurements on high-voltage PV strings could make this technique unique and preferable to detect PID-affected modules in a string compared to the I-V curve method. In this work, a CdTe module was stressed for PID using the Aluminum (Al) foil method in a walk-in environmental chamber, which resulted in a reduction of module's peak current (I max ), peak voltage (Vmax), and fill factor (FF), and hence power (Pmax). Outdoor light I-V, EL, and ESV measurements were performed pre- and post-PID to determine the effectiveness of the non-contact ESV technique. Further, the ESV technique successfully detected the change in V max , and hence Pmax, compared to the pre-and post-PID conditions. A difference of less than 2% was observed in the results of the non-contact and non-interruptive method compared to the conventionally used interruptive voltmeter or I-V tracer method. This technique and the test results demonstrate a significant promise to identify poor-performing modules in PV string without disconnection of individual modules in the string.

14 SOLAR ENERGY↗

Optimization of multi-layer front-contact grid patterns for solar cells

In a front-contact grid pattern for a solar cell there is a trade-off necessary between shadowing loss and excessive power loss due to voltage drop in the metalization itself. If the metalization is too little there may be excessive contact resistance to the underlying semiconductor and insufficient coverage to control losses in the thin front-surface layer of the solar cell. Optimization of grid pattern area and geometry is considered analytically to minimize total losses. Worthwhile performance advantages are shown to be possible, particularly in concentrator systems, if multi-layer grid patterns are used. The current carrying fingers should be approximately square in metal cross section and the main current feedout bars should not only be wider but also thicker than the primary collecting fingers. This is termed multi-level metalization. Effective use of multi-level grid metalization allows much greater concentration-to-loss ratio for a cell of large area and permits good performance from cells of high front-layer sheet resistance.

Flat, A.↗

The ball bearing as a rheological test device

An angular-contact ball bearing provides an easily obtainable, precise mechanical system for rheological tests on thin films under high pressure. The test conditions are by definition similar to those found in practice. Accessible independent variables include size, pressure, bulk temperature, roughness, adsorbed surfactant, fluid type, fluid quantity, fluid supply rate, film thickness, entrainment velocity, transit time, and combined strain. Easily measured or inferred variables include slip, changes in film thickness with time (transients), strain rate, lubricant elastic modulus (thin film, high pressure), tractive force, lubricant chemical degradation rate, and lubricant degradation product. Methods for setting and obtaining these quantities in a bearing are discussed, together with experimental limitations on them.

Kingsbury, E.↗

Bias Selective Operation of Sb-Based Two-Color Photodetectors

Multicolor detectors have a strong potential to replace conventional single-color detectors in application dealing with the simultaneous detection of more than one wavelength. This will lead to the reduction of heavy and complex optical components now required for spectral discrimination for multi-wavelengths applications. This multicolor technology is simpler, lighter, compact and cheaper with respect to the single-color ones. In this paper, Sb-based two-color detectors fabrication and characterization are presented. The color separation is achieved by fabricating dual band pn junction on a GaSb substrate. The first band consists of an InGaAsSb pn junction for long wavelength detection, while the second band consists of a GaSb pn junction for shorter wavelength detection. Three metal contacts were deposited to access the individual junctions. Surface morphology of multi-layer thin films and also device characteristics of quasi-dual band photodetector were characterized using standard optical microscope and electro-optic techniques respectively. Dark current measurements illustrated the diode behavior of both lattice-matched detector bands. Spectral response measurements indicated either independent operation of both detectors simultaneously, or selective operation of one detector, by the polarity of the bias voltage, while serially accessing both devices.

Abedin, M. N.↗

Bare Conductive Tether for Decelerating a Spacecraft

A document describes a prototype of electrically conductive tethers to be used primarily to decelerate spacecraft and/or generate electric power for the spacecraft. Like prior such tethers, this tether is designed so that when it is deployed from a spacecraft in orbit, its motion across the terrestrial magnetic field induces an electric current. The Lorentz force on the current decelerates the spacecraft. Optionally, the current can be exploited to convert some orbital kinetic energy to electric energy for spacecraft systems. Whereas the conductive portions of prior such tethers are covered with electrical insulation except for end electrodes that make contact with the ionosphere, this tether includes a conductive portion that is insulated along part of its length but deliberately left bare along a substantial remaining portion of its length to make contact with the ionosphere. The conductive portions of the tether are made of coated thin aluminum wires wrapped around strong, lightweight aromatic polyamide braids. The main advantages of the present partly-bare-tether design over the prior all-insulated-tether design include greater resistance to degradation by the impact of monatomic oxygen at orbital altitude and speed and greater efficiency in collecting electrons from the ionosphere.

Johnson, Les↗

Using Holey Graphene for Improved Interfacial Contact in Solid Electrolyte Ionic Conductivity Measurements

Solid-state batteries (SSBs) are poised to become the batteries of the future with advantages such as higher energy density, lighter weight, versatile geometry, and greater safety due to low flammability risk. An important parameter of the solid electrolyte (SE) used is its ionic conductivity. The ionic conductivity is generally calculated from the bulk resistance of a SE pellet, measured from the electrochemical impedance spectroscopy data. The SE pellet is typically prepared from the electrolyte powder by dry compression and is sandwiched between two blocking current collectors to obtain the impedance spectroscopy data. One of the challenges in conducting this measurement is poor interfacial contacts between the SE pellet and the current collector surfaces. Therefore, measurements reported in the literature may underestimate the true ionic conductivity of a given electrolyte. Holey graphene is a carbon nanomaterial with high electrical conductivity and unique dry compressibility, which is unusual for carbon materials but similar to many oxide and sulfide SEs. In this work, it is demonstrated that adding a thin layer of holey graphene between the electrolyte and the stainless steel current collectors significantly improves the interfacial contact. The ionic conductivity values obtained in the effort were sometimes several times higher than the data measured for SEs without the holey graphene layers. This work calls for more standardized measurement procedures to reduce the discrepancies in reported ionic conductivity values.

Solid state battery↗

Thermally-rearranged polymer blends for gas separation membranes

Polymer blends comprising an ortho-functionalized polyimide homo or copolymer and a polybenzimidazole homo or copolymer, wherein the ortho-functionalized polyimide thermally rearranges to a polymer comprising a phenylene heterocyclic group, such as, polybenzoxazole, polybenzothiazole, polybenzimidazole and/or other heterocyclic structure upon heating. Also disclosed are method of forming a polymer blend comprising dissolving an ortho-functionalized polyimide homo or copolymer and a polybenzimidazole homo or copolymer in a solvent, and optional compatibilizer, to form a polymer solution; contacting a support with the polymer solution; and evaporating the solvent to provide a thin layer comprising the polymer blend on the support. Further, methods of heat treating these polymer blends to thermally rearrange the disclosed polyimides are disclosed, as are the polymer blends prepared thereby. Methods of using these polymer blends to separate gases are also disclosed.

Freeman, Benny D.↗

Ceramic Strain Gages for Use at Temperatures up to 1500 Celsius

Indium-tin-oxide (ITO) thin film strain gages were successfully demonstrated at temperatures beyond 1500 C. High temperature static strain tests revealed that the piezoresistive response and electrical stability of the ceramic sensors depended on the thickness of the ITO films comprising the active strain elements. When 2.5 microns-thick ITO films were employed as the active strain elements, the piezoresistive response became unstable at temperatures above 1225 C. In contrast to this, ceramic sensors prepared with 5 microns-thick ITO were stable beyond 1430 C and sensors prepared with 8 microns-thick ITO survived more than 20 hr of operation at 1481 C. Very thick (10 microns) ITo strain gages were extremely stable and responsive at 1528 C. ESCA depth profiles confirmed that an interfacial reaction between the ITO strain gage and alumina substrate was responsible for the high temperature electrical stability observed. Similar improvements in high temperature stability were achieved by doping the active ITO strain elements with aluminum. Several Sic-Sic CMC constant strain beams were instrumented with ITO strain gages and delivered to NASA for testing. Due to the extreme surface roughness of the CMC substrates, new lithography techniques and surface preparation methods were developed. These techniques relied heavily on a combination of Sic and A12O3 cement layers to provide the necessary surface finish for efficient pattern transfer. Micro-contact printing using soft lithography and PDMS stamps was also used to successfully transfer the thin film strain gage patterns to the resist coated CMC substrates. This latter approach has considerable potential for transferring the thin film strain gage patterns to the extremely rough surfaces associated with the CMC's.

Gregory, Otto↗