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At least 541 records · Page 30

Ultra-power-efficient heterogeneous III–V/Si MOSCAP (de-)interleavers for DWDM optical links

We discuss the design and demonstration of various III–V/Si asymmetric Mach–Zehnder interferometer (AMZI) and ring-assisted AMZI (de-)interleavers operating at O-band wavelengths with 65 GHz channel spacing. The wafer-bonded III–V/Si metal-oxide-semiconductor capacitor (MOSCAP) structure facilitates ultra-low-power phase tuning on a heterogeneous platform that allows for complete monolithic transceiver photonic integration. The second- and third-order MOSCAP AMZI (de-)interleavers exhibit cross-talk (XT) levels down to − 22 dB and − 32 dB with tuning powers of 83.0 nW and 53.0 nW, respectively. The one-, two-, and three-ring-assisted MOSCAP AMZI (de-)interleavers have XT levels down to − 27 dB, − 22 dB, and − 20 dB for tuning powers of 10.0 nW, 7220.0 nW, and 33.6 nW, respectively. The leakage current density is measured to be in the range of 1.6 – 27 μA / cm 2 . To the best of our knowledge, we have demonstrated for the first time, athermal III–V/Si MOSCAP (de-)interleavers with the lowest XT and reconfiguration power consumption on a silicon platform.

Cheung, Stanley (ORCID:0000000248860013)↗

Development of a compact fast-neutron spectrometer for nuclear emergency response applications

We have developed a Compact Fast Neutron Spectrometer (CFNS) for passive assay of special nuclear material (SNM) through the observation of fast neutrons. The CFNS consists of eight organic glass scintillators (OGS) coupled to silicon photomultipliers and a waveform digitizer, which are integrated within a human-portable box. The CFNS determines the neutron energy profile by spectrum unfolding using the Maximum-Likelihood Expectation Maximization method. The detector acquisition system was optimized to have a dynamic range of up to 10 MeV neutron energy. Bulk special nuclear material (SNM) measurements from the National Criticality Experiments Research Center were analyzed for SNM validation/examination. Additionally, the results show that the CFNS can be used to distinguish between fission and (α, n) neutron emitters, regardless of intervening material type (Cu and polyethylene) and thickness, by taking the ratio of neutron counts at different regions in the unfolded energy spectrum. Additionally, by fitting an exponential curve to the unfolded energy spectrum of PuO 2 and Pu neutron emitters, the CFNS showed the ability of distinguishing between pure Pu oxide, pure Pu metal and mixed oxide-metal configurations.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

AOI [1]: Passive Wireless Sensor Systems Fabricated by Direct-Writing for Temperature and Health Monitoring of Energy Systems in Harsh-Environments (Final Report)

Researchers at West Virginia University (WVU) propose to demonstrate a wireless, high-temperature sensor system for monitoring the temperature and health of energy-system components. The active sensor and electronics for wireless communication will be composed entirely of an electroceramic materials (conductive ceramics) which are capable of withstanding the harsh-environments required for fossil energy-based technologies. This work will focus primarily on the fabrication and testing of temperature (thermocouples and thermistors) and health (strain/stress and crack propagation sensors) that function at extreme temperatures (up to 700-1700ºC). The electronics will accompany the high-temperature sensor, which will include a passive wireless communication circuit that allows the transmission of the data based on the LCR resonance principle to a near-by reader antenna. This passive transmission of data will reduce the need for interconnect wires near the active, and possibly rotating, energy-system component. The research will include process development to permit the 2D/3D direct-writing of the entire sensor and communication circuit onto the energy-system component. The direct-writing will be facilitated by using silicon-based polymer-derived precursors to form the high-temperature, stable electroceramic compositions. In addition, methods for direct-writing the circuit onto a fugitive carrier substrate will be completed, which will permit a “peel-and-stick”-like transfer of the sensor circuit to the energy-system component. This feature will allow the economical and precise placement of the sensor circuit onto components of various shapes and locations, without altering the geometry and active features of the manufactured component, or the removal (or decommissioning) of the component for installation. The proposed work will be directed at the following areas: 1) Investigation of phase formation, sintering/grain growth, and electrical properties of polymer-derived electroceramic composites; 2) Definition of processes to direct-write through ink-jet and robo-casting the polymer-derived electroceramic composites onto oxide and polymer surfaces; 3) Development of methods to form monolithic "peel-and-stick" preforms that will efficiently transfer the sensor circuit to ceramic surfaces after thermal treatment; 4) Design of passive wireless LCR circuits and receiver (reader) antennas for communication and testing at high temperatures; 5) Investigation of the passive wireless sensor system developed (and method of transferring sensor system) for temperature and stress/strain measurements on a SOFC repeat unit and a singular gas turbine blade prototype as example applications.

01 COAL, LIGNITE, AND PEAT↗

Grid-to-rod fretting wear study of SiC/SiC composite accident-tolerant fuel claddings using an autoclave fretting bench test

Grid-to-rod-fretting (GTRF) in pressurized water reactors (PWRs) is known to cause wear and surface damage on the fuel claddings, potentially leading to radioactive leakage. One of the accident-tolerant fuel (ATF) concepts is to use advanced cladding materials that could withstand higher temperatures. Here, we investigated the wear behavior of candidate silicon carbide (SiC)-based composite claddings with different levels of surface finish in fretting against a commercial ZIRLO alloy grid using a unique bench-scale autoclave GTRF rig. The experiments mimicked the environment in an industrial full-assembly PWR simulator. Fretting tests were conducted with a realistic load (~0.5 N) in deionized water under a pressure of 20–23 bar at 204 °C for 100 h. While the SiC/SiC composite claddings showed significantly higher wear resistance than the commercial ZIRLO alloy cladding as expected, the smoother versions experienced surprisingly higher wear than the much softer counterface, ZIRLO grid. The wear mechanism of the SiC/SiC cladding was attributed to the SiC wear debris that was trapped at the fretting interface causing both 3-body and 2-body (embedded into the grid surface) abrasion of the cladding. Rougher SiC/SiC claddings had less material loss but caused more wear on the ZIRLO grid. Finally, pre-oxidized ZIRLO grid showed better compatibility with the SiC/SiC cladding to protect both the cladding and grid as a result of reduced wear debris trapping.

36 MATERIALS SCIENCE↗

Rheology improvement for silicon nitride and resin slurries for vat photopolymerization printing and sintering

This work presents the formulation, rheological characterization, and sintering of silicon nitride (Si₃N₄) slurries for vat photopolymerization (VPP) using digital light processing (DLP). Bimodal Si₃N₄ powder was dispersed into commercial photopolymer resin using two different dispersants with opposing effects on surface charge, resulting in varied slurry stability and flow behavior. Slurries were engineered to exhibit shear-thinning behavior suitable for VPP, and their flow properties were quantified using a power-law fluid model. The formulations achieved cure depths of approximately 40 µm and enabled printing of green bodies. Post-processing included thermal debinding and liquid-phase sintering, yielding primarily β-Si₃N₄ with a minor Y-Si-Al-O-N glass phase. The sintered parts reached ~85% of theoretical density and demonstrated a flexural strength of ~330 MPa. Microstructural analysis revealed closed porosity along with some defects related to powder agglomeration and interlayer adhesion. These findings provide insights into slurry formulation strategies for additive manufacturing of high-performance non-oxide ceramics.

Aerospace engineering↗

Evaluating the Effect of Electrolyte Additive Functionalities on NMC622/Si Cell Performance

Unstable electrode/electrolyte interface is the major cause of degradation for silicon (Si)-based anodes for lithium (Li)-ion batteries. Development of functional electrolyte additives can provide a viable path toward stabilizing the dynamic Si/electrolyte interface, which will benefit the development of high energy density Li-ion batteries. Here, we evaluate polymerizable electrolyte additives with varying functional groups (fluorocarbon, thiophosphate, and fluorophosphazene). The additives are examined using LiNi 0.6 Mn 0.2 Co 0.2 O 2 /Si full cells where the cycle performance and impedance are measured. Electrochemical tests show that the fluorine-containing additives provide better passivation at the Si electrode, leading to enhanced full cell performance. Here, among the three additives examined, best electrochemical performance is observed from the fluorocarbon-containing compound, followed by fluorophosphazene- and thiophosphate-containing compounds. Characterization of the solid electrolyte interphase (SEI) on cycled electrodes using Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), and attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) reveal that higher concentration of fluorine and lithium oxide, and lower concentration of carbonate and organic species correlate with enhanced electrochemical performance.

25 ENERGY STORAGE↗

High-bandwidth density silicon photonic resonators for energy-efficient optical interconnects

The growth of artificial intelligence applications demands ever larger and more complex deep learning models, dominating today's—and tomorrow's—data center and high-performance computing systems. While traditional electronics are failing to keep pace with application demands, silicon photonic (SiPh) interconnects have emerged as a necessary technology to support these systems. SiPh-driven wavelength-division multiplexing (WDM) offers a particularly promising path toward supporting incredibly high-aggregate link bandwidth in a compact and efficient form factor. One of the basic building blocks of these integrated WDM interconnects is the SiPh resonator. Their inherent wavelength selectivity and compact footprint allow for efficient data transmission multiplexed across dozens of carrier wavelengths. Used as add-drop (AD) filters, SiPh resonators are critical to constructing integrated tunable wavelength-selective optical circuit switches as well as for demultiplexing the different carrier wavelengths toward independent wavelength-insensitive photodiodes in a dense wavelength-division multiplexing receiver. Resonators in the all-pass (AP) configuration are widespread as well, allowing for wavelength-selective modulation to drive aggregate link bandwidths far beyond the individual channel data rate. Unlike SiPh Mach–Zehnder modulators (MZM), resonant modulators can be driven using low, complementary metal-oxide-semiconductor drive voltages, allowing for tight co-integration between photonic integrated circuits, fabricated with larger process node technologies, and electronic integrated circuits, designed to exploit the advantages of the latest node. To push toward practical peta-scale interconnects, a comprehensive review of SiPh resonators is required, addressing bottlenecks and design constraints at both the architecture and device levels. We first describe the predominant integrated link architectures and identify their limits. We then discuss the device-level design considerations that can be made for both AD and AP configuration resonators to overcome the system level limits with novel resonator device designs. Analytical models and numerical simulation of resonators are validated by experimental measurement of devices fabricated in a commercial 300-mm foundry, showing a clear path toward volume manufacturing. The demonstrated resonant modulators and filters support the feasibility of increasing the aggregate bandwidth of resonator-driven SiPh interconnects into the peta-scale regime.

42 ENGINEERING↗

Development of Stable Solid Oxide Electrolysis Cells for Low-Cost Hydrogen Production

The project objective was to demonstrate a solid oxide cell-based steam electrolysis stack that exhibits robustness, reliability, endurance, hydrogen purity, and produces hydrogen at elevated pressure of 2 to 3 bar. Innovative materials and processing methods were evaluated to improve degradation characteristics. Performance improvement focused on nearly all layers involved in the cell and stack assembly. Primary attention was paid to zirconia-ceria interface resistance control via sintering optimization and decrease in degradation from the oxygen electrode by evaluating low strontium (Sr) or Sr-free composition for both the oxygen electrode and current collection layer. Stack robustness was addressed by validating redox tolerance of fuel electrode, confirming capability of cells to survive repeated thermal cycles, studying the effect of pressure on performance and degradation, evaluating the effect of contamination on fuel and oxygen electrode performance and degradation, and identifying mitigation strategies to improve performance. The characterization included evaluation of electrochemical performance and stability followed by microstructural analysis. At the cell level, performance and stability improvements were achieved by incorporating a Sr-free oxygen electrode and a denser oxygen electrode barrier layer. At the stack level, pressurized operation reduces demand on first stage compression, the redox tolerant fuel electrode mitigates risk from service interruptions, and improvements to interconnect coating alleviate chromium (Cr) contamination effects. The denser barrier layer was achieved by adding a sintering aid to the samaria-doped ceria (SDC) composition that reduced sintering temperature by 150 °C. The resulting density was on par with the baseline SDC barrier layer density and the lower sintering temperature resulted in less resistive phase formation during sintering. Button cell tests did not demonstrate a change in performance when exposed to silicon (Si) or manganese (Mn) impurities to the fuel electrode and Cr impurity to the oxygen electrode. More detailed study however is warranted. The project addressed SOEC performance and stability at the cell and stack levels through a systematic approach to known sources of degradation that were combined and tested in three stack tests using an electrolyte supported cell design to allow for evaluation of a variety of fuel and oxygen electrode compositions. STK-82 and STK-83 had identical compositions. STK-100 incorporated the best materials and processing variables developed under this and concurrent projects, and was tested at elevated pressure in steam electrolysis. • STK-82 recovered performance after redox and thermal cycling, demonstrating the robustness of the stack and seals. It exhibited stable performance in testing for 500 hours in SOEC mode, followed by 300 hours of cycling between SOEC and SOFC tests. Degradation during SOEC operation was 1.8 %/ 1,000 hours. • STK-83 generated hydrogen at >80% steam conversion, and oxygen above 98.5 % purity during pressurized operation. Both hydrogen and oxygen were generated at 3 barg pressure without the use of a pressure vessel. In addition to balanced pressure, electrolysis operation at 1 bar differential pressure across anode and cathode was also demonstrated to substantial the robustness of the cell and seal. • STK-100 measured at initial ambient pressure conditions showed an area specific resistance of 1.1 ohm-cm 2 , and STK-83 had 1.3 ohm-cm 2 .

08 HYDROGEN↗

High-performance ammonia oxidation catalysts for anion-exchange membrane direct ammonia fuel cells

Low-temperature direct ammonia fuel cells (DAFCs) use carbon-neutral ammonia as a fuel, which has attracted increasing attention recently due to ammonia's low source-to-tank energy cost, easy transport and storage, and wide availability. However, current DAFC technologies are greatly limited by the kinetically sluggish ammonia oxidation reaction (AOR) at the anode. Herein, we report an AOR catalyst, in which ternary PtIrZn nanoparticles with an average size of 2.3 ± 0.2 nm were highly dispersed on a binary composite support comprising cerium oxide (CeO 2 ) and zeolitic imidazolate framework-8 (ZIF-8)-derived carbon (PtIrZn/CeO 2 -ZIF-8) through a sonochemical-assisted synthesis method. Additionally, the PtIrZn alloy, with the aid of abundant OH ad provided by CeO 2 and uniform particle dispersibility contributed by porous ZIF-8 carbon (surface area: ~600 m 2 g -1 ), has shown highly efficient catalytic activity for the AOR in alkaline media, superior to that of commercial PtIr/C. The rotating disk electrode (RDE) results indicate a lower onset potential (0.35 vs. 0.43 V), relative to the reversible hydrogen electrode at room temperature, and a decreased activation energy (~36.7 vs. 50.8 kJ mol -1 ) relative to the PtIr/C catalyst. Notably, the PtIrZn/CeO 2 -ZIF-8 catalyst was assembled with a high-performance hydroxide anion-exchange membrane to fabricate an alkaline DAFC, reaching a peak power density of 91 mW cm -2 . Unlike in aqueous electrolytes, supports play a critical role in improving uniform ionomer distribution and mass transport in the anode. PtIrZn nanoparticles on silicon dioxide (SiO 2 ) integrated with carboxyl-functionalized carbon nanotubes (CNT–COOH) were further studied as the anode in a DAFC. A significantly enhanced peak power density of 314 mW cm -2 was achieved. Density functional theory calculations elucidated that Zn atoms in the PtIr alloy can reduce the theoretical limiting potential of *NH 2 dehydrogenation to *NH by ~0.1 V, which can be attributed to a Zn-modulated upshift of the Pt–Ir d-band that facilitates the N–H bond breakage.

25 ENERGY STORAGE↗

Understanding EBC Lifetimes and Performance for Industrial Gas Turbines

Hydrogen or hydrogen blend fuels are expected to replace natural gas in land-based industrial gas turbines (IGTs) to support a greener power economy. Silicon carbide (SiC) base ceramic matrix composites (CMCs) are considered for replacement of Ni-based superalloys to facilitate future efficiency improvements. SiC CMCs require environmental barrier coatings (EBCs) to mitigate volatilization from high-temperature steam, thus making the EBC lifetime critical information for identifying CMC component lifetimes. The goal of this project is to determine the maximum bond coating temperature underneath the EBC for achieving an IGT component lifetime goal of 25,000 h, which is far greater than current CMC component lifetime requirements for aero-turbine applications. To provide data for the lifetime model, laboratory testing used plasma-sprayed rare-earth silicate EBCs on monolithic SiC substrates with an intermediate Si bond coating. Specimens exposed to 1-h thermal cycles in flowing air-steam environments and reaction kinetics were assessed from 700°-1350°C by measuring the thickness of the thermally grown silica scales. The silica growth and phase transformation appear critical in predicting EBC lifetime and several strategies have been explored to reduce the oxide growth rate and improve EBC durability at elevated temperatures. Advanced characterization using Raman spectroscopy has helped clarify this system.

Ridley, Mackenzie↗

Understanding Environmental Barrier Coating Lifetimes and Performance for Industrial Gas Turbines

Hydrogen or hydrogen blend fuels are expected to replace natural gas in land-based industrial gas turbines (IGTs) to support a greener power economy. Silicon carbide (SiC) base ceramic matrix composites (CMCs) are considered for replacement of Ni-based superalloys to facilitate future efficiency improvements. SiC CMCs require environmental barrier coatings (EBCs) to mitigate volatilization from high-temperature steam, thus making the EBC lifetime critical information for identifying CMC component lifetimes. Here, the goal of this project is to determine the maximum bond coating temperature underneath the EBC for achieving an IGT component lifetime goal of 25,000 h, which is far greater than current CMC component lifetime requirements for aeroturbine applications. To provide data for the lifetime model, laboratory testing used atmospheric plasma-sprayed rare-earth silicate EBCs on monolithic SiC substrates with an intermediate Si bond coating. Specimens exposed to 1-h thermal cycles in flowing air–steam environments and reaction kinetics were assessed from 700 °C to 1350 °C by measuring the thickness of the thermally grown silica scales. The silica growth and phase transformation appear critical in predicting EBC lifetime and several strategies have been explored to reduce the oxide growth rate and improve EBC durability at elevated temperatures. Advanced characterization using Raman spectroscopy has helped clarify this system.

08 HYDROGEN↗

Direct Transformation of SiH 4 to a Molecular L(H) 2 Co=Si=Co(H) 2 L Silicide Complex

The synthesis of bimetallic molecular silicide complexes is reported, based on the use of multiple Si–H bond activations in SiH 4 at the metal centers of 14-electron LCo I fragments (L = Tp", HB(3,5-diisopropylpyrazolyl) 3 – ; [BP 2 tBu Pz], PhB(CH 2 P t Bu 2 ) 2 (pyrazolyl)). Upon exposure of (Tp"Co) 2 (μ-N 2 ) (1) to SiH 4 , a mixture of (Tp"Co) 2 (μ-H) (2) and (Tp"Co) 2 (μ-H) 2 (3) was formed and no evidence for Si–H oxidative addition products was observed. In contrast, [BP 2 tBu Pz]-supported Co complexes led to Si–H oxidative additions with the generation of silylene and silicide complexes as products. Notably, the reaction of ([BP 2 tBu Pz]Co) 2 (μ-N 2 ) (5) with SiH 4 gave the dicobalt silicide complex [BP 2 tBu Pz](H) 2 Co=Si=Co(H) 2 [BP 2 tBu Pz] (8) in high yield, representing the first direct route to a symmetrical bimetallic silicide. Here, the effect of the [BP 2 tBu Pz] ligand on Co–Si bonding in 7 and 8 was explored by analysis of solid-state molecular structures and density functional theory (DFT) investigations. Upon exposure to CO or DMAP (DMAP = 4-dimethylaminopyridine), 8 converted to the corresponding [BP 2 tBu Pz]Co(L) x adducts (L = CO, x = 2; L = DMAP, x = 1) with concomitant loss of SiH 4 , despite the lack of significant Si–H interactions in the starting complex. On heating to 60 °C, 8 underwent reaction with MeCl to produce small quantities of Me x SiH 4–x (x = 1–3), demonstrating functionalization of the μ-silicon atom in a molecular silicide to form organosilanes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Evaluation of XCT for Matrix Density Measurement of Particle Fuel Forms

Particle fuel forms generally consist of a dispersion of fuel, such as tristructural isotropic (TRISO) particles, within a refractory matrix (e.g., graphite or silicon carbide). The density of matrix materials for particle fuel forms is of interest for modeling fuel form strength and thermal properties and may be specified as a quality control parameter, depending on reactor design. Some of the uncertainty associated with traditional, manual approaches can be eliminated by performing x-ray computed tomography (XCT) on the fuel forms and applying image processing methods to generate a precise count of the number of particles. This also removes the need to include determination of particle count within each individual fuel form during fabrication. Unfortunately, reconstruction artifacts from high-Z uranium-bearing kernels prevent accurate measurement of individual particle volumes using this approach, so the use of mean particle mass and volume are still necessary for computation of average fuel form matrix density. This method of using XCT to count particles in individual fuel form for determination of average matrix density was applied to three archived compacts from the Advanced Gas Reactor Fuel Development and Qualification (AGR)-1 campaign, four archived compacts with uranium carbide/uranium oxide (UCO) TRISO from the AGR-2 campaign, and three archived UO 2 -TRISO compacts from the AGR-2 campaign. The resulting density values were compared with those previously reported, showing slight changes due to uncertainties in the previously used number of particles in each of these cylindrical, graphite matrix compacts.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Tribological behavior of spark plasma sintered Ti 3 SiC 2 MAX phase composites

Ti₃SiC₂ MAX phases are considered promising candidates for tribological applications; but, their low hardness (5-6 GPa) can lead to increased abrasive wear and higher wear rates. This study investigates the effect of incorporating hard SiC particles on microstructure, mechanical, and tribological behavior of Ti₃SiC₂-SiC-based MAX phase composites prepared using spark plasma sintering at 1400 °C, 40 MPa, 15-minute holding time. Phase and microstructural characterization of composites confirmed the formation of Ti₃SiC₂ MAX phase (90%) along with TiC as a minor phase (10%). For Ti₃SiC₂-SiC, homogeneous distribution of SiC grains within Ti₃SiC₂ matrix resulted in increased hardness from ~11.6 GPa to ~14.8 GPa; however, the flexural strength decreased from ~615 MPa to ~597 MPa due to coefficient of thermal expansion mismatch. Tribological behavior of Ti₃SiC₂-SiC MAX phase composites was assessed using unidirectional sliding ball-on-flat tests with a 52100 steel ball at different loads and a constant speed of 0.05 m/s. SiC reinforced composites exhibited a decreased friction coefficient from 0.39 to 0.29 and wear rates comparable to Ti₃SiC₂ (7-10×10⁻³ mm³/N·m). SEM and EDS analysis of the worn surfaces indicated material transfer from the steel ball counter body and its oxidation due to frictional heating, at lower loads (2N and 5N), whereas at higher load (10N), fracture of the transfer layer dominated, with the presence of microcracks, delamination, grain pull-outs, and wear debris. Improved mechanical properties and good adhesion of SiC with Ti₃SiC₂ matrix resulted in reduced microcracks and grain pull-outs, making Ti₃SiC₂-SiC/Steel tribo-pair more suitable for tribological applications.

36 MATERIALS SCIENCE↗

Energetic Tug-of-War between Pt and Leaky TiO 2 : Positive and Negative Effects on the Function of Molecularly-Modified p -Si(111)|TiO 2 |Pt Photocathodes

Photoelectrochemical solar energy conversion to chemical products is a promising avenue towards renewable fuels, and TiO 2 deposition on semiconductor photocathodes is a widespread surface protection strategy. However, the electronic, thermodynamic, and kinetic effects of protection layers on interfacial energetics remains poorly understood. Here, electrochemical data (photocurrent onset and flatband potentials) of p-Si(111)|TiO 2 |Pt is collected in contact with an outer-sphere redox couple. We find that onset potentials shift negatively as a function of increasing oxide thickness, but this effect is not reflected in the flatband potentials. This reveals the mechanism of these shifts is kinetic rather than thermodynamic,and suggests that hole leakage through the TiO 2 is responsible. When Pt nanoparticles are deposited onto the TiO 2 , positive shifts in both the onset and flatband potentials are observed, revealing Pt catalysts are beneficial for more than just increased catalytic rates. These results highlight the importance of understanding the effects of surface modifications on the energetics at the interface in both catalytic and simple electron transfer systems.

14 SOLAR ENERGY↗

In-situ hydrogen microstructural characterization of Si heterojunction passivation: Addressing V OC degradation and mitigation pathways

Si heterojunction (SHJ) solar cells have demonstrated record efficiency >27%, approaching the theoretical limit of ≈ 29%, primarily due to best surface/interface defect passivation provided by deposited thin layers of hydrogenated amorphous silicon (a-Si:H). Such excellent surface/interface passivation reduces recombination loss and result in >100 mV improvement of cell open circuit voltage (V OC ) to ≈ 750 mV, thus the cell efficiency. However, fielded SHJ modules exhibit loss of V OC and hence efficiency over time in years, presumably due to degradation related to a-Si:H layers. This adversely affects the technology’s market acceptance, and levelized cost of energy (LCOE). It is hypothesized that the origin of a-Si:H degradation is somehow related to the presence of weak Si–Si bonds and hydrogen in a-Si:H films. The objective of this project is to test this hypothesis by directly measuring chemical and structural changes occurring within SHJ component layers and solar cells. This is achieved by developing an innovative in-situ Fourier transform infrared (FTIR) spectrometry apparatus to monitor hydrogen microstructural changes occurring within amorphous silicon and decipher hydrogen evolution kinetics over time when samples are exposed to heat and/or light stress. These in-situ measured hydrogen microstructural changes are correlated to the changes in effective minority carrier lifetime (τ eff ), implied V OC (iV OC ), surface recombination velocity (S), and cell V OC . These mechanistic understandings will provide critical guidance to mitigate the V OC -driven degradation of SHJ solar cell performance. Passivation optimization and degradation analysis of individual SHJ component structures were achieved through systematic deposition of three symmetric structures and the completed SHJ solar cell structure. The three symmetric structures used were intrinsic a-Si:H [(i)a-Si:H] layers in a bilayer structure, intrinsic and p-type doped stacked layers [(i-p)a-Si:H] representing the front heterojunction in the SHJ cell, and intrinsic and n-typed doped stacked layers [(i-n)a-Si:H] representing the back-side back surface field (BSF) in the SHJ cell. State-of-the-art passivation qualities are demonstrated by a champion iV OC of 740 mV for the (i)a-Si:H layers, and the (i-n)a-Si:H symmetric structure. A 725 mV iV OC is observed for the (i-p)a-Si:H symmetric structure. These symmetric passivated SHJ component structures were subsequently subjected to different accelerated lifetime (ALT) stressors to identify which conditions contribute the most to iV OC degradation. Degradation of the thin (10 nm) (i)a-Si:H passivation layers without any additional overlying layers is minimal; complexity of this study arises due to unavoidable surface oxidation of (i)a-Si:H layer during most of the stress application, which is likely irrelevant for a full SHJ cell configuration with overlying protective layers. The iV OC degradation of symmetric structures is found to occur primarily at the (i-p)a-Si:H passivation stack under dark heat stress with associated hydrogen loss from the (p)a-Si:H layer. An activation energy for increase in S (defect creation) of 0.65 eV can be correlated to the activation energy of ≈ 0.4 eV for hydrogen loss from the (i-p)a-Si:H stack. This also suggests the presence of weakly bonded hydrogen in the (p)a-Si:H films, which effuses out of the film stack at such low activation energy. When light and heat stress are applied together, similar hydrogen loss from (i-p)a-Si:H stack is observed, however, does not appreciably degrade iV OC or increase S. This is an important result and departure from direct correlation between hydrogen loss and defect creation. This perhaps indicates additional defect chemistries or annealing that might be occurring in the presence of light requiring further detailed defect measurements. The full SHJ cell structure used for this project is depicted in Fig.1(d). SHJ cells with an initial V OC ≈ 700 mV were fabricated and subjected to similar ALT stress conditions. Cell V OC is found to degrade the most under dark heat stress and is confirmed by observed hydrogen migration out of the (i-p)a-Si:H stack. However, hydrogen cannot escape from the cell stack, it accumulates near the (p)a-Si:H/ITO contact interface, where ITO acts as a barrier preventing hydrogen loss. Furthermore, light-heat combined stress does not degrade V OC appreciably, confirming the occurrence of a defect annealing process.

14 SOLAR ENERGY↗

Thermal shock resistance of multilayer silicon carbide receiver tubes for 800°C molten salt concentrating solar power application

CSP power tower receiver systems during rapid transient weather periods can be vulnerable to thermal shock conditions from rain that which can facilitate the onset of leaks and failures that can have catastrophic consequences. Silicon carbide (SiC) materials have attractive receiver application characteristics for being light weight, having high-strength and excellent thermal shock resistance performance which make them a particularly good fit for receiver absorber materials in CSP. In this investigation, the performance characteristics of Ceramic Tubular Products (CTP) SiC ceramic matrix composite (CMC), multilayered tubes were explored with respect to thermal shock performance for solar receiver applications in next generation CSP plants. Here, thermal shock testing was performed at the Sandia National Laboratories (SNL) Solar Furnace facility using a dynamic stage and thermal shock tube test setup. The tubes tested under incident solar heat flux of 100 W/cm2 were heated with inner tube temperatures reaching approximately 800 °C, with outer temperatures exceeding or just reaching 1000 El for the multilayer and monolithic SiC tubes respectively. The tubes were then quenched with simulated rain. The tubes were then cooled and subjected to hoop stress analysis using an Instron device to assess their subsequent mechanical strength. Furthermore, the on-sun study experimental results indicate an average of 24.2% and 97% higher hoop strength for the CMC tubes than those composed of monolithic SiC and aluminum oxide (A1203) respectively.

14 SOLAR ENERGY↗

Pool Boiling Reliability Tests and Degradation Mechanisms of Microporous Copper Inverse Opal (CuIOs) Structures

The rising power density in electronic systems requires thermal management solutions that are both high-performing and reliable. Porous materials such as Copper Inverse Opal (CuIOs) have unique structural features, including high permeability and high thermal conductivity, to enhance pool boiling performance. However, there is little understanding of the degradation mechanism of such porous materials under pool boiling conditions. In this study, samples of 10 ..mu..m thick CuIOs with 4.8 ..mu..m diameter, covering silicon substrate of area 11 mm x 11 mm, with various heated areas ranging from 2.5 mm x 2.5 mm to 10 mm x 10 mm, were tested in 100 degrees C deionized water at a constant heat flux of 110 Wcm -2 for 3-to-7 days. The combined effect of erosion and corrosion caused structural degradation of the CuIOs. The directly heated area had the most severe degradation while the edge of the heater and the unheated area showed progressively less degradation, maintaining some CuIOs structure even after the 7-day reliability test. Among all the tested samples with various heater sizes, the 2.5 mm x 2.5 mm heater sample - in which the heater size was designed to be comparable to the water bubble characteristic length - had the largest critical heat flux (CHF) up to 300 Wcm -2 with a superheat ~ 13 degrees C. Additionally, CuIOs with a smaller heated area performed better in terms of reliability. This study offers preliminary insights into CuIOs degradation mechanisms, contributing to the development of more robust thermal management solutions. We expect that electroless plating of CuIOs with gold (Au), nickel (Ni), and atomic layer deposition (ALD) aluminum oxide (Al 2 O 3 ) in combination with appropriate application-specific coolants will further improve the reliability and lifetime of the CuIOs.

boiling-induced degradation↗