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At least 739 records · Page 41

Note: Expanding the bandwidth of the ultra-low current amplifier using an artificial negative capacitor

The bandwidth and low noise characteristics are often contradictory in ultra-low current amplifier, because an inevitable parasitic capacitance is paralleled with the high value feedback resistor. In order to expand the amplifier’s bandwidth, a novel approach was proposed by introducing an artificial negative capacitor to cancel the parasitic capacitance. The theory of the negative capacitance and the performance of the improved amplifier circuit with the negative capacitor are presented in this manuscript. The test was conducted by modifying an ultra-low current amplifier with a trans-impedance gain of 50 GΩ. The results show that the maximum bandwidth was expanded from 18.7 Hz to 3.3 kHz with more than 150 times of increase when the parasitic capacitance (∼0.17 pF) was cancelled. Meanwhile, the rise time decreased from 18.7 ms to 0.26 ms with no overshot. Any desired bandwidth or rise time within these ranges can be obtained by adjusting the ratio of cancellation of the parasitic and negative capacitance. This approach is especially suitable for the demand of rapid response to weak current, such as transient ion-beam detector, mass spectrometry analysis, and fast scanning microscope.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

On the theory of electric double layer with explicit account of a polarizable co-solvent

We present a continuation of our theoretical research into the influence of co-solvent polarizability on a differential capacitance of the electric double layer. We formulate a modified Poisson-Boltzmann theory, using the formalism of density functional approach on the level of local density approximation taking into account the electrostatic interactions of ions and co-solvent molecules as well as their excluded volume. We derive the modified Poisson-Boltzmann equation, considering the three-component symmetric lattice gas model as a reference system and minimizing the grand thermodynamic potential with respect to the electrostatic potential. We apply present modified Poisson-Boltzmann equation to the electric double layer theory, showing that accounting for the excluded volume of co-solvent molecules and ions slightly changes the main result of our previous simplified theory. Namely, in the case of small co-solvent polarizability with its increase under the enough small surface potentials of electrode, the differential capacitance undergoes the significant growth. Oppositely, when the surface potential exceeds some threshold value (which is slightly smaller than the saturation potential), the increase in the co-solvent polarizability results in a differential capacitance decrease. However, when the co-solvent polarizability exceeds some threshold value, its increase generates a considerable enhancement of the differential capacitance in a wide range of surface potentials. We demonstrate that two qualitatively different behaviors of the differential capacitance are related to the depletion and adsorption of co-solvent molecules at the charged electrode. We show that an additive of the strongly polarizable co-solvent to an electrolyte solution can shift significantly the saturation potential in two qualitatively different manners. Namely, a small additive of strongly polarizable co-solvent results in a shift of saturation potential to higher surface potentials. On the contrary, a sufficiently large additive of co-solvent shifts the saturation potential to lower surface potentials. We obtain that an increase in the co-solvent polarizability makes the electrostatic potential profile longer-ranged. However, increase in the co-solvent concentration in the bulk leads to non-monotonic behavior of the electrostatic potential profile. An increase in the co-solvent concentration in the bulk at its sufficiently small values makes the electrostatic potential profile longer-ranged. Oppositely, when the co-solvent concentration in the bulk exceeds some threshold value, its further increase leads to decrease in electrostatic potential at all distances from the electrode.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Design and development of line type modulators for high impedance electron gun

Conventional line type modulators are routinely used for powering pulsed power microwave devices such as magnetrons and klystrons used for radar, medical and scientific applications. The load impedance (operating point) is fairly well defined in these cases, and makes the design of the discharging circuit of the modulator straight forward. This paper describes the Line type modulators that have been developed and being routinely used for powering the Triode Electron Gun of industrial electron linacs. The beam parameters of such guns are user defined and the pulse current varies from few mA to 800mA (typ). The beam energies requirement varies from 40 keV to 80 keV. Hence the impedance offered by the electron gun to the power source (modulator) is not well defined. The load capacitance which is inclusive of the various stray capacitances along with the intrinsic gun capacitance is ∼ 200-400 pF. This capacitance, which depends on the configuration, shunts the load and makes the effective load highly capacitive with the resistive part varying over a wide range. The paper describes the design and development of conventional line type modulators for powering Electron gun load of the type described above. (author)

43 PARTICLE ACCELERATORS↗

Hybrid Graphene Ribbon/Carbon Electrodes for High‐Performance Energy Storage

Abstract The utility of supercapacitors for both fixed and portable energy storage would be greatly enhanced if their energy density could be increased while maintaining their high power density, fast charging time, and low cost. This study describes a simple, solution‐phase, scalable modification of carbon materials by a covalently bonded “brush” of hydrogen‐terminated graphene ribbons (GRs) with layer thicknesses of 2–20 nm, resulting in a 20–100 times increase in the areal capacitance of the unmodified electrode surface. On a flat sp 2 carbon surface modified by GRs, the capacitance exceeds 1200 µF cm −2 in 0.1 m H 2 SO 4 due to a distinct type of pseudocapacitance during constant current charge/discharge cycling. Modification of high surface area carbon black electrodes with GRs yields capacitances of 950–1890 F g −1 , power densities >40 W g −1 , and minimal change in capacitance during 1500 charge/discharge cycles at 20 A g −1 . A capacitance of 1890 F g −1 affords an energy density of 318 Wh kg −1 operating at 1.1 V and 590 Wh kg −1 at 1.5 V. The projected energy density of a hybrid GR/carbon supercapacitor greatly exceeds the current 10 Wh kg −1 for commercial supercapacitors and approaches that of lithium ion batteries.

Farquhar, Anna K.↗

Fabrication of ultrafine manganese oxide-decorated carbon nanofibers for high-performance electrochemical capacitors

Ultrafine manganese oxide-decorated carbon nanofibers (MnOn-CNF) as a new type of electrode materials are facilely fabricated by direct conversion of Mn, Zn-trimesic acid (H3BTC) metal organic framework fibers (Mn-ZnBTC). The construction and evolution of Mn-ZnBTC precursors are investigated by SEM and in situ high-energy XRD. The manganese oxides are highly dispersed onto the porous carbon nanofibers formed simultaneously, verified by TEM, X-ray absorption fine structure (XAFS), Raman, ICP-AES and N2 adsorption techniques. As expected, the resulting MnOn-CNF composites are highly stable, and can be cycled up to 5000 times with a high capacitance retention ratio of 98% in electrochemical capacitor measurements. They show a high capacitance of up to 179 F g–1 per mass of the composite electrode, and a remarkable capacitance of up to 18290 F g–1 per active mass of the manganese(IV) oxide, significantly exceeding the theoretical specific capacitance of manganese(IV) oxide (1370 F g–1). The maximum energy density is up to 19.7 Wh kg–1 at the current density of 0.25 A g–1, even orders higher than those of reported electric double-layer capacitors and pseudocapacitors. The excellent capacitive performance can be ascribed to the joint effect of easy accessibility, high porosity, tight contact and superior conductivity integrated in final MnOn-CNF composites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Liquid crystalline phase synthesis of nanoporous MnO{sub 2} thin film arrays as an electrode material for electrochemical capacitors

Graphical abstract: Three-dimensional (3D) MnO{sub 2} thin film arrays with nanoporous structure is electrodeposited on Ti foil from hexagonal lyotropic liquid crystalline phase. Low-angle X-ray diffraction (XRD), wide-angle XRD, field emission scanning electron microscopy (FESEM), and transmission electron microscopy (TEM) are employed to study the morphology and the structure of the as-synthesized MnO{sub 2} materials. Galvanostatic charge/discharge measurements show the nanoporous, 3D electrode material exhibits excellent capacitive performance between the potential range of −0.1 to 0.9 V, and a maximum specific capacitance as high as 462 F g{sup −1} are achieved in 0.5 M Na{sub 2}SO{sub 4} solution at a charge/discharge current density of 4 A g{sup −1}. Highlights: ► 3D MnO{sub 2} thin film arrays with nanoporous structure is fabricated for the first time. ► A maximum specific capacitance as high as 462 F g{sup −1} is obtained. ► The 3D and nanoporous superarchitecture facilitate electrolyte penetration. -- Abstract: Three-dimensional (3D) MnO{sub 2} thin film arrays with nanoporous structure is electrodeposited on Ti foil from hexagonal lyotropic liquid crystalline phase. Low-angle X-ray diffraction (XRD), wide-angle XRD, field emission scanning electron microscopy (FESEM), and transmission electron microscopy (TEM) are employed to study the morphology and the structure of the as-synthesized MnO{sub 2} materials. Galvanostatic charge/discharge measurements show the nanoporous, 3D electrode material exhibits excellent capacitive performance between the potential range of −0.1 to 0.9 V, and a maximum specific capacitance as high as 462 F g{sup −1} are achieved in 0.5 M Na{sub 2}SO{sub 4} solution at a charge/discharge current density of 4 A g{sup −1}.

36 MATERIALS SCIENCE↗

Supercapacitive properties of hydrothermally synthesized sphere like MoS{sub 2} nanostructures

Highlights: • MoS{sub 2} nanostructures were synthesized by hydrothermal method. • Randomly stacked MoS{sub 2} was obtained. • FE-SEM studies show the sphere like morphology of MoS{sub 2}. • Specific capacitance of 92.85 F/g was achieved using charge–discharge analysis. • MoS{sub 2} electrode shows capacitance retention of about 93.8% after 1000 cycles. - Abstract: In this communication, we have investigated the supercapacitive behaviour of MoS{sub 2} nanostructures prepared by a facile one-pot hydrothermal approach using ammonium heptamolybdate and thiourea as starting materials. The X-ray diffraction study revealed the formation of randomly stacked layers of MoS{sub 2}. The field-emission scanning electron microscope studies suggested the formation of sphere like MoS{sub 2} nanostructures and a plausible mechanism for the formation of the obtained structure is discussed. The cyclic voltammetry study shows the typical rectangular shaped curves with a specific capacitance of 106 F/g at a scan rate of 5 mV/s. Galvanostatic charge–discharge measurements suggested the maximum specific capacitance of about 92.85 F/g at discharge current density of 0.5 mA/cm{sup 2}. Cyclic stability tests revealed the capacitance retention of about 93.8% after 1000 cycles suggesting a good cyclic capacity of the prepared MoS{sub 2}. The electrochemical impedance spectroscopic results such as Nyquist and Bode phase angle plots suggested that the hydrothermally synthesized MoS{sub 2} nanostructures will be a suitable candidate for electrochemical supercapacitor applications.

36 MATERIALS SCIENCE↗

Interplay between Ion Transport, Applied Bias, and Degradation under Illumination in Hybrid Perovskite p-i-n Devices

In this work, we studied ion transport in hybrid organic–inorganic perovskite p-i-n devices as a function of applied bias under device operating conditions. Using electrochemical impedance spectroscopy (EIS) and equivalent circuit modeling, we elucidated various resistive and capacitive elements in the device. We show that ion migration is predictably influenced by a low applied forward bias, characterized by an increased capacitance at the hole-transporting (HTM) and electron-transporting material (ETM) interfaces, as well as in bulk. However, unlike observations in n-i-p devices, we found that there is a capacitive discharge leading to ion redistribution in the bulk at high forward biases. Furthermore, we show that a chemical double-layer capacitance buildup as a result of ion accumulation impacts the electronic properties of the device, likely by inducing either charge pinning or charge screening, depending on the direction of the ion-induced field. Finally, we extrapolate ion diffusion coefficients (~10 –7 cm 2 s –1 ) and ionic conductivities (~10 –7 S cm –1 ) from the Warburg mass (ion) diffusion response and show that, as the device degrades, there is an overall depletion of capacitive effects coupled with increased ion mobility.

36 MATERIALS SCIENCE↗

Understanding the MXene Pseudocapacitance

MXenes have attracted great attention as next-generation capacitive energy-storage materials, but the mechanisms underlying their pseudocapacitive behavior are not well understood. Here we provide a theoretical description of the surface redox process of Ti3C2Tx (T = O, OH), a prototypical MXene, in 1 M H2SO4 electrolyte, based on joint density functional theory with an implicit solvation model and the analysis of Gibbs free energy under a constant-electrode potential. From the dependence of the O/OH ratio (or the surface H coverage) and the surface charge on the applied potential, we obtain a clear picture of the capacitive energy-storage mechanism of Ti3C2Tx that shows good agreement with previous experimental findings in terms of the integral capacitance and Ti valence change. We find a voltage-dependent redox/double-layer co-charging behavior: the capacitive mechanism is dominated by the redox process, but the electric double-layer charge works against the redox process. This new insight may be useful in improving the capacitance of MXenes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Self-Assembly of Monodisperse Starburst Carbon Spheres into Hierarchically Organized Nanostructured Supercapacitor Electrodes

We report a three-dimensional (3D) porous carbon electrode containing both nanoscale and microscale porosity, which has been hierarchically organized to provide efficient ion and electron transport. The electrode organization is provided via the colloidal self-assembly of monodisperse starburst carbon spheres (MSCSs). The periodic close-packing of the MSCSs provides continuous pores inside the 3D structure that facilitate ion and electron transport (electrode electrical conductivity ~0.35 S m –1 ), and the internal meso- and micropores of the MSCS provide a good specific capacitance. Here, the capacitance of the 3D-ordered porous MSCS electrode is ~58 F g –1 at 0.58 A g –1 , 48% larger than that of disordered MSCS electrode at the same rate. At 1 A g –1 the capacitance of the ordered electrode is 57 F g –1 (95% of the 0.24 A g –1 value), which is 64% greater than the capacitance of the disordered electrode at the same rate. The ordered electrode preserves 95% of its initial capacitance after 4000 charging/discharging cycles.

25 ENERGY STORAGE↗

Pseudocapacitive Storage in Nanolayered Ti 2 NT x MXene Using Mg-Ion Electrolyte

Electrochemical supercapacitors are hybrids of a capacitor and battery that rely on materials capable of storing charges via pseudocapacitive reactions in addition to conventional electrostatic double-layer charge storage. MXenes, a relatively new class of two-dimensional (2D) transition metal carbides and nitrides, are ideal candidates for supercapacitors due to their high electronic conductivity, high surface area, and ability to store charges via pseudocapacitive mechanisms. Nitride MXenes such as Ti 2 NT x are predicted to have higher pseudocapacitance than carbide MXenes but have not been explored experimentally. Here, we report on the synthesis, characterization, and pseudocapacitive charge storage mechanism in the Ti 2 NT x nitride MXene. Successful formation of nanolayered Ti 2 NT x MXene is characterized by XRD, SEM, and N 2 physisorption analyses. The identity of the surface terminating groups T x are assigned to primarily O and/or OH based on Raman, FTIR, and STEM-EELS. When tested in various electrolytes, the nanolayered Ti 2 NT x MXene exhibits pronounced reversible redox peaks and high areal capacitances (~1350 uF cm -2 in 1 M MgSO 4 aqueous electrolyte) well exceeding that expected from a double-layer charge storage (~50 uF cm -2 ) showing that charge is stored in the Ti 2 NT x MXene via a pseudocapacitive mechanism. We report a trend in the capacitance as a function of cation as follows: Mg 2+ > Al 3+ > H + > Li + > Na + > K + , that matches theoretical predictions. Remarkably, nanolayered Ti 2 NT x MXene exhibits >200 F g -1 capacitance over a 1.0 V range in the Mg-ion electrolyte, and the capacitance increases to 160% of its initial value after 1000 cycles owing to the 2 e - process and the distinctive multilayer adsorption characteristic of the Mg 2+ cation on the Ti 2 NT x MXene. Furthermore, these findings identify Ti 2 NT x MXene as a new pseudocapacitive material that possesses high capacitance and wide working voltage in a safe and environmentally friendly Mg-ion electrolyte.

2D MXene↗

Unrivaled combination of surface area and pore volume in micelle-templated carbon for supercapacitor energy storage

Here, we created Immense Surface Area Carbons (ISACs) by a novel heat treatment that stabilized the micelle structure in a biological based precursor prior to high temperature combined activation – pyrolysis. While displaying a morphology akin to that of commercial activated carbon, ISACs contain an unparalleled combination of electrochemically active surface area and pore volume (up to 4051 m 2 g –1 , total pore volume 2.60 cm 3 g –1 , 76% small mesopores). The carbons also possess the benefit of being quite pure (combined O and N: 2.6–4.1 at%), thus allowing for a capacitive response that is primarily EDLC. Tested at commercial mass loadings (~10 mg cm –2 ) ISACs demonstrate exceptional specific capacitance values throughout the entire relevant current density regime, with superior rate capability primarily due to the large fraction of mesopores. In the optimized ISAC, the specific capacitance ( C g ) is 540 F g –1 at 0.2 A g –1 , 409 F g –1 at 1 A g –1 and 226 F g –1 at a very high current density of 300 A g –1 (~0.15 second charge time). At intermediate and high currents, such capacitance values have not been previously reported for any carbon. Tested with a stable 1.8 V window in a 1 M Li 2 SO 4 electrolyte, a symmetric supercapacitor cell yields a flat energy–power profile that is fully competitive with those of organic electrolyte systems: 29 W h kg –1 at 442 W kg –1 and 17 W h kg –1 at 3940 W kg –1 . The cyclability of symmetric ISAC cells is also exceptional due to the minimization of faradaic reactions on the carbon surface, with 80% capacitance retention over 100 000 cycles in 1 M Li 2 SO 4 and 75 000 cycles in 6 M KOH.

25 ENERGY STORAGE↗

Si:SrTiO 3 -Al 2 O 3 -Si:SrTiO 3 multi-dielectric architecture for metal-insulator-metal capacitor applications

We present that metal-insulator-metal (MIM) capacitors comprised of amorphous Si:SrTiO 3 -Al 2 O 3 -Si:SrTiO 3 multi-dielectric architecture have been fabricated employing a combination of pulsed laser and atomic layer deposition techniques. The voltage linearity, temperature coefficients of capacitance, dielectric and electrical properties upon thickness were studied under a wide range of temperature (200–400 K) and electric field stress (61.5 MV/cm). A high capacitance density of 31 fF/μm 2 , a low voltage coefficient of capacitance of 363 ppm/V 2 , a low temperature coefficient of capacitance of <644 ppm/K, and an effective dielectric constant of 133 are demonstrated in a MIM capacitor with 1.4 nm capacitance equivalent thickness in a 40 nm thick ultra high-k multi-dielectric stack. Finally, all of these properties make this dielectric architecture of interest for next generation, highly scaled MIM capacitor applications.

36 MATERIALS SCIENCE↗

Increased Multilayer Fabrication and RF Characterization of a High-Density Stacked MIM Capacitor Based on Selective Etching

This paper presents the fabrication and characterization of a high-density multilayer stacked metal-insulator-metal (MIM) capacitor based on a novel process of depositing the MIM multilayer on pillars followed by polishing and selective etching steps to form a stacked capacitor with merely three photolithography steps. In this paper, the pillars were made of glass to prevent substrate loss, whereas an oxide-nitride-oxide dielectric was employed for lower leakage, better voltage/frequency linearity, and better stress compensation. MIM capacitors with six dielectric layers were successfully fabricated, yielding capacitance density of 3.8 fF/mu m(2), maximum capacitance of 2.47 nF, and linear and quadratic voltage coefficients of capacitance below 21.2 ppm/V and 2.31 ppm/V-2. The impedance was measured from 40 Hz to 3 GHz, and characterized by an analytically derived equivalent circuit model to verify the radio frequency applicability. The multilayer stacking-induced plate resistance mismatch and its effect on the equivalent series resistance (ESR) and effective capacitance was also investigated, which can be counteracted by a corrected metal thickness design. A low ESR of 800 m Omega was achieved, whereas the self-resonance frequency was >760 MHz, successfully demonstrating the feasibility of this method to scale up capacitance densities for high-quality-factor, high-frequency, and large-value MIM capacitors.

Tseng, VFG↗

Do Deep Eutectic Solvents Behave Like Ionic Liquid Electrolytes? A Perspective from the Electrode-Electrolyte Interface

The differential capacitance as a function of potential and composition for choline chloride (ChCl) and ethylene glycol (EG) at 1:2,1:4, 1:6, and 1:20 molar ratios were studied using electrochemical impedance spectroscopy (EIS) on glassy carbon. In addition, ChCl:EG at the known ethaline DES composition (1:2) and 1:20 molar ratio were studied on Au and Pt electrodes, and compared to glyceline (ChCl:glycerol, 1:2). The capacitance-potential curves on glassy carbon were best interpreted by the modified Gouy-Chapman model. A dampened U-shape was observed similar to dilute electrolytes, however, the non-negligible ionic and H-bonding interactions in these electrolytes resulted in ambiguity about the point of zero charge where capacitance was weakly dependent on potential. Additionally, the differential capacitance was independent of composition on glassy carbon due to limited availability of mobile free ions and constraints by solvated ion sizes within the interface. Increases in capacitance are observed with Au as a result of desolvation and specific adsorption of Cl, and with Pt upon decreased Cl concentrations. These results indicate DESs and H-bonded electrolytes with high salt concentrations are distinct from ionic liquids and present no pronounced over screening or crowding with applied potential.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Multidimensional Cyclic Voltammetry Simulations of Pseudocapacitive Electrodes with a Conducting Nanorod Scaffold

This paper aims to understand the effect of nanoarchitecture on the performance of pseudocapacitive electrodes consisting of conducting scaffold coated with pseudocapacitive material. To do so, two-dimensional numerical simulations of ordered conducting nanorods coated with a thin film of pseudocapacitive material were performed. The simulations reproduced three-electrode cyclic voltammetry measurements based on a continuum model derived from first principles. Two empirical approaches commonly used experimentally to characterize the contributions of surface-controlled and diffusion-controlled charge storage mechanisms to the total current density with respect to scan rate were theoretically validated for the first time. Moreover, the areal capacitive capacitance, attributed to EDL formation, remained constant and independent of electrode dimensions, at low scan rates. However, at high scan rates, it decreased with decreasing conducting nanorod radius and increasing pseudocapacitive layer thickness due to resistive losses. By contrast, the gravimetric faradaic capacitance, due to reversible faradaic reactions, decreased continuously with increasing scan rate and pseudocapacitive layer thickness but was independent of conducting nanorod radius. Note that the total gravimetric capacitance predicted numerically featured values comparable to experimental measurements. Finally, an optimum pseudocapacitive layer thickness that maximizes total areal capacitance was identified as a function of scan rate and confirmed by scaling analysis.

42 ENGINEERING↗

Assessment of Readout Techniques for Passive Monitors

This fiscal year (FY) 2023 report on passive temperature sensors covers two main objectives: to demonstrate that the optical dilatometer can successfully process disc shaped silicon carbide (SiC) temperature monitors (TMs), and to demonstrate proof of concept for using the capacitance readout method to read printed melt wires. The SiC objective was successfully met by annealing and analyzing, via optical dilatometry, all eight 3-mm SiC discs provided by the Nuclear Science User Facilities (NSUF) Idaho State University (ISU) Nanostructured Steels for Enhanced Radiation Tolerance (N SERT) experiment, which was irradiated at Idaho National Laboratory (INL)’s Advanced Test Reactor (ATR). Per the ISU N SERT experiment, capsule 1 (KGT 3828 1 and KGT 3828-2) had a design temperature of 300°C +/- 50°C and an exposure of 2 dpa +/- 10%; capsule 2 (KGT 4600 and KGT 4609) had a design temperature of 300°C +/- 50°C and an exposure of 6 dpa +/- 10%; capsule 3 (KGT 4639 C and KGT 4639-D) had a design temperature of 500°C +/- 50°C and an exposure of 6 dpa +/- 10%; and capsule 4 (KGT 3841 3 and KGT 3841 4) had a design temperature of 500°C +/- 50°C and an exposure of 2 dpa +/- 10%. The target exposure rates, in dpa, are the neutron damage for various types of nanostructured steels. All but three SiC TMs (KGT 4600, KGT 4639 D, and KGT 3841 4) revealed averaged peak irradiation temperatures that fell within the design temperature ranges. The three SiC TMs that did not fall within the design temperatures ranges were at least 100°C below that target temperature. Furthermore, SiC TM KGT 3841 C revealed two irradiation regimes: one closer to the 300°C design temperature, and the other closer to the 500°C design temperature. Also, all the SiC TMs’ averaged peak irradiation temperatures came in anywhere between 20°C and 240°C below the irradiation temperatures predicted by the thermal models. This showed the optical dilatometry method to be a reliable and less time intensive process for determining averaged peak irradiation temperatures from passive SiC TMs such as rods and discs. Under the Advanced Sensors and Instrumentation (ASI) program in FY-23, Boise State University (BSU) proposed to demonstrate proof of concept for using a capacitance readout technique applicable to printed melt wires; however, they were stymied by the complexity of the capacitance readout method. In support of the BSU work, INL developed an additively manufactured (AM) ceramic package for encapsulating the new melt wires. Inks were synthesized at BSU that used new protocols rather than following previously established protocols implemented at INL, and testing of various temperatures was conducted at BSU to evaluate the melting behaviors of the printed melt wires. The result was that the capacitance readout technique showed promise but also created more challenges than originally anticipated. For example, the tin ink synthesized at BSU showed unusual melting behaviors that did nothing to enhance the performance of the final printed melt wire prototype in terms of the capacitance readout method. To make the proof of concept work when applied to the printed melt wires, the ASI program would need to invest further resources and time. Consequently, the program is not planning to continue this proof of concept work in FY-24, based on the progress and findings achieved in FY-23.

36 MATERIALS SCIENCE↗

Giant Molecular Magnetocapacitance

Capacitance of a nanoscale system is usually thought of having two contributions, a classical electrostatic contribution and a quantum contribution dependent on the density of states and/or molecular orbitals close to the Fermi energy. In this letter we demonstrate that in molecular nano-magnets and other magnetic nanoscale systems, the quantum part of the capacitance becomes spin-dependent, and is tunable by an external magnetic field. This molecular magnetocapacitance can be realized using single molecule nano-magnets and/or other nano-structures that have antiferromagnetic ground states. As a proof of principle, first-principles calculation of the nano-magnet [Mn3O(sao)3(O2CMe)(H2O)(py)3] shows that the charging energy of the high-spin state is 260 meV lower than that of the low-spin state, yielding a 6% difference in capacitance. A magnetic field of ~40T can switch the spin state, thus changing the molecular capacitance. A smaller switching field may be achieved using nanostructures with a larger moment. Molecular magnetocapacitance may lead to revolutionary device designs, e.g., by exploiting the Coulomb blockade magnetoresistance whereby a small change in capacitance can lead to a huge change in resistance.

Wu, Yuning↗