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At least 19 records

In Situ TEM Study of Reversible and Irreversible Electroforming in Pt/Ti:NiO/Pt Heterostructures

Experimental verification of the microscopic origin of resistance switching in metal/oxide/metal heterostructures is needed for applications in non-volatile memory and neuromorphic computing. Numerous reports suggest that resistance switching in NiO is caused by local reduction of the oxide layer into nanoscale conducting filaments, but few reports have shown experimental evidence correlating electroforming with site-specific changes in composition. We have investigated the mechanisms of reversible and irreversible electroforming in 250–500 nm wide pillars patterned from a single Ta/Ti/Pt/Ti-doped NiO/Pt/Ta heterostructure and have shown that these can coexist within a single sample. We performed in situ transmission electron microscopy (TEM) electroform- ing and switching on each pillar to correlate the local electron transport behavior with microstructure and composition in each pillar. DFT calculations fitted to electron energy loss spectroscopy data showed that the Ti-doped NiO layer is partially reduced after reversible electroforming, with the formation of oxygen vacancies ordered into lines in the <110> direction. However, under the same probing conditions, adjacent pillars show irreversible electroforming caused by electromigration of metallic Ta to form a single bridge across the oxide layer. We propose that the different electroforming behaviors are related to microstructural variations across the sample and may lead to switching variability.

Environmental Molecular Sciences Laboratory↗

Optimizing the Electroforming Process to Enhance the Thickness Uniformity of Full Shell X-Ray Optics

Electroforming replication technology at Marshall Space Flight Center has a long heritage of producing highquality full-shell X-ray mirrors for various applications. Nickel alloys are electroformed onto a super-polished mandrel in the electroforming process, then separated to form the replicated full-shell optic. Various parameters in the electroplating configuration could result in the nonuniformity of the shell’s thickness. Thickness nonuniformities primarily occur due to non-uniform electric field distributions in the electroforming tank during the deposition. Using COMSOL Multiphysics simulations, we have studied the electric field distributions during the deposition process. Using these studies, we have optimized the electric fields inside the tank using customized shields and insulating gaskets on the mandrel. These efforts reduced thickness non-uniformity from over 20% to under 5% percent. Improving the thickness uniformity of the shell aids in better mounting and alignment of shells in the optics module. Optimization of the electroforming process, in some cases, improved the optical performance of the shells. COMSOL optimizing of the electroforming process and the experimental results validating these simulations are presented in this article.

X-ray optics↗

New Alloys for Electroformed Replicated X-Ray Optics

The process of electroforming x-ray mirror shells off a superpolished mandrel has been widely used. The recently launched XMM mission is a good example of this, containing 174 such mirror shells of diameters ranging from 0.3-0.7 m and thicknesses of 0.47-1.07 mm. To continue to utilize this technique for the next generation of x-ray observatories, where ever-larger collecting areas will be required within the constraints of tight weight budgets, demands that new alloys be developed that can withstand the large stresses imposed on very thin shells by the replication and handling processes. Towards this end, we began a development program in late 1997 to produce a high-strength alloy suitable for electroforming very thin high-resolution x-ray optics. The requirements for this task are quite severe; not only must the electroformed deposit be very strong, it must also have extremely low residual stresses to prevent serious figure distortions in large thin-walled shells. Further, the electroforming must be performed at near room temperature, as large temperature changes will modify the figure of the mandrel, in an environment that is not corrosive for the mandrel. The figure of merit for the strength of the electroformed deposit is its Precision Elastic Limit (PEL). This is a measure of permanent strain, at the few parts per million level, under applied stress. Pure nickel is very ductile and will permanently deform, at the parts-per-million level under loads of a few x 10(exp 7) Pa. These stresses are easily exceeded when thin-walled shells (150 micron thick) are replicated. Our goal was to develop an alloy an order of magnitude stronger than this. We will present the results of our development program, showing the evolution of our plating baths through to our present 'glassy' nickel alloy that satisfies the goals above. For each we will show the electroforming characteristics of the bath and the PEL measurements for the resulting alloys. We estimate the ultimate limit on shell thickness and mass for x-ray mirrors produced in these baths.

Engelhaupt, D.↗

Fabrication of liquid-rocket thrust chambers by electroforming

Electroforming has proven to be an excellent fabrication method for building liquid rocket regeneratively cooled thrust chambers. NASA sponsored technology programs have investigated both common and advanced methods. Using common procedures, several cooled spool pieces and thrust chambers have been made and successfully tested. The designs were made possible through the versatility of the electroforming procedure, which is not limited to simple geometric shapes. An advanced method of electroforming was used to produce a wire-wrapped, composite, pressure-loaded electroformed structure, which greatly increased the strength of the structure while still retaining the advantages of electroforming.

Duscha, R. A.↗

Relation between the electroforming voltage in alkali halide-polymer diodes and the bandgap of the alkali halide

Electroforming of indium-tin-oxide/alkali halide/poly(spirofluorene)/Ba/Al diodes has been investigated by bias dependent reflectivity measurements. The threshold voltages for electrocoloration and electroforming are independent of layer thickness and correlate with the bandgap of the alkali halide. We argue that the origin is voltage induced defect formation. Frenkel defect pairs are formed by electron–hole recombination in the alkali halide. This self-accelerating process mitigates injection barriers. The dynamic junction formation is compared to that of a light emitting electrochemical cell. A critical defect density for electroforming is 10{sup 25}/m{sup 3}. The electroformed alkali halide layer can be considered as a highly doped semiconductor with metallic transport characteristics.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Influence of the Silicon Dioxide Layer Thickness on Electroforming in Open TiN–SiO{sub 2}–W Sandwiches

Based on experimental data for electroforming in open TiN–SiO{sub 2}–W sandwich structures (the end face of d = 10–30-nm-thick SiO{sub 2} films exposed to vacuum served as an insulating trench), it has been shown that the voltage at which conducive particles (CPs) arise (i.e., the electroforming onset voltage) changes insignificantly with decreasing thickness d. The electroforming process is initiated by a voltage with a threshold near 8.5 V, rather than by electric field strength. This value far exceeds the CP formation voltage threshold when already formed structures switch over (3–4 V). This points to the existence of two nonthermal mechanisms that activate CP formation under electron impact. In the case of electroforming, this is dissociative attachment of an electron, which causes an oxygen atom to escape into vacuum and, hence, an increase in the silicon atom concentration on the surface of the insulating trench. In the case of switching, this is a change in the molecular state of oxygen (or hydrogen) on the surface.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Using galvanostatic electroforming of Bi 1–x Sb x nanowires to control composition, crystallinity, and orientation

When using galvanostatic pulse deposition, we studied the factors influencing the quality of electroformed Bi 1–x Sb x nanowires with respect to composition, crystallinity, and preferred orientation for high thermoelectric performance. Two nonaqueous baths with different Sb salts were investigated. The Sb salts used played a major role in both crystalline quality and preferred orientations. Nanowire arrays electroformed using an SbI 3 -based chemistry were polycrystalline with no preferred orientation, whereas arrays electroformed from an SbCl 3 -based chemistry were strongly crystallographically textured with the desired trigonal orientation for optimal thermoelectric performance. From the SbCl 3 bath, the electroformed nanowire arrays were optimized to have nanocompositional uniformity, with a nearly constant composition along the nanowire length. Moreover, nanowires harvested from the center of the array had an average composition of Bi 0.75 Sb 0.25 . However, the nanowire compositions were slightly enriched in Sb in a small region near the edges of the array, with the composition approaching Bi 0.70 Sb 0.30 .

36 MATERIALS SCIENCE↗

Method of electroforming a rocket chamber

A transpiration cooled rocket chamber is made by forming a porous metal wall on a suitably shaped mandrel. The porous wall may be made of sintered powdered metal, metal fibers sintered on the mandrel or wires woven onto the mandrel and then sintered to bond the interfaces of the wires. Intersecting annular and longitudinal ribs are then electroformed on the porous wall. An interchamber wall having orifices therein is then electroformed over the annular and longitudinal ribs. Parallel longitudinal ribs are then formed on the outside surface of the interchamber wall after which an annular jacket is electroformed over the parallel ribs to form distribution passages therewith. A feed manifold communicating with the distribution passages may be fabricated and welded to the rocket chamber or the feed manifold may be electroformed in place.

Fortini, A.↗

Surface Self-nanocrystallization in Copper Electroforming

The coarse columnar grain layer generated on top of electroforming deposits leads to low surface strength and poor global performance of deposits. Here, we introduce a particle abrasive-induced surface self-nanocrystallization process, which is a part of the electroforming process rather than involving complex poststeps using special equipment. It can generate a thickness-controllable surface nanocrystalline layer on top of copper deposits for performance enhancement. In this study, surface nanocrystalline layers of 10, 20, 50 and 120 μm were fabricated on top of 500-μm-thick copper deposits. The tensile strength of copper deposits increases from 234 to 246, 330, 383 and 421 MPa, with a corresponding decrease in elongation from 26 to 25, 24, 15 and 6%, respectively. The moderately thick surface nanocrystalline layer makes the copper deposits exhibit good comprehensive mechanical properties. In addition, the surface self-nanocrystallization also makes the copper deposits show a better corrosion resistance in a neutral aqueous 0.1 M NaCl solution. This study aims to promote a convenient, controllable and reliable surface self-nanocrystallization process in electroforming for improving the global performance of deposits.

36 MATERIALS SCIENCE↗

Optical microcavities and enhanced electroluminescence from electroformed Al-Al{sub 2}O{sub 3}-Ag diodes

Electroluminescence (EL) and electron emission into vacuum (EM) occur when a non-destructive dielectric breakdown of Al-Al{sub 2}O{sub 3}-Ag diodes, electroforming, results in the development of a filamentary region in which current-voltage (I-V) characteristics exhibit voltage-controlled negative resistance. The temperature dependence of I-V curves, EM, and, particularly, EL of Al-Al{sub 2}O{sub 3}-Ag diodes with anodic Al{sub 2}O{sub 3} thicknesses between 12 nm and 30 nm, has been studied. Two filters, a long-pass (LP) filter with transmission of photons with energies less than 3.0 eV and a short-pass (SP) filter with photon transmission between 3.0 and 4.0 eV, have been used to characterize EL. The voltage threshold for EL with the LP filter, V{sub LP}, is ∼1.5 V. V{sub LP} is nearly independent of Al{sub 2}O{sub 3} thickness and of temperature and is 0.3–0.6 V less than the threshold voltage for EL for the SP filter, V{sub SP}. EL intensity is primarily between 1.8 and 3.0 eV when the bias voltage, V{sub S} ≲ 7 V. EL in the thinnest diodes is enhanced compared to EL in thicker diodes. For increasing V{sub S}, for diodes with the smallest Al{sub 2}O{sub 3} thicknesses, there is a maximum EL intensity, L{sub MX}, at a voltage, V{sub LMX}, followed by a decrease to a plateau. L{sub MX} and EL intensity at 4.0 V in the plateau region depend exponentially on Al{sub 2}O{sub 3} thickness. The ratio of L{sub MX} at 295 K for a diode with 12 nm of Al{sub 2}O{sub 3} to L{sub MX} for a diode with 25 nm of Al{sub 2}O{sub 3} is ∼140. The ratio of EL intensity with the LP filter to EL intensity with the SP filter, LP/SP, varies between ∼3 and ∼35; it depends on Al{sub 2}O{sub 3} thickness and V{sub S}. Enhanced EL is attributed to the increase of the spontaneous emission rate of a dipole in a non-resonant optical microcavity. EL photons interact with the Ag and Al films to create surface plasmon polaritons (SPPs) at the metal-Al{sub 2}O{sub 3} interfaces. SPPs generate large electromagnetic fields in the filamentary region of the electroformed Al-Al{sub 2}O{sub 3}-Ag diode, which then acts as an optical microcavity. A model is proposed for electronic processes in electroformed Al-Al{sub 2}O{sub 3}-Ag diodes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Spectra of surface plasmon polariton enhanced electroluminescence from electroformed Al-Al{sub 2}O{sub 3}-Ag diodes

Narrow band-pass filters have been used to measure the spectral distribution of electroluminescent photons with energies between 1.8 eV and 3.0 eV from electroformed Al-Al{sub 2}O{sub 3}-Ag diodes with anodic Al{sub 2}O{sub 3} thicknesses between 12 nm and 18 nm. Electroforming of metal-insulator-metal (MIM) diodes is a non-destructive dielectric breakdown that results in a conducting channel in the insulator and changes the initial high resistance of the MIM diode to a low resistance state. It is a critical step in the development of resistive-switching memories that utilize MIM diodes as the active element. Electroforming of Al-Al{sub 2}O{sub 3}-Ag diodes in vacuum results in voltage-controlled negative resistance (VCNR) in the current-voltage (I-V) characteristics. Electroluminescence (EL) and electron emission into vacuum (EM) develop simultaneously with the current increase that results in VCNR in the I-V characteristics. EL is due to recombination of electrons injected at the Al-Al{sub 2}O{sub 3} interface with radiative defect centers in Al{sub 2}O{sub 3}. Measurements of EL photons between 1.8 eV and 3.0 eV using a wide band-pass filter showed that EL intensity is exponentially dependent on Al{sub 2}O{sub 3} thickness for Al-Al{sub 2}O{sub 3}-Ag diodes between 12 nm and 20 nm thick. Enhanced El intensity in the thinnest diodes is attributed to an increase in the spontaneous emission rate of recombination centers due to high electromagnetic fields generated in Al{sub 2}O{sub 3} when EL photons interact with electrons in Ag or Al to form surface plasmon polaritons at the Al{sub 2}O{sub 3}-Ag or Al{sub 2}O{sub 3}-Al interface. El intensity is a maximum at 2.0–2.2 eV for Al-Al{sub 2}O{sub 3}-Ag diodes with Al{sub 2}O{sub 3} thicknesses between 12 nm and 18 nm. EL in diodes with 12 nm or 14 nm of Al{sub 2}O{sub 3} is enhanced by factors of 8–10 over EL from a diode with 18 nm of Al{sub 2}O{sub 3}. The extent of EL enhancement in the thinnest diodes can vary significantly between samples. A narrow band of recombination centers was found in one Al-Al{sub 2}O{sub 3}-Ag diode with 12 nm of Al{sub 2}O{sub 3}; it had EL intensity 100 times greater at 2.15 eV than the diode with 18 nm of Al{sub 2}O{sub 3}. EL intensity for photons with energies greater than 2.6 eV is nearly the same for all diodes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Development of improved electroforming technique

Techniques were studied to reinforce or strengthen electroformed nickel to allow a fuller utilization of electroforming as a reliable and low cost fabrication technique for regenerately cooled thrust chambers. Techniques for wire wrapping while electrodepositing were developed that can result in a structurally strong wall with less weight than a conventional electroformed wall. Also a technique of codepositing submicron sized THO2 particles with the nickel to form a dispersion strengthened structure was evaluated. The standard nickel cylinders exhibited an average hoop strength of 80,000 psi with a yield strength of 65,000 psi and a modulus of 25.6 x 10 to the 6th power psi. The as produced dispersion strengthened nickel showed a hoop strength of 97,000 psi with a yield strength of 67,000 psi. This is an increase of 17,000 psi or 21% over the standard nickel hoop strength. The wire wrapping cylinders showed an increased strength over the standard nickel test samples of 26,000 to 66,800 psi which is in the range of 26 to 104% increase in strength over the base standard nickel. These latter test results are indicative of a volume percent wire reinforcement from 15 to 31. The measured hoop strengths agree with calculated composite strengths based upon rule of mixtures.

Mccandles, L. C.↗

Investigation of electroforming techniques, literature analysis report

A literature analysis is presented of reports, specifications, and documented experiences with the use of electroforming to produce copper and nickel structures for aerospace and other engineering applications. The literature period covered is from 1948 to 1974. Specific effort was made to correlate mechanical property data for the electrodeposited material with known electroforming solution compositions and operating conditions. From this survey, electrolytes are suggested for selection to electroform copper and nickel outer shells on regeneratively cooled thrust chamber liners, and other devices subject to thermal and pressure exposure, based on mechanical properties obtainable, performance under various thermal environments, and ease of process control for product reproducibility. Processes of potential value in obtaining sound bonds between electrodeposited copper and nickel and copper alloy substrates are also discussed.

Malone, G. A.↗

Study of high performance alloy electroforming

Using the two nickel-manganese alloy electroforming baths of near identical compositions, panels were electroformed under the same deposition parameters of current density, bath temperature, pH, and pulse plating conditions of duty cycle and frequency. By changing the electrolyte agitation conditions, significant effects on mechanical properties were noted. Since electrolyte agitation conditions on the typical flat panels studied to date will not be identical to those existing on a complex curved shape such as the SSME combustion chamber simulation, it is most important that these effects be evaluated prior to Phase B studies. The subscale chamber has been fabricated and shield support tooling is being made. Electroforming of optimized alloy test bars is being deferred until the electrolyte agitation effects are more fully appraised.

Malone, G. A.↗

High performance alloy electroforming

Electroformed copper and nickel are used in structural applications for advanced propellant combustion chambers. An improved process has been developed by Bell Aerospace Textron, Inc. wherein electroformed nickel-manganese alloy has demonstrated superior mechanical and thermal stability when compared to previously reported deposits from known nickel plating processes. Solution chemistry and parametric operating procedures are now established and material property data is established for deposition of thick, large complex shapes such as the Space Shuttle Main Engine. The critical operating variables are those governing the ratio of codeposited nickel and manganese. The deposition uniformity which in turn affects the manganese concentration distribution is affected by solution resistance and geometric effects as well as solution agitation. The manganese concentration in the deposit must be between 2000 and 3000 ppm for optimum physical properties to be realized. The study also includes data regarding deposition procedures for achieving excellent bond strength at an interface with copper, nickel-manganese or INCONEL 718. Applications for this electroformed material include fabrication of complex or re-entry shapes which would be difficult or impossible to form from high strength alloys such as INCONEL 718.

Malone, G. A.↗

Simplified Models Speed Electroforming Tests

Method of evaluating configurations of electroforming shields reduces cost of evaluation. Applicable to electroformed parts that have axes of symmetry. Involves electroforming material onto two-dimensional approximation of part in question, using side shields to be evaluated. Eliminates expense of constructing full three-dimensional model but makes possible to perform evaluation almost immediately.

Bodemeijer, Ronnald↗

Exchange of Ions across the TiN/TaO x Interface during Electroformation of TaO x -Based Resistive Switching Devices

The valence change model describes the resistive switching in metal oxide-based devices as due to electroreduction of the oxide and subsequent electromigration of oxygen vacancies. Here, we present cross-sectional X-ray energy-dispersive spectroscopy elemental maps of Ta, O, N, and Ti in electroformed TiN/TaO 2.0 /TiN structures. O, N, and Ti were exchanged between the anode and the functional oxide in devices formed at high power (~1 mW), but the exchange was below the detection limit at low power (<0.5 mW). All structures exhibit a similar Ta-enriched and O-depleted filament formed by the elemental segregation in the functional oxide by the temperature gradient. The elemental interchange is interpreted as due to Fick’s diffusion caused by high temperatures in the gap of the filament and is not an essential part of electroformation.

36 MATERIALS SCIENCE↗