Study of failure modes of multilevel large scale integrated circuits Interim report, 15 Apr. - 14 Oct. 1967
Electrical properties and failure modes of integrated multilevel microcircuits with silicon oxide-silicon interfaces
Schlegel, E. S.↗
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Results for “SILICON OXIDE”
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Surface chemistry, microstructure and friction properties of some ferrous-base metallic glasses at temperatures to 750 C
X-ray photoelectron spectroscopy analysis, transmission electron microscopy, diffraction studies, and sliding friction experiments were conducted with ferrous-base metallic glasses in sliding contact with aluminum oxide at temperatures from room to 750 C in a vacuum of 30 nPa. The results indicate that there is a significant temperature influence on the friction properties, surface chemistry, and microstructure of metallic glasses. The relative concentrations of the various constituents at the surface of the sputtered specimens were very different from the normal bulk compositions. Contaminants can come from the bulk of the material to the surface upon heating and impart boric oxide and silicon oxide at 350 C and boron nitride above 500 C. The coefficient of friction increased with increasing temperature to 350 C. Above 500 C the coefficient of friction decreased rapidly. The segregation of contaminants may be responsible for the friction behavior.
Miyoshi, K.↗
High-efficiency silicon solar cells
Fabrication and characterization of high-efficiency metal insulator, n-p (MINP) cells is described. Particular attention was paid to development of measurement methods for surface recombination and density of surface states. A modified Rosier test structure was used successfully for density of surface states. Silicon oxide and silicon nitride passivants were studied. Heat treatment after plasma enhanced chemical vapor deposition (CVD) of silicon nitride was shown to be beneficial. A more optimum emitter concentration profile was modeled.
Olsen, L. C.↗
Guided-wave approaches to spectrally selective energy absorption
Results of experiments designed to demonstrate spectrally selective absorption in dielectric waveguides on semiconductor substrates are reported. These experiments were conducted with three waveguides formed by sputtering films of PSK2 glass onto silicon-oxide layers grown on silicon substrates. The three waveguide samples were studied at 633 and 532 nm. The samples differed only in the thickness of the silicon-oxide layer, specifically 256 nm, 506 nm, and 740 nm. Agreement between theoretical predictions and measurements of propagation constants (mode angles) of the six or seven modes supported by these samples was excellent. However, the loss measurements were inconclusive because of high scattering losses in the structures fabricated (in excess of 10 dB/cm). Theoretical calculations indicated that the power distribution among all the modes supported by these structures will reach its steady state value after a propagation length of only 1 mm. Accordingly, the measured loss rates were found to be almost independent of which mode was initially excited. The excellent agreement between theory and experiment leads to the conclusion that low loss waveguides confirm the predicted loss rates.
Stegeman, G. I.↗
Measurements of complex permittivity of microwave substrates in the 20 to 300 K temperature range from 26.5 to 40.0 GHz
A knowledge of the dielectric properties of microwave substrates at low temperatures is useful in the design of superconducting microwave circuits. Results are reported for a study of the complex permittivity of sapphire (Al2O3), magnesium oxide (MgO), silicon oxide (SiO2), lanthanum aluminate (LaAlO3), and zirconium oxide (ZrO2), in the 20 to 300 Kelvin temperature range, at frequencies from 26.5 to 40.0 GHz. The values of the real and imaginary parts of the complex permittivity were obtained from the scattering parameters, which were measured using a HP-8510 automatic network analyzer. For these measurements, the samples were mounted on the cold head of a helium gas closed cycle refrigerator, in a specially designed vacuum chamber. An arrangement of wave guides, with mica windows, was used to connect the cooling system to the network analyzer. A decrease in the value of the real part of the complex permittivity of these substrates, with decreasing temperature, was observed. For MgO and Al2O3, the decrease from room temperature to 20 K was of 7 and 15 percent, respectively. For LaAlO3, it decreased by 14 percent, for ZrO2 by 15 percent, and for SiO2 by 2 percent, in the above mentioned temperature range.
Miranda, Felix A.↗
Measurements of complex permittivity of microwave substrates in the 20 to 300 K temperature range from 26.5 to 40.0 GHz
A knowledge of the dielectric properties of microwve substrates at low temperatures is useful in the design of superconducting microwave circuits. Results are reported for a study of the complex permittivity of sapphire (Al2O3), magnesium oxide (MgO), silicon oxide (SiO2), lanthanum aluminate (LaAlO3), and zirconium oxide (ZrO2), in the 20 to 300 Kelvin temperature range, at frequencies from 26.5 to 40.0 GHz. The values of the real and imaginary parts of the complex permittivity were obtained from the scattering parameters, which were measured using an HP-8510 automatic network analyzer. For these measurements, the samples were mounted on the cold head of a helium gas closed cycle refrigerator, in a specially designated vacuum chamber. An arrangement of wave guides, with mica windows, was used to connect the cooling system to the network analyzer. A decrease in the value of the real part of the complex permittivity of these substrates, with decreasing temperature, was observed. For MgO and Al2O3, the decrease from room temperature to 20 K was of 7 and 15 percent, respectively. For LaAlO3, it decreased by 14 percent, for ZrO2 by 15 percent, and for SiO2 by 2 percent, in the above mentioned temperature range.
Miranda, Felix A.↗
Radiation hardening of thermal oxides on silicon via ion implantation
Ion implantation for reducing space charge buildup in thermal oxides on silicon exposed to ionizing radiation
Donovan, R. P.↗
Atomic Layer Deposition of Chemical Passivation Layers and High Performance Anti-Reflection Coatings on Back-Illuminated Detectors
A back-illuminated silicon photodetector has a layer of Al2O3 deposited on a silicon oxide surface that receives electromagnetic radiation to be detected. The Al2O3 layer has an antireflection coating deposited thereon. The Al2O3 layer provides a chemically resistant separation layer between the silicon oxide surface and the antireflection coating. The Al2O3 layer is thin enough that it is optically innocuous. Under deep ultraviolet radiation, the silicon oxide layer and the antireflection coating do not interact chemically. In one embodiment, the silicon photodetector has a delta-doped layer near (within a few nanometers of) the silicon oxide surface. The Al2O3 layer is expected to provide similar protection for doped layers fabricated using other methods, such as MBE, ion implantation and CVD deposition.
Hoenk, Michael E.↗
Optical waveguides in oxygen-implanted buried-oxide silicon-on-insulator structures
An analysis is made of the waveguiding properties of the oxygen-implanted, buried-oxide, silicon-on-insulator structures currently being developed for use in microelectronics. It is found that in spite of the fact that the buried-oxide layer is only a few tenths of a micrometer thick, the single-crystal overlayer can support TEo guided-wave propagation, at subbandgap wavelengths, with losses due to substrate radiation leakage at or below the benchmark level of 1 dB/cm.
Kurdi, B. N.↗
Research on the Mechanism and Kinetics of Oxidation of Silicon in Air Second Semiannual Report, 1 Dec. 1965 - 31 May 1966
Ellipsometer studies of oxide thin film growth on silicon in air
SILICON↗
Methods for forming silicon-silicon oxide-carbon composites for lithium ion cell electrodes
Composite silicon based materials are described that are effective active materials for lithium ion batteries. The composite materials comprise processed, e.g., high energy mechanically milled, silicon suboxide and graphitic carbon in which at least a portion of the graphitic carbon is exfoliated into graphene sheets. The composite materials have a relatively large surface area, a high specific capacity against lithium, and good cycling with lithium metal oxide cathode materials. The composite materials can be effectively formed with a two-step high energy mechanical milling process. In the first milling process, silicon suboxide can be milled to form processed silicon suboxide, which may or may not exhibit crystalline silicon x-ray diffraction. In the second milling step, the processed silicon suboxide is milled with graphitic carbon. Composite materials with a high specific capacity and good cycling can be obtained in particular with balancing of the processing conditions.
Anguchamy, Yogesh Kumar↗
Metal oxide barrier layers for terrestrial and space perovskite photovoltaics
Perovskite photovoltaics are attractive for both terrestrial and space applications. Although terrestrial conditions require durability against stressors such as moisture and partial shading, space poses different challenges: radiation, atomic oxygen, vacuum and high-temperature operation. Here we demonstrate a silicon oxide layer that hardens perovskite photovoltaics to critical space stressors. A 1-um-thick silicon oxide layer evaporated atop the device contacts blocks 0.05 MeV protons at fluences of 10 15 cm -2 without a loss in power conversion efficiency, which results in a device lifetime increase in low Earth orbit by x20 and in highly elliptical orbit by x30. Silicon-oxide-protected Cs 0.05 (MA 0.17 FA 0.83 ) 0.95 Pb(I 0.83 Br 0.17 ) 3 ) (MA, methylammonium; FA, formamidinium cation) and CsPbI 2 Br cells survive submergence in water and N,N-dimethylformamide. Furthermore, moisture tolerance of Sn-Pb and CsPbI 2 Br devices is boosted. Devices are also found to retain power conversion efficiencies on exposure to alpha irradiation and atomic oxygen. So, this barrier technology is a step towards lightweight packaging designs for both space and terrestrial applications.
14 SOLAR ENERGY↗
Nafion Passivation of c-Si Surface and Edge for Electron Paramagnetic Resonance
Effective surface passivation of crystalline silicon (c-Si) surface by reducing the carrier recombination rate has led to modern c-Si solar cells with efficiencies > 25% in both laboratory and industrial settings. Typical mainstream surface passivation techniques include high-temperature silicon oxide (SiOx), amorphous silicon (a-Si:H), hydrogen-rich silicon nitride (SiNx), and aluminum oxide (Al2O3) [1]. They have demonstrated excellent surface recombination velocity of < 1 cm/s owing to both chemical passivation (via the hydrogen saturation of Si dangling bonds at the c-Si surface), and field-effect passivation (via the band bending from the fixed charge of the dielectric layers). Recently, several groups have studied solution-based organic materials for c-Si passivation, including bis(trifluoromethane)sulfonimide (TFSI), polystyrenesulfonate, and Nafion [2, 3] via spin or dip coating. All films were processed at ambient room temperature, and a high lifetime of 12 ms, as well as a low saturation current density (J0) of 16 fA/cm2, have been demonstrated using Nafion passivation [2]. However, despite the air instability, Nafion has several advantages when introduced to PV applications: (a) Wafer quality can be measured at high throughput after several process stages. (b) It is compatible with PL mapping, compared to HF liquid passivation which cannot be performed in room ambient. (c) Nafion process is fast and poses fewer constraints on process complexity, and cleanness, compared to Al2O3 and a-Si:H passivation. (d) Nafion is the ideal room temperature passivation, which can be applied onto a small fragment of a degraded module to investigate microscopic mechanisms when studying degradation mechanisms. Edge passivation is needed for advanced characterization tests such as Electron Paramagnetic Resonance (EPR), Electrically Detected Magnetic Resonance (EDMR), Deep Level Transient Spectroscopy (DLTS), local cell current-voltage (J-V), and Suns-Voc. In such cases, the laser-damaged minicell edges will obscure the true degradation mechanisms, and Nafion can effectively passivate them without causing further degradation through elevated-temperature processes. In this contribution, we show the passivation results of Nafion on bare nCz and compare it with a Al2O3 witness. We highlight the importance of edge pre-treatment before Nafion to achieve good passivation. We show that Nafion can reach decent passivation without undergoing high-temperature processes. We also explore the temperature dependency of Nafion through photoluminescence (PL) study and demonstrate the application of Nafion under cryogenic temperature (~6 K) through EPR. Our results reveal that Nafion can reduce surface and edge Si dangling bonds at low temperatures. Thus, it can be used as an effective room temperature passivation technique for advanced characterization methods.
c-Si↗
Tracking the Oxidation of Silicon Anodes Using Cryo-EELS upon Battery Cycling
Silicon is a high-capacity material for the anode of a rechargeable lithium-ion battery. One of the fundamental challenges for using Si in anodes is capacity fading, which has been revealed to be partially associated with the interfacial instability between the Si and liquid electrolyte due to the large volume swing of Si upon charging and discharging. Smart nanoscale design concepts, either pre-synthesized or formed in-situ, have led to the mitigation of the detrimental factors associated with the volume swing of Si. However, it has never been clear as how the chemical state of Si evolves and contributes to the capacity fading upon battery cycling. Here, we use cryo-electron energy loss spectroscopy (EELS) to directly monitor, at sub-nanometer scale, the chemical evolution of Si upon battery cycling. We discover that during the cycling process, Si particles are progressively oxidized to form SiO 2 , which is initiated from the particle surface and gradually penetrates toward the interior of the particle, directly contributing to the capacity fading. Possible mechanisms of Si oxidation are postulated. We further show how the cycling stability can be improved by an electrolyte additive to form an effective passivation layer, representatively, even a small concentration of fluoroethylene carbonate (FEC) causes the formation of an LiF layer on the Si nanoparticle surface that prevents Si oxidation and improves cycling stability. Furthermore, the present work unveils Si oxidation as a previously unrecognized factor that contributes to capacity fading, therefore providing insight into the design of anodes with Si based materials.
25 ENERGY STORAGE↗
Unusual Electrochemical Activity of Thin SiO 2 Layers Leads to Instability of Molecular Attachment in Hybrid Photoelectrodes
Hybrid photoelectrodes, comprised of a light-absorbing semiconductor and a surface-integrated molecular catalyst, are attractive for applications in artificial photosynthesis, since they combine the advantages of broadband semiconductor light absorption with the selectivity of molecular catalysis. A widely used class of hybrid photoelectrodes is based on Si substrates passivated by a thin (<3 nm) layer of silicon oxide, which is commonly prepared by controlled chemical or thermal oxidation, resulting in chemical oxide (ChO) or thermal oxide (ThO) layers, respectively. However, the electrochemical stability of these oxide layers, and the chemical stability of the semiconductor-molecule assembly in hybrid photoelectrodes, are not well understood, with evidence that covalently-bound molecules detach from the oxide surface upon application of cathodic bias. We have examined the intrinsic electrochemical reactivity of silicon oxide layers and how it affects the attachment of molecular monolayers. We determined that the surface of Si|ThO is primarily terminated with hydrophobic siloxane moieties, whereas that of Si|ChO contains a higher concentration of hydrophilic silanol groups. Initial high current densities for Si|ChO under applied bias up to -2 V vs. Ag/AgCl, decrease during repeated cyclic voltammetry scans, due to the consumption of surface-bound water. This is manifested by a reversible wave around -0.5 V in CH 3 CN solution, and a similar pH-dependent wave in water, revealing the pK a of the silanol groups to be ~4. Here, our combined observations support the electrochemically-induced dehydration of the SiO 2 surface, which converts silanol groups to siloxanes and proceeds through an H-atom intermediate that is most likely stabilized by pentavalent Si. We propose that similar reactivity is responsible for the electrochemical loss of alkylsiloxane-attached molecules under cathodic bias, which has important implications for the choice of catalyst attachment strategy in hybrid photoelectrodes.
14 SOLAR ENERGY↗
Research on the mechanism and kinetics of oxidation of silicon in air Semiannual report, 1 Dec. 1967 - 31 May 1968
Ellipsometric method for measuring optical parameters of substrate and oxidation surface layer thickness on silicon
Knausenberger, W.↗
Photoemission measurements of interface barrier energies for tunnel oxides on silicon
Internal photoemission measurements of the Si/SiO2 and Al/SiO2 barrier heights on oxides of tunneling thickness (43-56 A) are compared with measurements on thick oxides (310 A and greater) and the barrier heights are found to be the same. The results suggest that substantially thinner oxides, grown by the same method, can be characterized by the same barrier heights. Limits to the experimental technique posed by photovoltaic and displacement currents, and transport of hot carriers in the tunnel oxide are discussed.
Dressendorfer, P. V.↗
Active-to-passive transition in the oxidation of silicon carbide and silicon nitride in air
The active-to-passive transition in the oxidation of SiC and Si3N4 was determined in a flowing air environment as a function of temperature and total pressure. The experimentally observed transition temperatures ranged from a low of 1347 C to a high of 1543 C for partial pressures of oxygen of 2.5 and 123.2 Pa, respectively. The SiC and Si3N4 samples had approximately the same transition point for a given pressure. In general, the higher the flow rate, the higher the transition temperature for a given pressure. The transitions for SiC measured in this study agree with previous data for the transition of SiC measured in pure oxygen at reduced pressures and in oxygen inert gas mixtures.
Vaughn, Wallace L.↗