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Diazonium-Functionalized Silicon Hybrid Photoelectrodes: Film Thickness and Composition Effects on Photoelectrochemical Behavior
Aryl diazonium electrografting is a powerful method for imparting molecular functionality onto various substrates by forming a stable carbon-surface covalent bond. While the high reactivity of the aryl radical intermediate makes this method fast and reliable, it can also lead to the formation of an insulating and disordered multilayer film. These thick films affect electrochemical performance, especially for semiconductor substrates used in photoelectrochemical applications. For this work we studied the effects of film thickness and composition by electrografting in situ-generated aminobenzene diazonium salts onto both n-type and p-type silicon electrodes at fixed potentials. Next, we attached ferrocene to the amine-terminated films and probed their (photo)electrochemical behavior. Cyclic voltammetry measurements showed decreased electrochemical reversibility with increasing diazonium film thickness; this reversibility was restored when ferrocene was incorporated throughout the film with a layer-by-layer deposition process. Finally, we compared the behavior of dark p-type electrodes to n-type photoelectrodes and observed differences in the electrochemical reversibility that we attribute to the change in potential drop across the two interfaces.
Methyl Termination of p-Type Silicon Enables Selective Photoelectrochemical CO 2 Reduction by a Molecular Ruthenium Catalyst
Methyl-terminated p-type silicon photoelectrodes selectively drive CO 2 reduction by a homogeneous [Ru(tpy)(Mebim-py)(NCCH 3 )] 2+ catalyst (tpy = 2,2′:6′,2″-terpyridine, Mebim-py = 1-methylbenzimidazol-2-ylidene-3-(2′-pyridine)). A 460 mV photovoltage is quantified for the photoelectrode. Under 1 sun illumination, this system achieves a Faradaic efficiency of 87% for CO at −1.7 V vs Fc +/0 , matching reports of the same catalyst at metallic electrodes operating at −2.1 V. When 5% water is introduced, the CH 3 -terminated Si photoelectrode remains stable, selectivity for CO is retained, and current density increases. Methyl termination suppresses the competitive hydrogen evolution observed for H-terminated Si photoelectrodes, which under the same conditions produce ca. 60% CO and 8% H 2 and have unstable performance. Furthermore, these results establish that a semiconductor photoelectrode can power a molecular CO 2 reduction catalyst without hydrogen evolution by the photoelectrode itself. Methyl termination of p-Si allows CO 2 reduction to kinetically outcompete proton reduction, revealing an important design principle for selective fuel formation.
Investigation of the luminescent phenomena of high resistivity silicon and study of electrical characteristics of tunneling into low resistivity silicon Semiannual progress report, 20 Sep. - 20 Mar. 1969
High resolution luminescence spectra of electron irradiated silicon
Investigation of the luminescent phenomena of high resistivity silicon and study of electrical characteristics of tunneling into low resistivity silicon Annual progress report, 20 Sep. 1968 - 19 Sep. 1969
Recombination luminescence and electron tunneling in silicon
Solar absorptivity and thermal emissivity of aluminum coated with silicon oxide films prepared by evaporation of silicon monoxide
Silicon oxide films coated satellite aluminum surfaces solar absorptivity and thermal emissivity, noting suitability as temperature control coatings
Effects of lithium doping on the behavior of silicon and silicon solar cells
Lithium doped silicon solar cells for improved radiation resistance to neutrons, protons, and electrons
Structure of silicon films deposited on oxidized silicon wafers
Silane for polycrystalline films deposition on oxidized silicon wafers, noting substrate temperature effects on preferred orientation of deposits
Silicon Ingot Casting - Heat Exchanger Method Multi-wire Slicing - Fixed Abrasive Slicing Technique. Phase 3 Silicon Sheet Growth Development for the Large Area Sheet Task of the Low-cost Solar Array Project
Several 20 cm diameter silicon ingots, up to 6.3 kg. were cast with good crystallinity. The graphite heat zone can be purified by heating it to high temperatures in vacuum. This is important in reducing costs and purification of large parts. Electroplated wires with 45 um synthetic diamonds and 30 um natural diamonds showed good cutting efficiency and lifetime. During slicing of a 10 cm x 10 cm workpiece, jerky motion occurred in the feed and rocking mechanisms. This problem is corrected and modifications were made to reduce the weight of the bladeheat by 50%.
Bend strengths of reaction bonded silicon nitride prepared from dry attrition milled silicon powder
Dry attrition milled silicon powder was compacted, sintered in helium, and reaction bonded in nitrogen-4 volume percent hydrogen. Bend strengths of bars with as-nitrided surfaces averaged as high as 210 MPa at room temperature and 220 MPa at 1400 C. Bars prepared from the milled powder were stronger than those prepared from as-received powder at both room temperature and at 1400 C. Room temperature strength decreased with increased milling time and 1400 C strength increased with increased milling time.
Reaction bonded silicon nitride prepared from wet attrition-milled silicon
Silicon powder wet milled in heptane was dried, compacted into test bar shape, helium-sintered, and then reaction bonded in nitrogen-4 volume percent hydrogen. As-nitrided bend strengths averaged approximately 290 MPa at both room temperature and 1400 C. Fracture initiation appeared to be associated with subsurface flaws in high strength specimens and both subsurface and surface flaws in low strength specimens.
Develop Silicone Encapsulation Systems for Terrestrial Silicon Solar Arrays
A cost effective encapsulant system was identified and a silicone acrylic cover material containing a durable ultraviolet screening agent was prepared. The effectiveness of the cover material in protecting photo-oxidatively sensitive polymers was demonstrated.
Reaction bonded silicon nitride prepared from wet attrition-milled silicon
Silicon powder wet milled in heptane was dried, compacted into test bar shape, helium-sintered, and then reaction bonded in nitrogen-4 vol% hydrogen. As-nitrided bend strengths averaged approximately 290 MPa at both room temperature and 1400 C. Fracture initiation appeared to be associated with subsurface flaws in high-strength specimens and both subsurface and surface flaws in low-strength specimens.
The MSFC silicon gate silicon-on-sapphire standard cell library
A pictorial representation of the MSFC silicon-on-sapphire standard cell library is presented. The cells are intended to be used with the PR2D (Place, Route in 2 Dimensions) automatic layout computer program.
Low cost solar array project silicon materials task. Development of a process for high capacity arc heater production of silicon for solar arrays
The experimental verification system for the production of silicon via the arc heater-sodium reduction of SiCl4 was designed, fabricated, installed, and operated. Each of the attendant subsystems was checked out and operated to insure performance requirements. These subsystems included: the arc heaters/reactor, cooling water system, gas system, power system, Control & Instrumentation system, Na injection system, SiCl4 injection system, effluent disposal system and gas burnoff system. Prior to introducing the reactants (Na and SiCl4) to the arc heater/reactor, a series of gas only-power tests was conducted to establish the operating parameters of the three arc heaters of the system. Following the successful completion of the gas only-power tests and the readiness tests of the sodium and SiCl4 injection systems, a shakedown test of the complete experimental verification system was conducted.
Low cost solar array project: Experimental process system development unit for producing semiconductor-grade silicon using silane-to-silicon process
The design, fabrication, and installation of an experimental process system development unit (EPSDU) were analyzed. Supporting research and development were performed to provide an information data base usable for the EPSDU and for technological design and economical analysis for potential scale-up of the process. Iterative economic analyses were conducted for the estimated product cost for the production of semiconductor grade silicon in a facility capable of producing 1000-MT/Yr.