Electrical resistivity change in amorphous Ta42Si13N45 films by stress relaxation

In a first experiment, a reactively sputtered amorphous Ta₄₂Si₁₃N₄₅ film about 260 nm thick deposited on a flat and smooth alumina substrate was thermally annealed in air for 30 min and let cooled again repeatedly at successively higher temperatures from 200 to 500 °C. This treatment successively and irreversibly increases the room temperature resistivity of the film monotonically from its initial value of 670 μΩ cm to a maximum of 705 μΩ cm (+5.2 %). Subsequent heat treatments at temperatures below 500 °C and up to 6 h have no further effect on the room temperature resistivity. The new value remains unchanged after 3.8 years of storage at room temperature. In a second experiment, the evolution of the initially compressive stress of a film similarly deposited by reactive sputtering on a 2-inch silicon wafer was measured by tracking the wafer curvature during similar thermal annealing cycles. A similar pattern of irreversible and reversible changes of stress was observed as for the film resistivity. Transmission electron micrographs and secondary ion mass profiles of the film taken before and after thermal annealing in air establish that both the structure and the composition of the film scarcely change during the annealing cycles. We reason that the film stress is implicated in the resistivity change. In particular, to interpret the observations, a model is proposed where the interface between the film and the substrate is mechanically unyielding.

Amorphous thin films for solar-cell applications : final report for period September 11, 1979 - September 10, 1980 /

"Work Performed Under Contract No. AC02-77CH00178."

Amorphous thin films for solar-cell applications : quarterly report no. 1 for September 11- December 10, 1979 /

"Work Performed Under Contract No. AC02-77CH00178."

The study of ultra-low energy deposition of hydrogenated amorphous carbon thin films

This thesis is dedicated to the production and analysis of thin hydrogenated amorphous carbon films. A cascaded arc plasma source was used to produce a high density plasma of hydrocarbon radicals that deposited on a substrate at ultra low energies. The work was intended to create a better understanding of the mechanisms responsible for the film formation, by an extensive analysis on the properties of the films in correlation with the conditions used in the plasma cell. Two different precursors were used: methane and acetylene. They revealed a very different picture for the mechanism of film formation and properties. Methane was less successful, and the films formed were soft, with poor adhesion to the substrate and decomposing with time. Acetylene was the better option, and the films formed in this case were harder, with better adhesion to the substrate and stable over time. The plasma parameters could be varied to change the character of films, from polymer-like to diamond-like carbon. Films deposited from methane were grown at low deposition rates, which increased with the increase in process pressure and source power and decreased with the increase in substrate temperature and in hydrogen fraction in the carrier gas. The films had similar hydrogen content, sp3 fractions, average roughness (Ra) and low hardness. Above a deposition temperature of 350°C graphitization occurred - an increase in the sp2 fraction. A deposition mechanism was proposed, based upon the reaction product of the dissociative recombination of CH4+. There were small differences between the chemistries in the plasma at low and high precursor flow rates and low and high substrate temperatures; all experimental conditions led to formation of films that were either polymer-like, soft amorphous hydrogenated carbon or graphitic-like in structure. Films deposited from acetylene were grown at much higher deposition rates on different substrates (silicon, glass and plastics). The film quality increased noticeably with the increase of relative acetylene to argon flow rate, up to a certain value, where saturation occurred. With the increase in substrate temperature and the lowering of the acetylene injection ring position further improvements in film quality were achieved. The deposition process was scaled up to large area (5 x 5 cm) substrates in the later stages of the project. A deposition mechanism was proposed, based upon the reaction products of the dissociative recombination of C2H2 +. There were large differences between the chemistry in the plasma at low and medium/high precursor flow rates. This corresponded to large differences in film properties from low to medium flow rates, when films changed their character from polymer-like to diamond-like, whereas the differences between films deposited at medium and high precursor flow rates were small. Modelling of the film growth on silicon substrates was initiated and it explained the formation of sp2 and sp3 bonds at these very low energies. However, further improvements to the model are needed.

Efficient THz radiation from a nanocrystalline silicon-based multi-layer photomixer

In this paper we propose a novel type of multiple-layer photomixer based on amorphous/nano-crystalline-Si. Such a device implies that it could be possible to enhance the conversion efficiency from optical power to THz emission by increasing the absorption length and by reducing the device overheating through the use of substrates with higher thermal conductivity compared to GaAs. Our calculations show that the output power from a two-layer Si-based photomixer is at least ten times higher than that from conventional LT-GaAs photomixers at 1 THz.

Preparation of a microporous silicon oximide gel from the reaction of tris(dimethylamino)silylamine with formamide and its pyrolytic conversion into a silicon oxynitride based glass

A high-surface-area silicon oximide-based gel [SiOC(H)=NSi]m[Si2N-C(H)=O]n[SiN(H)-C(H)=O]p[SiOC(H)=NH]q[SiNH]r[SiNH2]s[SiNMe2]t was prepared via a formamide-based aminolysis of tris(dimethylamino)silylamine, (Me2N)3SiNH2. The structure of the gel and the mechanism of formation are elucidated. Pyrolysis of the gel at 1000 °C under N2 flow gave an amorphous microporous oxynitride-based glass with a BET surface area of 195 m2 g−1. © The Royal Society of Chemistry 2005.

Increasing the fracture toughness of silicon by ion implantation

Previous studies have shown that moderate doses of radiation can lead to increased fracture toughness in ceramics. An experimental investigation was conducted to determine the effects of ion implantation on fracture toughness in silicon. Specimens implanted with Ne showed increased fracture toughness, over the entire range of implantations tested. Using ions of various energies to better distribute implantation damage further increased the fracture toughness even though the region of amorphous damage was slightly decreased. The implantation damage accumulated in a predictable manner so that fracture toughness could be optimized.

Synthesis and characterization of cyclotriphosphazenes containing silicon as single solid-state precursors for the formation of silicon/phosphorus nanostructured materials

The synthesis and characterization of new organosilicon derivatives of N3P3Cl6, N3P3[NH(CH2)3Si(OEt)3]6 (1), N3P3[NH(CH2)3Si(OEt)3]3[NCH3(CH2)3CN]3 (2), and N3P3[NH(CH2)3Si(OEt)3]3[HOC6H4(CH2)CN]3 (3) are reported. Pyrolysis of 1, 2, and 3 in air and at several temperatures results in nanostructured materials whose composition and morphology depend on the temperature of pyrolysis and the substituents of the phosphazenes ring. The products stem from the reaction of SiO2 with P2O5, leading to either crystalline Si5(PO4)6O, SiP2O7 or an amorphous phase as the glass Si5(PO4)6O/3SiO2·2P2O5, depending on the temperature and nature of the trimer precursors. From 1 at 800 °C, core−shell microspheres of SiO2 coated with Si5(PO4)6O are obtained, while in other cases, mesoporous or dense structures are observed. Atomic force microscopy examination after deposition of the materials on monocrystalline silicon wafers evidences morphology strongly dependent on the precursors. Isolated islands of size ∼9 nm are observed from 1, whereas dense nanostructures with a mean height of 13 nm are formed from 3. Brunauer−Emmett−Teller measurements show mesoporous materials with low surface areas. The proposed growth mechanism involves the formation of cross-linking structures and of vacancies by carbonization of the organic matter, where the silicon compounds nucleate. Thus, for the first time, unique silicon nanostructured materials are obtained from cyclic phosphazenes containing silicon.

Electronic states of trans-polyacetylene, poly(p-phenylene vinylene) and sp-hybridised carbon species in amorphous hydrogenated carbon probed by resonant Raman scattering

Inclusions of sp-hybridised, trans-polyacetylene [trans-(CH)x] and poly(p-phenylene vinylene) (PPV) chains are revealed using resonant Raman scattering (RRS) investigation of amorphous hydrogenated carbon (a-C:H) films in the near IR – UV range. The RRS spectra of trans-(CH)x core Ag modes and the PPV CC-H phenylene mode are found to transform and disperse as the laser excitation energy ћωL is increased from near IR through visible to UV, whereas sp-bonded inclusions only become evident in UV. This is attributed to ћωL probing of trans-(CH)x chain inhomogeneity and the distribution of chains with varying conjugation length; for PPV to the resonant probing of phelynene ring disorder; and for sp segments, to ћωL probing of a local band gap of end-terminated polyynes. The IR spectra analysis confirmed the presence of sp, trans-(CH)x and PPV inclusions. The obtained RRS results for a-C:H denote differentiation between the core Ag trans-(CH)x modes and the PPV phenylene mode. Furthermore, it was found that at various laser excitation energies the changes in Raman spectra features for trans-(CH)x segments included in an amorphous carbon matrix are the same as in bulk trans-polyacetylene. The latter finding can be used to facilitate identification of trans-(CH)x in the spectra of complex carbonaceous materials.

Selective growth of carbon nanotubes on bare silicon : MWNT sinthesys on patterned substrates without predeposition of metal catalyst

Carbon nanotubes (CNTs) are expected to become the ideal constituent of many technologes, in particular for future generation electronics. This considerable interest is due to their unique electrical and mechanical properties. They show indeed super-high current-carrying capacity, ballistic electron transport and good field-emission properties. Then, these superior features make CNTs the most promising building blocks for electronic devices, as organic solar cells and organic light emitting devices (OLED). By using Focused Ion Beam (FIB) patterning it is possible to a obtain a high control on position, relative distances and diameter of CNTs. The present work shows how to grow three-dimensional architecture made of vertical-aligned CNTs directly on silicon. Thanks to the higher activity of a pre-patterned surface the synthesis process results very quick, cheap and simple. Such large area growths of CNTs could be used in preliminary test for application as electrodes for organic solar cells.