The coefficient of thermal expansion ͑CTE͒, biaxial modulus, and stress of some amorphous semiconductors ͑a-Si:H, a-C:H, a-Ge:H, and a-GeC x :H͒ and metallic ͑Ag and Al͒ thin films were studied. The thermal expansion and the biaxial modulus were measured by the thermally induced bending technique. The stress of the metallic films, deposited by thermal evaporation ͑Ag and Al͒, is tensile, while that of the amorphous films deposited by sputtering ͑a-Si:H, a-Ge:H, and a-GeC x :H͒ and by glow discharge (a-C:H) is compressive. We observed that the coefficient of thermal expansion of the tetrahedral amorphous thin films prepared in this work, as well as that of the films reported in literature, depend on the network strain. The CTE of tensile films is smaller than that of their corresponding crystalline semiconductors, but it is higher for compressive films. On the other hand, we found out that the elastic biaxial modulus of the amorphous and metallic films is systematically smaller than that of their crystalline counterparts. This behavior stands for other films reported in the literature that were prepared by different techniques and deposition conditions. These differences were attributed to the reduction of the coordination number and to the presence of defects, such as voids and dangling bonds, in amorphous films. On the other hand, columnar structure and microcrystallinity account for the reduced elasticity of the metallic films.
Neutral species and positive ions were extracted directly from a C2H2:NH3 plasma used to grow vertically aligned carbon nanotubes (CNTs) and analyzed by mass spectrometry. We observe that NH3 suppresses C2H2 decomposition and encourages CNT formation. We show that the removal of excess carbon, essential for obtaining nanotubes without amorphous carbon deposits, is achieved through gas phase reactions which form mainly HCN. We determine an optimum C2H2:NH3 gas ratio which is consistent with previous observations based upon postdeposition analysis. We find, in contrast to thin film growth by plasma-enhanced chemical vapor deposition, that the optimum condition does not correspond to the highest level of ionization. We also provide evidence that C2H2 is the dominant precursor for CNTs in our experiments.
The coefficient of thermal expansion (CTE) of hydrogenated amorphous carbon (a-C:H) was investigated as a function of the concentration of sp2 hybridization. The CTE, determined using the thermally induced bending technique, depends on the concentration of sp2 bonded carbon, increasing to the value of graphite as the sp2 concentration approaches 100%. By using a combination of the thermally induced bending technique and nanohardness measurements, we extract separately the Young’s modulus and Poisson’s ratio of the a-C:H films as function of the sp2 concentration.
Analysis of hard a-C:H films with low stress prepared by methane plasma decomposition is reported. Films with hardness as high as 14 GPa and stress as low as 0.5 GPa were obtained. These films have a high Raman Id/Ig ratio (∼1.0), and small Tauc’s band gap (∼0.4 eV). This letter also supplies strong evidence that the subimplantation deposition model, used to explain the formation of ta-C and ta-C:H films, is also valid for a-C:H films deposited by methane plasma decomposition. It is proposed that the rigidity of the films is basically provided by a matrix of dispersed cross-linked sp2 sites, in addition to the contribution of the sp3 sites.
Noble gases ͑Ar, Kr, and Xe͒ were trapped in an amorphous carbon matrix in the 1-11-GPa pressure range. Extended and near-edge x-ray-absorption spectroscopies indicate clustering of noble gases induced by the host matrix internal pressure. Simultaneously, the matrix pressure promotes a shift of the noble-gas core-level binding energy of ϳ1 eV. The Auger parameter reveals that both the initial state and the host relaxation terms contribute to the binding-energy shift. Ab initio calculations performed on an Ar 7 cluster and on Ar atoms clustered in aromatic molecules support the experimental findings.
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