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Melt Infiltration Studies of 2D Tyranno SA3(R) Ceramic Matrix Composite Preforms with CrSi2 Intermetallic Alloy

The present paper reports the results of melt infiltrating 2D Tyranno SA3@ fiber woven preforms with molten CrSi2 between 1768 and 1896 K under a vacuum of 1.3 x 10-4 Pa (10-6 torr). The infiltration times varied between 1800 and 7200 s, which did not have any significant effect on the volume fraction of voids filled with the metal. Optical and scanning electron microscopy, back scattered electron imaging, energy dispersion spectroscopy and Raman spectroscopy were used to characterize the infiltrated preforms. A plot of the volume fraction of open voids infiltrated against the absolute melt infiltration temperature showed a sharp peak at 1773 K with almost complete infiltration of the voids at this temperature. The extent of silicide infiltration of the preforms dropped steeply above 1773 K with increasing melt infiltration temperature irrespective of the amount of infiltration time. Above 1805 K, the volume fraction of voids infiltrated with the melt was nearly 0%. It is demonstrated that CrSi2 did not show evidence of a reaction with the SiC fibers. The possibility that a resisting force due to contact angle hysteresis (CAH) may have influenced the diminishing amount of voids filled with increasing temperature above 1773 K was examined. The resistance force was estimated to be extremely small to be consequential. Another possibility that the CrSi2 may have decomposed into Cr(g) and Si(g) in the vacuum melt infiltration furnace appeared to be more plausible based on thermodynamic analyses. An empirical equation is proposed to calculate the amount of remaining charge left to infiltrate the preforms at the infiltration temperature. It is shown that an initial charge of 10 g would rationalize the present observations. While the decomposition of the CrSi2 appeared to mostly explain the present results, some discrepancies were observed, which were inconsistent with the decomposition model.

CrSi2, chromium silicide, ceramic matrix composite↗

Molecular-Beam Epitaxy Of CrSi2 on Si(111)

Crystalline layers grown in commercial apparatus. Experiments show CrSi2 grown on (111) face of single-crystal Si substrate by molecular-beam epitaxy. Epitaxial CrSi2 produced thus far not in desired single-crystal form. Because CrSi2 semiconductor with band gap of 0.3 eV, experimental process potential for monolitic integration of microelectronic devices based on CrSi2 (e.g., infrared detectors) with signal-processing circuitry based on Si.

Fathauer, Robert W.↗

Temperature-dependent ion mixing and diffusion during sputtering of thin films of CrSi2 on silicon

Measurements of sputtering yields and composition profiles have been carried out using backscattering spectrometry for samples of CrSi2 on Si irradiated wth 200-keV Xe ions. When the CrSi2 layer is thinner than the ion range, the sputtering yield ratio of Si to Cr increases from 3.5 for room-temperature irradiation to 65 at 290 C. For a thick sample, the corresponding increase is from 2.4 to 4.0 only. These changes are explained in terms of a rise in the Si surface concentration ot 290 C. The driving force for this process seems to be the establishment of stoichiometric CrSi2 compound. Transport of Si to the surface is by ion mixing in the thin sample and thermal diffusion through the thick layer.

Shreter, U.↗

Molecular-beam epitaxy of CrSi2 on Si(111)

The growth of CrSi2 on Si(111) in a commercial MBE system with a base pressure in the low 10 to the -11th torr range is reported. CrSi2 layers grown on Si(111) exhibit a strong tendency to form islands. Two particular epitaxial relationships are identified. Thick (210 nm) layers have been grown by four different techniques, with best results obtained by codepositing Cr and Si at elevated temperature. The grain size is observed to increase with substrate temperature, reaching 1-2 microns in a layer deposited at 825 C.

Fathauer, R. W.↗

Dopant redistribution during the solid-phase growth of CrSi2 on Si(100)

The distribution pattern of As, B, and P dopants during the solid-phase growth of CrSi2 on Si(100) was investigated using Rutherford backscattering spectroscopy and SIMS. The results demonstrated that all three dopants did redistribute during the formation of CrSi2 layers; however, the nature of redistribution was different for different dopants. While B and P were transported from the Si substrate to the surface of the growing CrS2 layer, As accumulated at the CrSi2/Si interface. The formation of silicide was found to be inhibited by large concentrations of As. A model was developed to explain these results.

Rockett, A.↗

Nucleation and growth of CrSi2 on Si(111)

The nucleation and growth of CrSi2 on Si(111) by MBE and solid-phase epitaxy (SPE), was investigated using SEM and TEM observations of 2-mm-thick layers grown under a variety of conditions, including the use of a CoSi2 buffer. During growth, the wafers were monitored in situ using reflection high-energy electron diffraction. Island growth was observed, with islands found to nucleate with three epitaxial orientations. The morphology of CrSi2 islands was found to be affected by the degree and direction of substrate misorientation, the growth technique, and the use of CoSi2 buffer. However, the reconstruction of the Si surface does not appear to be an important factor in controlling SPE growth.

Fathauer, R. W.↗

Materials Data on CrSi2 by Materials Project

CrSi2 is Titanium Disilicide-like structured and crystallizes in the hexagonal P6_422 space group. The structure is three-dimensional. Cr is bonded in a distorted q6 geometry to ten equivalent Si atoms. There are a spread of Cr–Si bond distances ranging from 2.48–2.55 Å. Si is bonded in a 10-coordinate geometry to five equivalent Cr and five equivalent Si atoms. There are a spread of Si–Si bond distances ranging from 2.47–2.55 Å.

36 MATERIALS SCIENCE↗

Materials Data on CrSi2 by Materials Project

CrSi2 is Titanium Disilicide-like structured and crystallizes in the hexagonal P6_222 space group. The structure is three-dimensional. Cr is bonded in a distorted q6 geometry to ten equivalent Si atoms. There are a spread of Cr–Si bond distances ranging from 2.48–2.55 Å. Si is bonded in a 10-coordinate geometry to five equivalent Cr and five equivalent Si atoms. There are a spread of Si–Si bond distances ranging from 2.47–2.55 Å.

36 MATERIALS SCIENCE↗

Materials Data on CrSi2 by Materials Project

CrSi2 is Titanium Disilicide-like structured and crystallizes in the tetragonal I4/mmm space group. The structure is three-dimensional. Cr is bonded in a distorted q6 geometry to ten equivalent Si atoms. There are eight shorter (2.50 Å) and two longer (2.54 Å) Cr–Si bond lengths. Si is bonded in a 10-coordinate geometry to five equivalent Cr and five equivalent Si atoms. There are one shorter (2.46 Å) and four longer (2.54 Å) Si–Si bond lengths.

36 MATERIALS SCIENCE↗

Narrow bandgap semiconducting silicides: Intrinsic infrared detectors on a silicon chip

Work done during the final report period is presented. The main technical objective was to achieve epitaxial growth on silicon of two semiconducting silicides, ReSi2 and CrSi2. ReSi2 thin films were grown on (001) silicon wafers by vacuum evaporation of rhenium onto hot substrates in ultrahigh vacuum. The preferred epitaxial relationship was found to be ReSi2(100)/Si(001) with ReSi2(010) parallel to Si(110). The lattice matching consists of a common unit mesh of 120 A(sup 2) area, and a mismatch of 1.8 percent. Transmission electron microscopy revealed the existence of rotation twins corresponding to two distinct but equivalent azimuthal orientations of the common unit mesh. MeV He(+) backscattering spectrometry revealed a minimum channeling yield of 2 percent for an approximately 1,500 A thick film grown at 650 C. Although the lateral dimension of the twins is on the order of 100 A, there is a very high degree of alignment between the ReSi2(100) and the Si(001) planes. Highly oriented films of CrSi2 were grown on (111) silicon substrates, with the matching crystallographic faces being CrSi2(001)/Si(111). The reflection high-energy electron diffraction (RHEED) patterns of the films consist of sharp streaks, symmetrically arranged. The predominant azimuthal orientation of the films was determined to be CrSi2(210) parallel to Si(110). This highly desirable heteroepitaxial relationship has been obtained previously by others; it may be described with a common unit mesh of 51 A(sup 2) and mismatch of 0.3 percent. RHEED also revealed the presence of limited film regions of a competing azimuthal orientation, CrSi2(110) parallel to Si(110). A channeling effect for MeV He(+) ions was not found for this material. Potential commercial applications of this research may be found in silicon-integrated infrared detector arrays. Optical characterizations showed that semiconducting ReSi2 is a strong absorber of infrared radiation, with the adsorption constant increasing above 2 x 10(exp 4) cm(sup -1) for photon energies above 0.2 eV. CrSi2 is of potential utility for detection at photon energies above approximately 0.3 eV.

Mahan, John E.↗

Narrow bandgap semiconducting silicides: Intrinsic infrared detectors on a silicon chip

Polycrystalline thin films of CrSi2, LaSi2, and ReSi2 were grown on silicon substrates. Normal incidence optical transmittance and reflectance measurements were made as a function of wavelength. It was demonstrated that LaSi2 is a metallic conductor, but that CrSi2 and ReSi2 are, in fact, narrow bandgap semiconductors. For CrSi2, the complex index of refraction was determined by computer analysis of the optical data. From the imaginary part, the optical absorption coefficient was determined as a function of photon energy. It was shown that CrSi2 possesses an indirect forbidden energy gap of slightly less than 0.31 eV, and yet it is a very strong absorber of light above the absorption edge. On the other hand, the ReSi2 films exhibit an absorption edge in the vicinity of 0.2 eV. Measurements of the thermal activation energy of resistivity for ReSi2 indicate a bandgap of 0.18 eV. It is concluded that the semiconducting silicides merit further investigation for development as new silicon-compatible infrared detector materials.

Mahan, John E.↗

Chromium silicide formation by ion mixing

The formation of CrSi2 by ion mixing was studied as a function of temperature, silicide thickness and irradiated interface. Samples were prepared by annealing evaporated couples of Cr on Si and Si on Cr at 450 C for short times to form Si/CrSi2/Cr sandwiches. Xenon beams with energies up to 300 keV and fluences up to 8 x 10 to the 15th per sq cm were used for mixing at temperatures between 20 and 300 C. Penetrating only the Cr/CrSi2 interface at temperatures above 150 C induces further growth of the silicide as a uniform stoichiometric layer. The growth rate does not depend on the thickness of the initially formed silicide at least up to a thickness of 150 nm. The amount of growth depends linearly on the density of energy deposited at the interface. The growth is temperature dependent with an apparent activation energy of 0.2 eV. Irradiating only through the Si/CrSi2 interface does not induce silicide growth. It is concluded that the formation of CrSi2 by ion beam mixing is an interface-limited process and that the limiting reaction occurs at the Cr/CrSi2 interface.

Shreter, U.↗

Columnar epitaxy of hexagonal and orthorhombic silicides on Si(111)

Columnar grains of PtSi and CrSi2 surrounded by high-quality epitaxial silicon are obtained by ultrahigh vacuum codeposition of Si and metal in an approximately 10:1 ratio on Si(111) substrates heated to 610-840 C. This result is similar to that found previously for CoSi2 (a nearly-lattice-matched cubic-fluorite crystal) on Si(111), in spite of the respective orthorhombic and hexagonal structures of PtSi and CrSi2. The PtSi grains are epitaxial and have one of three variants of the relation defined by PtSi(010)/Si(111), with PtSi 001 line/Si 110 line type.

Fathauer, R. W.↗

Interaction of metal layers with polycrystalline Si

Solid-phase reactions of metal films deposited on 0.5-micron-thick polycrystalline layers of Si grown by chemical vapor deposition at 640 C were investigated by MeV He-4 backscattering spectrometry, glancing angle X-ray diffraction, and SEM observations. For the metals Al, Ag, and Au, which form simple eutectics, heat treatment at temperatures below the eutectic results in erosion of the poly-Si layer and growth of Si crystallites in the metal film. Crystallite formation is observed at temperatures exceeding 550 C for Ag, at those exceeding 400 C for Al, and at those exceeding 200 C for Au films. For Pd, Ni, and Cr, heat treatment results in silicide formation. The same initial silicides (Pd2Si, Ni2Si, and CrSi2), are formed at similar temperatures on single-crystal substrates.

Nakamura, K.↗

An investigation of the optical constants and band gap of chromium disilicide

Optical properties of polycrystalline thin films of CrSi2 grown by the diffusion couple method on silicon substrates were investigated. An analysis of the energy dependence of the absorption coefficient indicates that the material is an indirect forbidden gap semiconductor with a band-gap value of slightly less than 0.35 eV. This result was confirmed by measurements of the temperature dependence of the intrinsic conductivity. The value of the bandgap corresponds well to an important window of transparency in the earth's atmosphere (3-5 microns), which makes the material of potential interest for IR detector applications.

Bost, M. C.↗

High Temperature Lightweight Self-Healing Ceramic Composites for Aircraft Engine Applications

The present research effort was undertaken to develop a new generation of SiC fiber- reinforced engineered matrix composites (EMCs) with sufficient high temperature plasticity to reduce crack propagation and self-healing capabilities to fill surface-connected cracks to prevent the oxygen ingress to the fibers. A matrix engineered with these capabilities is expected to increase the load bearing capabilities of SiCSiC CMCs at high temperatures. Several matrix compositions were designed to match the coefficient of thermal expansion (CTE) of the SiC fibers using a rule of mixture (ROM) approach. The CTE values of these matrices were determined and it was demonstrated that they were generally in good agreement with that of monolithic SiC between room temperature and 1525 K. The parameters to hot press the powders were optimized, and specimens were fabricated for determining bend strength, CTE, oxidation and microstructural characteristics of the engineered matrices. The oxidation tests revealed that some of the matrices exhibited catastrophic oxidation, and therefore, these were eliminated from further consideration. Two promising compositions were down selected based on these results for further development. Four-point bend tests were conducted on these two promising matrices between room temperature and 1698 K. Although theses matrices were brittle and failed at low stresses at room temperature, they exhibited high temperature ductility and higher stresses at the higher temperatures. The effects of different additives on the self-healing capabilities of these matrices were investigated. The results of preliminary studies conducted to slurry and melt infiltration trials with CrSi2 are described.

Silicides↗