T. A. Friedmann

Thick stress-free amorphous-tetrahedral carbon films with hardness near that of diamond

We have developed a process for making thick, stress-free, amorphous-tetrahedrally bonded carbon (a-tC) films with hardness and stiffness near that of diamond. Using pulsed-laser deposition, thin a-tC films (0.1–0.2 μm) were deposited at room temperature. The intrinsic stress in these films (6–8 GPa) was relieved by a short (2 min) anneal at 600 °C. Raman and electron energy-loss spectra from single-layer annealed specimens show only subtle changes from as-grown films. Subsequent deposition and annealing steps were used to build up thick layers. Films up to 1.2 μm thick have been grown that are adherent to the substrate and have low residual compressive stress (<0.2 GPa). The values of hardness and modulus determined directly from an Oliver–Pharr analysis of nanoindentation experimental data were 80.2 and 552 GPa, respectively. We used finite-element modeling of the experimental nanoindentation curves to separate the “intrinsic” film response from the measured substrate/film response. We found a hardness ...

Finite-element modeling of nanoindentation

Procedures have been developed based on finite-element modeling of nanoindentation data to obtain the mechanical properties of thin films and ion-beam-modified layers independently of the properties of the underlying substrates. These procedures accurately deduce the yield strength, Young’s elastic modulus, and layer hardness from indentations as deep as 50% of the layer thickness or more. We have used these procedures to evaluate materials ranging from ion implanted metals to deposited, diamond-like carbon layers. The technique increases the applicability of indentation testing to very thin layers, composite layers, and modulated compositions. This article presents an overview of the procedures involved and illustrates them with selected examples.

Ion‐assisted pulsed laser deposition of cubic boron nitride films

Ion‐assisted pulsed laser deposition has been used to produce films containing ≳85% sp3‐bonded cubic boron nitride (c‐BN). By ablating from a target of hexagonal boron nitride (h‐BN), BN films have been deposited on heated (50–800 °C) Si(100) surfaces. The growing films are irradiated with ions from a broad beam ion source operated with Ar and N2 source gasses. Successful c‐BN synthesis has been confirmed by Fourier transform infrared (FTIR) spectroscopy, high‐resolution transmission electron microscopy (TEM), selected‐area electron diffraction, electron energy‐loss spectroscopy, and x‐ray diffraction. The films are polycrystalline and show grain sizes up to 300 A. In addition, Rutherford backscattering, elastic recoil detection, and Auger electron spectroscopies have been used to further characterize the samples. The effects of varying ion current density, substrate growth temperature, growth time, and ion energy have been investigated. It is found that stoichiometric films with a high c‐BN percentage ca...

Thermal stability of amorphous carbon films grown by pulsed laser deposition

The thermal stability in vacuum of amorphous tetrahedrally coordinated carbon (a‐tC) films grown on Si has been assessed by in situ Raman spectroscopy. Films were grown in vacuum on room‐temperature substrates using laser fluences of 12, 22, and 45 J/cm2 and in a background gas of either hydrogen or nitrogen using a laser fluence of 45 J/cm2. The films grown in vacuum at high fluence (≳20J/cm2) show little change in the a‐tC Raman spectra with temperature up to 800 °C. Above this temperature the films convert to glassy carbon (nanocrystalline graphite). Samples grown in vacuum at lower fluence or in a background gas (H2 or N2) at high fluence are not nearly as stable. For all samples, the Raman signal from the Si substrate (observed through the a‐tC film) decreases in intensity with annealing temperature indicating that the transparency of the a‐tC films is decreasing with temperature. These changes in transparency begin at much lower temperatures (∼200 °C) than the changes in the a‐tC Raman band shape an...

Microstructure of cubic boron nitride thin films grown by ion‐assisted pulsed laser deposition

A microstructural study of boron nitride films grown by ion‐assisted pulsed laser deposition is presented. Fourier transform infrared spectroscopy, electron‐energy‐loss spectroscopy, and electron‐diffraction measurements indicate that within the ion‐irradiated region on the substrate, the film consists of a high fraction of the cubic phase (cBN) with a small amount of the turbostratic phase; outside the irradiated region, only the turbostratic phase is detected. Conventional and high‐resolution electron microscopic observations show that the cBN is in the form of twinned crystallites, up to 40 nm in diameter. Particulates, formed by the laser ablation process, reduce the yield of cBN in the irradiated regions by shadowing local areas from the ion beam. The films exhibit a layered structure with an approximately 30‐nm‐thick layer of oriented turbostratic material forming initially at the silicon substrate followed by the cBN. The observations of oriented turbostratic material and twinned cBN crystallites a...

Characterization of electron emission from planar amorphous carbon thin films using in situ scanning electron microscopy

Electron emission characteristics combined with in situ scanning electron microscope images have been measured on a series of amorphous carbon films grown by pulsed laser deposition. Uniform, reproducible current–voltage characteristics without morphological damage are only observed with sequential voltage ramps ⩽5 V/s for anode-cathode gaps of 10–200 μm. The field threshold and emission barrier increase with laser energy density used during film growth. This dependence of emission parameters on film growth conditions appears to be correlated with the presence of conducting filaments extending through the film thickness.

Amorphous-tetrahedral diamondlike carbon layered structures resulting from film growth energetics

High-resolution transmission electron microscopy (HRTEM) shows that amorphous-tetrahedral diamondlike carbon (a-tC) films grown by pulsed-laser deposition on Si(100) consist of three-to-four layers, depending on the growth energetics. We estimate the density of each layer using both HRTEM image contrast and Rutherford backscattering spectrometry. The first carbon layer and final surface layer have relatively low density. The bulk of the film between these two layers has higher density. For films grown under the most energetic conditions, there exists a superdense a-tC layer between the interface and bulk layers. The density of all four layers, and the thickness of the surface and interfacial layers, correlate well with the energetics of the depositing carbon species.

Elasticity, strength, and toughness of single crystal silicon carbide, ultrananocrystalline diamond, and hydrogen-free tetrahedral amorphous carbon

In this work, the authors report the mechanical properties of three emerging materials in thin film form: single crystal silicon carbide (3C-SiC), ultrananocrystalline diamond, and hydrogen-free tetrahedral amorphous carbon. The materials are being employed in micro- and nanoelectromechanical systems. Several reports addressed some of the mechanical properties of these materials but they are based in different experimental approaches. Here, they use a single testing method, the membrane deflection experiment, to compare these materials’ Young’s moduli, characteristic strengths, fracture toughnesses, and theoretical strengths. Furthermore, they analyze the applicability of Weibull theory [Proc. Royal Swedish Inst. Eng. Res. 153, 1 (1939); ASME J. Appl. Mech. 18, 293 (1951)] in the prediction of these materials’ failure and document the volume- or surface-initiated failure modes by fractographic analysis. The findings are of particular relevance to the selection of micro- and nanoelectromechanical systems m...

Crystallographic texture in cubic boron nitride thin films

We examine the crystallographic texture exhibited by cubic boron nitride (cBN) in thin films grown by ion‐assisted deposition. Our analysis indicates that the cBN is preferentially oriented such that individual crystallites have at least one [111] direction lying in the plane of the film but are otherwise randomly oriented about (1) the substrate normal and (2) the in‐plane cBN [111] axis. This preferential orientation is consistent with an alignment between the cBN {111} planes and the basal planes of the layer of highly oriented graphitic boron nitride that forms in the initial stages of film growth.

Electron emission induced modifications in amorphous tetrahedral diamondlike carbon

The cold-cathode electron emission properties of amorphous tetrahedral diamondlike carbon are promising for flat-panel display and vacuum microelectronics technologies. The onset of electron emission is, typically, preceded by “conditioning” where the material is stressed by an applied electric field. To simulate conditioning and assess its effect, we combined the spatially localized field and current of a scanning tunneling microscope tip with high-spatial-resolution characterization. Scanning force microscopy shows that conditioning alters surface morphology and electronic structure. Spatially resolved electron-energy-loss spectroscopy indicates that the predominant bonding configuration changes from predominantly fourfold to threefold coordination.