Micromechanical properties of carbon nitride films deposited by radio-frequency-assisted filtered cathodic vacuum arc

Super-hard and elastic carbon nitride films have been synthesized by using an off-plane double-bend filtered cathodic vacuum arc combined with a radio-frequency nitrogen-ion beam source. A nanoindenter was used to determine the micromechanical properties of the deposited films. X-ray photoelectron spectroscopy was used to study the composition and bonding structure of the deposited films. The influence of nitrogen ion energy on the structure and micromechanical properties of the deposited films was systematically studied. As the nitrogen ion energy is increased, the microhardness, Young’s modulus and elastic recovery also increase, reaching a maximum of 47 GPa, 400 GPa, and 87.5%, respectively, at a nitrogen ion energy of 100 eV. Further increase in nitrogen ion energy results in a decrease in microhardness, Young’s modulus and elastic recovery of the deposited films. The formation of five-membered rings, as indicated by XPS, which causes bending of the basal planes and forms a three-dimensional rigid covalent bond network, contributes to the super-hardness, Young’ s modulus and high elastic recovery of the films deposited at a nitrogen ion energy of 100 eV. Revised version: 29 October 2001 / Accepted: 7 November 2001 / Published online: 2 May 2002     

Transport and dynamics of optically excited electrons in metals

Time-resolved two-photon photoemission, based on the equal-pulse correlation technique, is used to measure the energy relaxation and the transport of the photoexcited carriers in thin Ag and Au films. The energy-dependent relaxation time shows a significant thickness dependence in the Ag film, whereas for Au a much smaller effect is observed. These experimental observations are compared with a theoretical model based on the Boltzmann equation, which includes secondary (Auger) electrons and transport. A good agreement between experimental and theoretical results is found for Au. However, in our calculations, we did not find any significant change in the thickness dependence in the case of Ag. In order to explain the strong effect in Ag, we discuss the possibility of surface excitations. Received: 15 May 2000 / Accepted: 2 September 2000 / Published online: 12 October 2000     

Patterning of YBa2Cu3O7-δ films using a near-field optical configuration

2 Cu₃O_7-δ films have been patterned by means of an arrangement employed in scanning near-field optical microscopy (SNOM). Standard SNOM probes were modified to achieve high transmission for direct writing by oxygen depletion in N₂ atmosphere. The written lines are about 1.5 μm wide and show a semiconductor-like resistivity behavior (δ≥0.5). The morphology of illuminated regions is about the same as that of the YBCO films. Received: 3 July 1998/Accepted: 6 July 1998     

Time-resolved thermoreflectivity of thin gold films and its dependence on film thickness

\valunit{10}{nm} to have been measured by femtosecond time-resolved pump-probe experiments. A conspicuous change of the relaxation behavior was found around for pump pulse fluences of . Thicker films show a nearly exponential decay of the transient linear reflectivity, which turns into a linear decay during the first for films with thicknesses of or less. This observation is evidence of a mean free path of about for hot electrons with temperatures around . Received: 17 December 1996     

Structural and electrical properties of tantalum nitride thin films fabricated by using reactive radio-frequency magnetron sputtering

TaN thin film is an attractive interlayer as well as a diffusion barrier layer in [FeN/TaN]_n multilayers for the application as potential write-head materials in high-density magnetic recording. We synthesized two series of TaN films on glass and Si substrates by using reactive radio-frequency sputtering under 5-mtorr Ar/N₂ processing pressure with varied N₂ partial pressure, and carried out systematic characterization analyses of the films. We observed clear changes of phases in the films from metallic bcc Ta to a mixture of bcc Ta(N) and hexagonal Ta₂N, then sequentially to fcc TaN and a mixture of TaN with N-rich phases when the N₂ partial pressure increased from 0.0% to 30%. The changes were associated with changes in the grain shapes as well as in the preferred crystalline orientation of the films from bcc Ta [100] to [110], then to random and finally to fcc TaN [111], correspondingly. They were also associated with a change in film resistivity from metallic to semiconductor-like behavior in the range of 77–295 K. The films showed a typical polycrystalline textured structure with small, crystallized domains and irregular grain shapes. Clear preferred (111) stacks parallel to the substrate surface with embedded amorphous regions were observed in the film. TaN film with [111]-preferred orientation and a resistivity of 6.0 mΩ cm was obtained at 25% N₂ partial pressure, which may be suitable for the interlayer in [FeN/TaN]_n multilayers. Received: 6 December 1999 / Accepted: 24 July 2000 / Published online: 9 November 2000     

Synthesis of carbon nitride films by low-power inductively coupled plasma-activated transport reactions from a solid carbon source

Thin films of carbon nitride were prepared by low-power inductively coupled plasma chemical vapor deposition from a solid carbon source by utilizing transport reactions. The maximum deposition rate achieved was 10 nm/min and depended mainly on the substrate position in the reactor. The nitrogen fraction in the films was not so sensitive to the process parameters and was at about 0.5 for all experiments as measured by Auger electron spectroscopy (AES) and elastic recoil detection (ERD) analysis. The chemical bonding structure studied by Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) showed the presence of triple, double and single bonds between carbon and nitrogen atoms. Received: 12 May 1999 / Accepted: 12 May 1999 / Published online: 24 June 1999     

Core-level and valence-band characteristics of carbon nitride films with high nitrogen content

Carbon nitride films with high nitrogen content were prepared by reactive pulsed-laser deposition at nitrogen partial pressures varying from 0.1 to 20.0 Torr. It was found that the nitrogen content in the films first increases with increase of the nitrogen pressure, reaches a maximum of 46 at. % at 5.0 Torr, and then decreases to 37 at. % at 20.0 Torr. The almost pure carbon nitride films were systematically characterized by using X-ray photoelectron spectroscopy (XPS) concerning the core-level and valence-band structures. Some fingerprint information, which shows the role of nitrogen in controlling the electronic structure of carbon nitride films, was found based on the XPS studies. With enhancing the nitrogen incorporation, both the binding energy and the peak intensity of the core-level and the valence-band spectra vary systematically as a function of nitrogen content in the films. Received: 26 June 2000 / Accepted: 26 June 2000 / Published online: 20 September 2000     

Effects of the indium doping on structural and optical properties of CdSe thin films deposited by laser ablation technique

Thin films of n-type CdSe have been grown on a quartz substrate by laser ablating a target obtained by mixing CdSe and metallic In powders. The effects of different doping concentration of In have been investigated. X-ray diffraction spectra show that at low In density only the CdSe lattice is present in the deposited film, whereas CdIn₂Se₄ and InSe compounds are deposited at higher In concentration. Band gap narrowing and band tails are observed in the absorption spectra when the In concentration increases. Photoluminescence spectra show band-band recombinations from 10 K to room temperature. Received 27 September 2002 Published online 11 April 2003 RID="a" ID="a"e-mail: giuseppe.perna@ba.infn.it     

Femtosecond optical second harmonic generation by metal clusters: The influence of inhomogeneous line broadening on the dephasing time of surface plasmon excitation

Received: 4 December 1998     

Raman characteristics of carbon nitride synthesized by nitrogen-ion-beam-assisted pulsed laser deposition

Raman characteristics of carbon nitride films synthesized by nitrogen-ion-beam-assisted pulsed laser deposition were investigated. In addition to the D (disorder) band and G (graphitic) band commonly observed in carbon nitride films, two Raman bands located at 1080–1100 and 1465–1480 cm^-1 were found from our carbon nitride films. These two bands were well matched with the predicted Raman frequencies for βC₃N₄ and the observed Raman bands reported for carbon nitride films, indicating their relation to carbon-nitrogen stretching vibrations. Furthermore, the relative intensity ratio of the two Raman bands to the D and G bands increased linearly with increasing nitrogen content of the carbon nitride films. Received: 30 October 2000 / Accepted: 5 February 2001 / Published online: 2 October 2001     

Optical studies on the deposition of carbon nitride films by laser ablation

2 radicals when the 355 and 1064 nm outputs of a Nd:YAG laser were applied. While for the 532 nm ablation, a relatively higher concentration of excited atomic carbon was obtained. Different Raman and FTIR spectral features were observed from the deposited films with different ablation wavelengths. The 532 nm laser ablation is proposed for the synthesis of high quality carbon nitride films. Received: 16 October 1996 / Accepted: 11 April 1997     

Investigation of the interaction of evaporated aluminum with vapor deposited Teflon AF films via X-ray photoelectron spectroscopy

The interfacial bonding and mixing between evaporated aluminum and a vapor deposited Teflon AF (abbreviated to AF) film have been investigated with X-ray photoelectron spectroscopy. Graphite carbon (C–C), and aluminum carbide (Al–C), oxide (Al–O–C) and fluoride (Al–F) are formed when aluminum atoms are deposited on to the AF film. With increasing deposition of aluminum, the concentrations of these newly formed components increase gradually. Moreover, in situ annealing results in remarkable increases in the C–C, Al–C, Al–O–C and Al–F configurations and a decrease in metallic aluminum. No significant diffusion of aluminum into the AF film was observed during the annealing. The Al compounds form a layer at the Al/AF interface that acts as an adhesion promoter and diffusion barrier. Received: 21 October 2002 / Accepted: 22 October 2002 / Published online: 15 January 2003 RID="*" ID="*"Corresponding author. Fax: +49-431/880-6229, E-mail: sjding@yahoo.com     

Observation of a sharp lambda peak in the third harmonic voltage response of high-T superconductor thin films

In this paper, we report on the sharp peak observed in the third harmonic voltage response generated by a bias sinusoidal current applied to several strips patterned in a YBa₂Cu₃O _{7 - δ} thin film and in two La_2-xSr_xCuO₄ thin films, when the temperature is close to the normal-superconductor transition. The lambda-shaped temperature dependence of the third harmonic signal on the current characteristics is studied. Several physical mechanisms of third harmonic generation are examined. Received 13 November 2002 / Received in final form 21 February 2003 Published online 7 May 2003     

Raman spectroscopy of a-C:H:N films deposited using ECR-CVD with mixed gas

Ultraviolet (UV) and visible Raman spectroscopy were used to study a-C:H:N films deposited using ECR-CVD with a mixed gas of CH₄ and N₂. Small percentage of nitrogen from 0 to 15% is selected. Raman spectra show that CN bonds can be directly observed at 2220 cm⁻¹ from the spectra of visible and UV Raman. UV Raman enhances the sp¹ CN peak than visible Raman. In addition, the UV Raman spectra can reveal the presence of the sp³ sites. For a direct correlation of the Raman parameter with the N content, we introduced the G peak dispersion by combining the visible and UV Raman. The G peak dispersion is directly relative to the disorder of the sp² sites. It shows the a-C:H:N films with higher N content will induce more ordered sp² sites. In addition, upper shift of T position at 244 nm excitation with the high N content shows the increment of sp² fraction of films. That means the films with high N content will become soft and contain less internal stress. Hardness test of films also confirmed that more N content is with less hardness.     

The determination of the lifetime of hot electrons in metals by time-resolved two-photon photoemission: the role of transport effects, virtual states, and transient excitons

Experience has shown that theoretically determined lifetimes of bulk states of hot electrons in real metals agree quantitatively with the experimental ones, if theory fully takes into account the crystal structure and many-body effects of the investigated metal, i.e., if the Dyson equation is solved at the ab initio level and the effective electron–electron interaction is determined beyond the plasmon-pole approximation. Therefore the hitherto invoked transport effect [Knoesel et al.: Phys. Rev. B 57, 12812 (1998)] does not seem to exist. In this paper we show that likewise neither virtual states [Hertel: et al. Phys. Rev. Lett. 76, 535 (1996)] nor damped band-gap states [Ogawa: et al.: Phys. Rev. B 55, 10869 (1997)] exist, but that the hitherto unexplained d-band catastrophe in Cu [Cu(111), Cu(110)] can be naturally resolved by the concept of the transient exciton. This is a new quasiparticle in metals, which owes its existence to the dynamical character of dielectric screening at the microscopic level. This means that excitons, though they do not exist under stationary conditions, can be observed under ultrafast experimental conditions. Received: 30 March 2000 / Accepted: 2 September 2000 / Published online: 12 October 2000     

Rapid crystallization of silicon films using Joule heating of metal films

50-nm thick amorphous silicon films formed on glass substrates were crystallized by rapid Joule heating induced by an electrical current flowing in 100-nm-thick Cr strips formed adjacently to 200-nm-thick SiO₂ intermediate layers. 3-μs-pulsed voltages were applied to the Cr strips. Melting of the Cr strips caused a high Joule heating intensity of about 1×10⁶ W/cm². Raman scattering measurements revealed complete crystallization of the silicon films at a Joule heating energy of 1.9 J/cm² via the SiO₂ intermediate layer. Transmission electron microscopy measurements confirmed a crystalline grain size of 50–100 nm. 1-μm-long crystalline grain growth was also observed just beneath the edge of the Cr strips. The electrical conductivity increased from 10^-5 S/cm to 0.3 S/cm for 7×10¹⁷-cm^-3-phosphorus-doped silicon films because of activation of the phosphorus atoms because of crystallization. The numerical analysis showed a density of localized defect states at the mid gap of 8.0×10¹⁷ cm^-3. Oxygen plasma treatment at 250 °C and 100 W for 5 min reduced the density of the defect states to 2.7×10¹⁷ cm^-3. Received: 3 April 2001 / Accepted: 9 April 2001 / Published online: 25 July 2001     

Characterization of ablation plumes and carbon nitride films produced by reactive pulsed laser deposition in the presence of a magnetic field

x ) films in a nitrogen atmosphere within the range 5×10^-4–4×10^-1 Torr. In the presence of a magnetic field, the emission intensities of N₂ (second positive system) and CN species in the graphite ablation plumes were altered significantly, depending on the pressure of the N₂ environment. Corresponding to an intense CN emission, a magnetic field-induced enhancement of N incorporation – for example, up to 37% at an N₂ pressure of 300 mTorr – and the formation of sp³ tetrahedral CN bonding were both observed in the films. This suggests that the arrival of CN species at the substrate surface with kinetic energies is important for film deposition. Received: 27 August 1997/Accepted: 8 September 1997     

Structural,optical and electrical properties of sulfur-incorporated amorphous carbon films

Amorphous carbon–sulfur (a-C:S) composite films were prepared by vapor phase pyrolysis technique. The structural changes in the a-C:S films were investigated by electron microscopy. A powder X-ray diffraction (XRD) study depicts the two-phase nature of a sulfur-incorporated a-C system. The optical bandgap energy shows a decreasing trend with an increase in the sulfur content and preparation temperature. This infers a sulfur incorporation and pyrolysis temperature induced reduction in structural disorder or increase in sp ² or π-sites. The presence of sulfur (S 2p) in the a-C:S sample is analyzed by the X-ray photoelectron spectroscopy (XPS). The sp ³/sp ² hybridization ratio is determined by using the XPS C 1s peak fitting, and the results confirm an increase in sp ² hybrids with sulfur addition to a-C. The electrical resistivity variation in the films depends on both the sulfur concentration and the pyrolysis temperature.     

Correlation between photoluminescence, optical and structural properties of amorphous nitrogen-rich carbon nitride films

Amorphous nitrogen-rich carbon nitride (CN_x) films have been prepared by inductively coupled plasma chemical vapour deposition (ICP-CVD) utilizing transport reactions from a solid carbon source. The nitrogen atomic fraction N/(C+N) is about 1 or even higher as detected by various surface and bulk sensitive methods. An investigation of the chemical bonding structure showed that the films are composed of >C=N units with a small fraction of C≡N groups. Based on these findings, several structural units derived from cis- and trans-conjugated carbon–nitrogen chains are proposed. The optical properties of the CN_x films were studied by transmission spectroscopy and spectral ellipsometry; the optical Tauc gap was determined to 2.1±0.05 eV. The photoluminescence characteristics were measured at three different excitation wavelengths (476, 488 and 515 nm) and revealed two individual contributions. These data are interpreted in terms of the different structural units comprising the nitrogen-rich CN_x films. Received: 14 July 2000 / Accepted:17 July 2000 / Published online: 22 November 2000     

Grain boundary diffusion of Cu in TiN film by X-ray photoelectron spectroscopy

In this study, the grain boundary diffusion of Cu through a TiN layer with columnar structure was investigated by X-ray photoelectron spectroscopy (XPS). It was observed that Cu atoms diffuse from the Cu layer to the surface along the grain boundaries in the TiN layer at elevated temperature. In order to estimate the grain boundary diffusion constants, we used the surface accumulation method. The diffusivity of Cu through TiN layer with columnar structure from 400 °C to 650 °C is D_b≈6×10⁻¹¹exp(−0.29/(k_BT )) cm²/s. Received: 18 May 1999 / Accepted: 8 September 1999 / Published online: 23 February 2000