Calculation of the electronic structure of carbon films using electron energy loss spectroscopy.

The detailed understanding of the electronic properties of carbon-based materials requires the determination of their electronic structure and more precisely the calculation of their joint density of states (JDOS) and dielectric constant. Low electron energy loss spectroscopy (EELS) provides a continuous spectrum which represents all the excitations of the electrons within the material with energies ranging between zero and about 100 eV. Therefore, EELS is potentially more powerful than conventional optical spectroscopy which has an intrinsic upper information limit of about 6 eV due to absorption of light from the optical components of the system or the ambient. However, when analysing EELS data, the extraction of the single scattered data needed for Kramers Kronig calculations is subject to the deconvolution of the zero loss peak from the raw data. This procedure is particularly critical when attempting to study the near-bandgap region of materials with a bandgap below 1.5 eV. In this paper, we have calculated the electronic properties of three widely studied carbon materials; namely amorphous carbon (a-C), tetrahedral amorphous carbon (ta-C) and C60 fullerite crystal. The JDOS curve starts from zero for energy values below the bandgap and then starts to rise with a rate depending on whether the material has a direct or an indirect bandgap. Extrapolating a fit to the data immediately above the bandgap in the stronger energy loss region was used to get an accurate value for the bandgap energy and to determine whether the bandgap is direct or indirect in character. Particular problems relating to the extraction of the single scattered data for these materials are also addressed. The ta-C and C60 fullerite materials are found to be direct bandgap-like semiconductors having a bandgaps of 2.63 and 1.59eV, respectively. On the other hand, the electronic structure of a-C was unobtainable because it had such a small bandgap that most of the information is contained in the first 1.2 eV of the spectrum, which is a region removed during the zero loss deconvolution.

Smooth thin film C/diamond membranes with controllable optical band gaps

Mixed phase carbon-diamond films which consist of small grain diamond in an a:C matrix were deposited on polished Si using a radio frequency CH4 Ar plasma CVD deposition process. Ellipsometry, surface profilometry, scanning electron microscopy (SEM) and spectrophotometry were used to analyse these films. Film thicknesses were typically 50-100 nm with a surface roughness of ± 30 A ̊ over centimetre length scans. SEM analysis showed the films were smooth and pinhole free. The Si substrate was etched using backside masking and a directional etch to give taut carbon-diamond membranes on a Si grid. Spectrophotometry was used to analyse the optical properties of these membranes. Band gap control was achieved by varying the dc bias of the deposition process. Band gaps of 1.2 eV to 4.0 eV were achieved in these membranes. A technique for controlling the compressive stress in the films, which can range from 0.02 to 7.5 GPa has been employed. This has allowed the fabrication of thin, low stress, high band gap membranes that are extremely tough and chemically inert. Such carbon-diamond membranes seem promising for applications as windows in analytical instruments. © 1992.

Spontaneous formation of highly ordered nanostructures: thermal instability and mode selection in surface-capped polymer films.

We demonstrate a controllable formation process of wave-like patterns in thermally unstable surface-capped polymer films on a rigid substrate. Self-ordered wave-like structures over a large area can be created by applying a small lateral tension to the film, whereupon it becomes unstable. A clear mode selection process which includes creation, decay and interference between coexisting waves at different annealing conditions has been observed, which makes it possible to restrain the patterns which are formed finally. Our results provide a clear and new evidence of spinodal behaviour in such a film due to thermal instability. Furthermore, we show that the well-controlled patterns generated in such a process can be used to fabricate nanostructures for various applications.

Effect of deposition conditions on the chemical bonding in sputtered carbon nitride films

A balanced planar r.f. powered magnetron sputter source has been used to deposit carbon nitride films from a graphite target under various conditions. Sample temperature, bias voltage and nitrogen content in the gas mixture were varied. The effects of oxygen, methane and ammonia on the film growth were also studied. Special attention was paid to the effects of the deposition parameters on the structure of the films, in particular the hybridisation of the carbon and nitrogen bonding. The chemical bonding of the carbon and nitrogen atoms was studied by electron energy loss spectroscopy (EELS). The chemical composition was evaluated by Rutherford back-scattering. The intensity of transitions to π antibonding orbitals, as revealed by EELS, was found to increase with the nitrogen content in the films. Ion bombardment of the films during growth and the addition of oxygen or hydrogen-rich gases further increased the proportion of π bonds of both the carbon and nitrogen atoms. It is suggested that the increase in the transitions to μ antibond orbitals is to be explained by increased sp2 or possibly sp hybridisation of the carbon and nitrogen. Also, the effect of annealing on the bonding of nitrogen rich films after deposition was tested. The changes caused by nitrogen and deposition conditions are consistent with previous reports on the formation of paracyanogen structures.

Density, sp3 content and internal layering of DLC films by X-ray reflectivity and electron energy loss spectroscopy

A variety of hydrogenated and non-hydrogenated amorphous carbon thin films have been characterized by means of grazing-incidence X-ray reflectivity (XRR) to give information about their density, thickness, surface roughness and layering. We used XRR to validate the density of ta-C, ta-C:H and a-C:H films derived from the valence plasmon in electron energy loss spectroscopy measurements, up to 3.26 and 2.39 g/cm3 for ta-C and ta-C:H, respectively. By comparing XRR and electron energy loss spectroscopy (EELS) data, we have been able for the first time to fit a common electron effective mass of m*/me = 0.87 for all amorphous carbons and diamond, validating the `quasi-free' electron approach to density from valence plasmon energy. While hydrogenated films are found to be substantially uniform in density across the film, ta-C films grown by the filtered cathodic vacuum arc (FCVA) show a multilayer structure. However, ta-C films grown with an S-bend filter show a high uniformity and only a slight dependence on the substrate bias of both sp3 and layering.

Preparation of tetrahedral amorphous carbon films by filtered cathodic vacuum arc deposition

Tetrahedrally bonded amorphous carbon (ta-C) and nitrogen doped (ta-C:N) films were obtained at room temperature in a filtered cathodic vacuum arc (FCVA) system incorporating an off-plane double bend (S-bend) magnetic filter. The influence of the negative bias voltage applied to substrates (from -20 to -350 V) and the nitrogen background pressure (up to 10-3 Torr) on film properties was studied by scanning electron microscopy (SEM), electron energy loss spectroscopy (EELS), Raman spectroscopy, X-ray photoemission spectroscopy (XPS), secondary ion mass spectroscopy (SIMS) and X-ray reflectivity (XRR). The ta-C films showed sp3 fractions between 84% and 88%, and mass densities around 3.2 g/cm3 in the wide range of bias voltage studied. In contrast, the compressive stress showed a maximum value of 11 GPa for bias voltages around -90 V, whereas for lower and higher bias voltages the stress decreased to 6 GPa. As for the ta-C:N films grown at bias voltages below -200 V and with N contents up to 7%, it has been found that the N atoms were preferentially sp3 bonded to the carbon network with a reduction in stress below 8 GPa. Further increase in bias voltage or N content increased the sp2 fraction, leading to a reduction in film density to 2.7 g/cm3.

Microwave power effects on the properties of phosphorus-doped SiC:H films prepared using ECR-CVD

There has been a growing interest in hydrogenated silicon carbide films (SiC:H) prepared using the electron cyclotron resonance-chemical vapour deposition (ECR-CVD) technique. Using the ECR-CVD technique, SiC:H films have been prepared from a mixture of methane, silane and hydrogen, with phosphine as the doping gas. The effects of changes in the microwave power (from 150 to 900 W) on the film properties were investigated in a series of phosphorus-doped SiC:H films. In particular, the changes in the deposition rate, optical bandgap, activation energy and conductivity were investigated in conjunction with results from Raman scattering and Fourier transform infra-red (FTIR) analysis. It was found that increase in the microwave power has the effect of enhancing the formation of the silicon microcrystalline phase in the amorphous matrix of the SiC:H films. This occurs in correspondence to a rapid increase in the conductivity and a reduction in the activation energy, both of which exhibit small variations in samples deposited at microwave powers exceeding 500 W. Analysis of IR absorption results suggests that hydrogen is bonded to silicon in the Si-H stretching mode and to carbon in the sp3 CHn rocking/wagging and bending mode in films deposited at higher microwave powers.

High velocity vortex channeling in vicinal YBCO thin films

We report on electrical transport measurements at high current densities on optimally doped YBa 2Cu 3O 7-δ thin films grown on vicinal SrTiO 3 substrates. Data were collected by using a pulsed-current technique in a four-probe arrangement, allowing to extend the current-voltage characteristics to high supercritical current densities (up to 24 MA cm -2) and high electric fields (more than 20 V/cm), in the superconducting state at temperatures between 30 and 80 K. The electric measurements were performed on tracks perpendicular to the vicinal step direction, such that the current crossed between ab planes, under magnetic field rotated in the plane defined by the crystallographic c axis and the current density. At magnetic field orientation parallel to the cuprate layers, evidence for the sliding motion along the ab planes (vortex channeling) was found. The signature of vortex channeling appeared to get enhanced with increasing electric field, due to the peculiar depinning features in the kinked vortex range. They give rise to a current-voltage characteristics steeper than in the more off-plane rectilinear vortex orientations, in the electric field range below approximately 1 V/cm. Roughly above this value, the high vortex channeling velocities (up to 8.6 km/s) could be ascribed to the flux flow, although the signature of ohmic transport appeared to be altered by unavoidable macroscopic self-heating and hot-electron-like effects. © 2012 Elsevier B.V. All rights reserved.

Optical and structural properties of Er2O3 films grown by magnetron sputtering

The structural properties and the room temperature luminescence of Er 2O3 thin films deposited by magnetron sputtering have been studied. In spite of the well-known high reactivity of rare earth oxides towards silicon, films characterized by good morphological properties have been obtained by using a SiO2 interlayer between the film and the silicon substrate. The evolution of the properties of the Er2O3 films due to thermal annealing processes in oxygen ambient performed at temperatures in the range of 800-1200°C has been investigated in detail. The existence of well defined annealing conditions (rapid treatments at a temperature of 1100°C or higher) allowing to avoid the occurrence of extensive chemical reactions with the oxidized substrate has been demonstrated; under these conditions, the thermal process has a beneficial effect on both structural and optical properties of the film, and an increase of the photoluminescence (PL) intensity by about a factor of 40 with respect to the as-deposited material has been observed. The enhanced efficiency of the photon emission process has been correlated with the longer lifetime of the PL signal. Finally, the conditions leading to a reaction of Er2O3 with the substrate have been also identified, and evidences about the formation of silicate-like phases have been collected. © 2006 American Institute of Physics.

High-density remote plasma sputtering of high-dielectric-constant amorphous hafnium oxide films

Hafnium oxide (HfOx) is a high dielectric constant (k) oxide which has been identified as being suitable for use as the gate dielectric in thin film transistors (TFTs). Amorphous materials are preferred for a gate dielectric, but it has been an ongoing challenge to produce amorphous HfOx while maintaining a high dielectric constant. A technique called high target utilization sputtering (HiTUS) is demonstrated to be capable of depositing high-k amorphous HfOx thin films at room temperature. The plasma is generated in a remote chamber, allowing higher rate deposition of films with minimal ion damage. Compared to a conventional sputtering system, the HiTUS technique allows finer control of the thin film microstructure. Using a conventional reactive rf magnetron sputtering technique, monoclinic nanocrystalline HfOx thin films have been deposited at a rate of ∼1.6nmmin-1 at room temperature, with a resistivity of 1013Ωcm, a breakdown strength of 3.5MVcm-1 and a dielectric constant of ∼18.2. By comparison, using the HiTUS process, amorphous HfOx (x=2.1) thin films which appear to have a cubic-like short-range order have been deposited at a high deposition rate of ∼25nmmin-1 with a high resistivity of 1014Ωcm, a breakdown strength of 3MVcm-1 and a high dielectric constant of ∼30. Two key conditions must be satisfied in the HiTUS system for high-k HfOx to be produced. Firstly, the correct oxygen flow rate is required for a given sputtering rate from the metallic target. Secondly, there must be an absence of energetic oxygen ion bombardment to maintain an amorphous microstructure and a high flux of medium energy species emitted from the metallic sputtering target to induce a cubic-like short range order. This HfOx is very attractive as a dielectric material for large-area electronic applications on flexible substrates. A remote plasma sputtering process (high target utilization sputtering, HiTUS) has been used to deposit amorphous hafnium oxide with a very high dielectric constant (∼30). X-ray diffraction shows that this material has a microstructure in which the atoms have a cubic-like short-range order, whereas radio frequency (rf) magnetron sputtering produced a monoclinic polycrystalline microstructure. This is correlated to the difference in the energetics of remote plasma and rf magnetron sputtering processes. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Characterization of the surface acoustic wave devices based on ZnO/nanocrystalline diamond structures

Nanocrystalline ZnO films with strong (0002) texture and fine grains were deposited onto ultra-nanocrystalline diamond (UNCD) layers on silicon using high target utilization sputtering technology. The unique characteristic of this sputtering technique allows room temperature growth of smooth ZnO films with a low roughness and low stress at high growth rates. Surface acoustic wave (SAW) devices were fabricated on ZnO/UNCD structure and exhibited good transmission signals with a low insertion loss and a strong side-lobe suppression for the Rayleigh mode SAW. Based on the optimization of the layered structure of the SAW device, a good performance with a coupling coefficient of 5.2% has been realized, promising for improving the microfluidic efficiency in droplet transportation comparing with that of the ZnO/Si SAW device. An optimized temperature coefficient of frequency of -23.4 ppm°C-1 was obtained for the SAW devices with the 2.72 μm-thick ZnO and 1.1 μm-thick UNCD film. Significant thermal effect due to the acoustic heating has been redcued which is related to the temperature stability of the ZnO/UNCD SAW device. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermal annealing effect on the nanomechanical properties and structure of P3HT:PCBM thin films

Nanostructured polymer-fullerene thin films are among the most prominent materials for application in high efficient polymer solar cells. Specifically, poly(3-hexylthiophene) (P3HT) and fullerene derivatives (PCBM) blends are used as the donor/acceptor materials forming a bulk heterojunction. Although P3HT:PCBM properties have been extensively studied, less light has been set on its nanomechanical properties, which affect the device service life. In this work Atomic Force Acoustic Microscopy (AFAM), Atomic Force Spectroscopy and Nanoindentation were used to study the effect of the fullerene presence and the annealing on the P3HT:PCBM nanomechanical behavior. The P3HT:PCBM thin films were prepared by spin coating on glass substrates and then annealed at 100 °C and 145 °C for 30 min. Large phase separation was identified by optical and Atomic Force Microscopy (AFM) for the annealed samples. Needle-like PCBM crystals were formed and an increase of the polymer crystallinity degree with the increase of the annealing temperature was confirmed by X-ray diffraction. AFAM characterization revealed the presence of aggregates close to stiff PCBM crystals, possibly consisting of amorphous P3HT material. AFM force-distance curves showed a continuous change in stiffness in the vicinity of the PCBM crystals, due to the PCBM depletion near its crystals, and the AFM indentation provided qualitative results about the changes in P3HT nanomechanical response after annealing. © 2011 Elsevier B.V. All rights reserved.