Magnetotransport properties of undoped amorphous carbon films

Anomalous positive magnetoresistance (MR) up to 36% was observed at 2 K and 12 T in the undoped amorphous carbon (a-C) film deposited on glass substrate by pulsed laser deposition at 500 °C. There is no tendency of saturation of MR with increase of the magnetic field. The MR decreases as the measurement temperature increases from 2 to 80 K, and could hardly be observed above 80 K. As the deposition temperature grows from 300 to 600 °C, the disorder degree of the a-C film decreases, and the value of MR also decreases, indicating that the lower disorder degree results in a smaller MR. The mechanism of this MR could be ascribed to the wave function shrinkage. It could help to understand the MR phenomenon in amorphous material systems.     

Optical properties and new carbon forms of sputtered amorphous carbon films

Amorphous carbon films were deposited by r.f. magnetron sputtering at various bias voltages V_b applied on Si substrate. We studied the optical properties of the films using in situ spectroscopic ellipsometry (SE) measurements in the energy region 1.5–5.5 eV. From the SE data analysis the dielectric function ε(ω) of the a-C films was obtained, providing information about the electronic structure and the bonding configuration of a-C films. Based on the SE data the films are classified in three categories. In Category I and II belong the films developed with V_b≥0 V (rich in sp² bonds) and −100≤V_b<0 V (rich in sp³ bonds), respectively. The dielectric function of the films belonging in these two categories can be described with two Lorentz oscillators located in the energy range 2.5–5 eV (π–π^*) and 9–12 eV (σ–σ^*). A correlation was found between the oscillator strength and the sp² and sp³ contents. The latter were calculated by analyzing the ε(ω) with the Bruggeman effective medium theory. In films deposited with V_b<−100 V (Category III), the formation of a new and dense carbon phase was detected which exhibits a semi-metallic optical behavior and the ε(ω) can be described with two oscillators located at ∼1.2 and ∼5.5 eV.     

Osteoinduction properties of graphite-like amorphous carbon films evaluated in-vitro

Graphite-like amorphous carbon (a-C) films were deposited by magnetron sputtering on medical grade stainless steel (SS) substrates. The purpose of the study was the evaluation of amorphous carbon as a coating for medical implants in contact with bone, in which the formation of bone on the surface is of special interest to improve the implant performance. The initial step consisted of the evaluation of the cytocompatibility of the a-C films. Cytocompatibility was evaluated by seeding human osteoblast cells on the surfaces and measuring their adhesion, proliferation and viability up to seven days. These data are also of interest for the osteoinduction process because the initial phase of the bone-forming activity of osteoblasts entails the attachment, proliferation, cell differentiation and extracellular matrix synthesis, followed by a second phase of bone matrix mineralization. The evaluation in-vitro of the osteoinduction properties of the surfaces consisted on the study of cell differentiation by measuring the alkaline phosphatase activity, the morphological examination of the mineralized extracellular matrix by electron microscopy, and the evaluation of a selection of proteins involved in the bone-formation process.The cytocompatibility (cell attachment, proliferation and viability) was determined in comparison with SS, titanium coatings and the plastic tissue control. We observed a superior cellular adhesion and proliferation in the a-C surfaces, while the viability was slightly better on the Ti coatings, but nevertheless, the a-C values were much higher than in the plastic control, indicating that the a-C films are no toxic and biocompatible. On the other hand, all the results of the osteoinduction; ALP specific activity and expression of bone-growth specific proteins indicated that the a-C surface significantly promotes the cell differentiation, leading to the formation of the extracellular matrix and its mineralization.     

Electro- and magneto-transport properties of amorphous carbon films doped with iron

Electro- and magneto-transport properties of amorphous carbon films doped with iron element have been systematically studied. The electro-transport mechanism of the films is dominated by thermal activation at T > 200 K, Mott-type variable range hopping (VRH) at 200 K > T > 60 K and Efros-Shklovskii type (ES-) VRH at T < 60 K. An anomalous giant positive magnetoresistance (MR) 6.40% is found at the ES-VRH range, which is attributed to the spin blockage effect. At high temperatures, an anomalous Hall effect (AHE) is also found with a large AHE coefficiency 49.6 μΩcm/T. Electron energy loss spectroscopy (EELS) reveals that iron atoms chemically bond with carbon matrix. These iron carbides exist as amorphous nanoparticles with a diameter of 6-12 nm, which is regarded as the origin of the MR and AHE. Besides, the films are p-type conductive at high temperature, which might be related with the iron doping. These properties make iron doped amorphous carbon films applicable in carbon-based solar cells, magnetic sensors or some other multifunctional devices.     

Defect studies and photoelectrical properties of phosphorus doped amorphous carbon films

This paper reports on the successful deposition of n-type phosphorus doped carbon (n-C:P) thin films and fabrication of n-C:P/p-Si cells by pulsed laser deposition (PLD) using graphite target at room temperature. The cell performances have been tested in the dark for the current–voltage (I–V) rectifying curve and I–V working curve under illumination when exposed to AM 1.5 SUN illumination condition (100 mW/cm², 25 °C). The cells fabricated using 7% of phosphorus by weight percentages in the graphite target (Pwt%) show the highest energy conversion efficiency, η=1.14% and fill factor, FF=41%. The quantum efficiency of the cells is observed to improve with Pwt%. The dependence of Pwt% on the optical and physical properties of the deposited films and the photovoltaic characteristic of the n-C:P/p-Si heterojunction cells are discussed.     

Electrical properties of ultrananocrystalline diamond/amorphous carbon nanocomposite films

The electrical surface properties of ultrananocrystalline diamond/amorphous carbon composite films have been investigated by four-point probe I/V and Hall measurements, whereas impedance spectroscopy has been used to establish the electrical bulk properties of the films. It turned out that the surface is p-type conductive with a resistivity of 0.14 Ω cm and a sheet carrier concentration of 7.6 × 10¹³ cm^?2. The bulk resistivity is higher by almost seven orders of magnitude (1.3 × 10⁶ Ω cm). The bulk conduction is thermally activated with an apparent activation energy of 0.17 eV. From Cole–Cole plots of the impedance spectra it can be concluded that there are three different contributions to the bulk conductivity. In order to try to identify these three components contributing to the electrical bulk conduction, Raman spectra have been recorded at five different wavelengths from the IR to UV region. These measurements showed that the UNCD/a-C films consist of at least three components: diamond nanocrystallites, an amorphous carbon matrix, and trans-polyacetylene-like structures probably at the interface between these two.     

Chemical analysis and vibrational properties of boronated tetrahedral amorphous carbon films

Boronated tetrahedral amorphous carbon (ta-C:B) films were prepared by filtered cathodic vacuum arc technique using boron mixed graphite targets. The effect of boron content on the chemical bonding and vibrational properties of these films has been investigated by X-ray photoelectron spectroscopy, Raman spectroscopy and Fourier transform infrared spectroscopy. It has been found that boron atoms are predominantly configured in a graphitic network, while the carbon atoms in the ta-C:B films are mainly in sp³ hybridization which tend to decrease as boron content increases. The Raman and infrared spectra of ta-C:B films both show prominent features in the regions of 1100–1900 cm^− 1 and 900–1600 cm^− 1 respectively. It was identified that the Raman parameters are strongly correlated with the boron content which is due to the clustering of sp² domains induced by B introduction. The activation of infrared spectrum of ta-C:B film is a consequence of heteroatomic (C–B) vibration combined with changes in the sp² carbon configuration. And the enhanced infrared absorption of ta-C:B with increased boron incorporation results from the increased effective charges in the delocalized sp² carbon phase.     

The relationship between structure and mechanical properties of hydrogenated amorphous carbon films

There is increasing interest in the relations between Raman fit parameters and the mechanical properties of diamond-like carbon films. The present work describes these relations in hydrogenated diamond-like carbon films (a-C:H) deposited by an ion beam source operated at varied discharge voltages, i.e. kinetic carbon species energies. A number of highly distinct relations between Raman fit parameters and mechanical properties are identified for the a-C:H films investigated. For example the nanohardness (H) and reduced elastic modulus (E) increase almost linearly with an increase in full width at half maximum of the G-band (FWHM (G)). The film elasticity, expressed as H³/E² increases with increasing FWHM (G). In addition, H and E increase linearly with decreasing intensity ratio of the D-band and the G-band (I_D/I_G). H and E also increase with the G-band dispersion (Disp. (G)), i.e. the rate of change of the G-band position vs. excitation energy. Hydrogen contents in all films are approximately equal and range from 21.2 to 23.5 at.% over the entire set of investigated samples.     

Structure,elastic properties and strength of amorphous and nanocomposite carbon

We study theoretically the equilibrium structure, as well as the response under external load, of characteristic carbon-based materials. The materials considered include diamond, amorphous carbon (a-C), “amorphous diamond” and nanocomposite amorphous carbon (na-C). A universal bulk modulus versus density curve is obeyed by all structures we consider. We calculate the dependence of elastic constants on the density. The strength of a-C was found to increase in roughly a linear manner, with increasing concentration of four-fold atoms, with the maximum stress of the strongest a-C sample being about half that of diamond. The response of na-C to external load is essentially identical to the response of the embedding a-C matrix.     

Anomalous electrical transport properties of amorphous carbon films on Si substrates

Amorphous carbon (a-C) films are deposited on n-Si substrates at different temperatures using pulsed laser deposition. Some anomalous current-voltage (I-V) characteristics of the a-C/n-Si are reported. The films deposited at 27 °C have an apparent voltage-induced switch effect, and the value of the switch voltage decreases with increasing temperature. However, the I-V characteristics of the a-C/n-Si deposited at 300 °C and 500 °C are completely different from those deposited at 27 °C. The anomalous I-V characteristics should be of interest for various applications such as field effect devices. In addition, the magnetoresistance (MR) and the resistance of the a-C/n-Si have been studied. Finally, we interpret the anomalous I-V characteristics and MR observed by use of energy band theory.     

Field emission properties from aligned carbon nanotube films with tetrahedral amorphous carbon coatings

Tetrahedral amorphous carbon (ta-C) film was coated on aligned carbon nanotube (CNT) films via filtered cathodic vacuum arc (FCVA) technique. Field electron emission properties of the CNT films and the ta-C/CNT films were measured in an ultra high vacuum system. The I–V measurements show that, with a thin ta-C film coating, the threshold electric field (E_thr) of CNTs can be significantly decreased from 5.74 V/μm to 2.94 V/μm, while thick ta-C film coating increased the E_thr of CNTs to around 8.20 V/μm. In addition, the field emission current density of CNT films reached 14.9 mA/cm² at 6 V/μm, while for CNTs film coated with thin ta-C film only 3.1 V/μm of applied electric field is required to reach equal amount of current density. It is suggested that different field emission mechanisms should be responsible for the distinction in field emission features of CNT films with different thickness of ta-C coating.     

Multi-walled carbon nanotubes on amorphous carbon films

Nanotubular structures composed of layered graphite sheets or other layered materials have been studied intensely by both scanning and transmission electron microscopy. In this paper, we will show how graphite structures, that are inherent to the production process of the amorphous carbon support films, used for both SEM and TEM studies can be easily mistaken for the actual sample structures. We will further report that these artifacts appear in both commercial as well as homemade holey carbon support films on copper grids, and suggest that to successfully study the “real” nanotubular structures only support films made from materials other than carbon should be used.     

Effects of acetylene addition on mechanical and dielectric properties of amorphous carbon films

The para-xylene added with acetylene from 15% to 50% was plasma polymerized at 50 to 150 W to deposit the a-C:H films. After the films were annealed from 200 to 400 °C, the network structure, hardness and dielectric constant of films were analyzed by FT-IR, Raman, nanoindentor and capacitance–voltage plot, respectively. Those measured results suggest that hydrocarbon bonds and oxygen related bonds of the a-C:H film effectively reduce and the number of ordered aromatic rings increases with decreasing the deposition power after annealing at 400 °C. In addition, both the dielectric constant and the hardness, respectively, increase up to 2.82 and 2.37 GPa, but the adhesion strength decreases with increasing the C₂H₂ concentration and deposition power. Therefore, the a-C:H films not only have a lower dielectric constant, but also have enough mechanical strength for the IC processing.     

The effect of annealing on electrical properties of fluorinated amorphous carbon films

Fluorinated amorphous carbon (a–C:F) films have been deposited by electron cyclotron resonance chemical vapor deposition (ECR–CVD) at room temperature using C₄F₈ and CH₄ as precursor gases. The chemical compositions and electrical properties of a–C:F films have been studied by X-ray photoelectron spectroscopy (XPS), capacitance–voltage (C–V) and current-voltage (I–V) measurements. The results show that C–CF_x and C–C species of a–C:F films increase and fluorine content decreases after annealing. The dielectric constant of the annealed a–C:F films increases as a result of enhancement of film density and reduction of electronic polarization. The densities of fixed charges and interface states decrease from 1.6 × 10¹⁰ cm^− 2 and (5–9) × 10¹¹ eV^− 1 cm^− 2 to 3.2 × 10⁹ cm^− 2 and (4–6) × 10¹¹ eV^− 1 cm^− 2 respectively when a–C:F films are annealed at 300 °C. The magnitude of C–V hysteresis decreases due to reduced dangling bonds at the a–C:F/Si interfaces after heat treatment. The conduction of a–C:F films shows ohmic behavior at lower electric fields and is explained by Poole–Frankel (PF) mechanism at higher electric fields. The PF current increases indicative of reduced trap energy when a–C:F films are subjected to higher annealing temperatures.     

Improved adhesion and tribological properties of fast-deposited hard graphite-like hydrogenated amorphous carbon films

Graphite-like hard hydrogenated amorphous carbon (a-C:H) was deposited using an Ar-C₂H₂ expanding thermal plasma chemical vapour deposition (ETP-CVD) process. The relatively high hardness of the fast deposited a-C:H material leads to high compressive stress resulting in poor adhesion between the carbon films and common substrates like silicon, glass and steel. A widespread solution to this problem is the use of an adhesion interlayer. Here we report on the changes in adhesion between the graphite-like a-C:H films and M2 steel substrates when different types of interlayers are used. Insignificant to very small improvements in adhesion were observed when using amorphous silicon oxide (a-SiO_x), amorphous organosilicon (a-SiC_xO_y:H_z) and amorphous hydrogenated silicon carbide (a-SiC_x:H_y) as adhesion layers. However, when sputtered Ti was used as an interlayer, the adhesion increased significantly. The dependence of the adhesive properties on the deposition temperature and interlayer thickness, as well as on the thickness of the a-C:H layer is presented and discussed. The low wear rates measured for the a-C:H/Ti/M2 stack suggest that these films are ideal for tribological applications.     

Electronic properties of hydrogenated amorphous carbon films deposited using ECR-RF plasma method

A combination of junction capacitance, electron spin resonance and electrical conductivity measurements are used to investigate the electronic properties of two different types of a-C:H films grown in a dual ECR-RF glow discharge system at substrate bias equal to −30 and −600 V, respectively. The analysis of the steady state admittance (both capacitance C and conductance G) as a function of frequency (ω=5 Hz–1 kHz) and temperature (20–350 K) allows an estimate of the density of states at the Fermi level of approximately 7×10¹⁵ and 9.7×10¹⁶ eV⁻¹ cm⁻³ for the −30 and −600 V deposited samples, respectively, values well below those deduced for the density of spins from the electron spin resonance experiments, of approximately 10¹⁹–10²⁰ cm⁻³. Concerning the conductance results, two transport processes operating, respectively, below and above 290 K are shown. The high temperature process is associated with an activation energy of 0.5 and 0.41 eV for the −30 and −600 V samples, respectively, in good agreement with the values obtained in the high temperature range (>300 K) for the activation energy of the electrical conductivity. Regarding the effect of the frequency and temperature on the conductance, we show that for temperatures below 290 K, a Variable Range Hopping mechanism is possible by facing our data to the Mott's model. Annealing at high temperature induces structural changes accompanied by an increase in the spin density in both types of samples with however, a different behaviour from one type to another.     

Osteoblasts attachment on amorphous carbon films

In this work we studied the osteoblasts response to amorphous carbon (a-C) films deposited on stainless steel substrates with different surface textures. For osteoblasts cells, attachment to the substrate is the first step in the process of cell/surface interactions which affects subsequent cellular and tissue response. Amorphous carbon films are characterized by very smooth surfaces that imaged the surface roughness of the substrate and many of their applications rely on this property. However, in the biomedical field the cell response is strongly influenced by the topography and particularly, for osteoblasts cells it has been shown that rough surfaces enhances cellular attachment and differentiation. Therefore, in this work we modified the surface roughness of the substrate in order to obtain carbon films with different values of average surface roughness. The substrates were abraded or fine-polished to obtain four different average roughness: 0.01, 1.5, 2.1 and 3.5 μm. Surface topography before and after deposition of the a-C films was evaluated by profilometry and scanning electron microscopy (SEM), while chemical composition was determined by X-ray photoelectron spectroscopy. Human osteoblasts cells were used to evaluate the effect of the different surface finishes on the adhesion. The number of attached cells was determined by a colorimetric technique after 24 h of incubation, while morphological and cytoskeletal changes were monitored using SEM. The cellular attachment on a-C surfaces increases monotonically with the roughness attaining up to 160% more cells than the positive control.     

Nanoindentation and nanoscratching studies of amorphous carbon films

Hydrogen-free amorphous carbon (a-C) films prepared by RF magnetron sputtering were deposited on Si substrates in thin films, at various negative bias voltages V_b (i.e. Ar-ion energies), and in thick layered-structure films with alternative values of V_b. The main purposes of this work are to present preliminary results concerning the effect of Ar-ion bombardment during deposition on the elastic properties of thin a-C films with Ar⁺ energies in the range 30–200 eV, and the adhesion failure which limits their thickness and usefulness for practical applications, and the enhancement of hardness and scratch resistance of sputtered a-C films developed in a layered structure. The results show a significant improvement in the elastic properties of layered structure films and their stability. The combination of high hardness and relative low elastic modulus which the layered films exhibit make them more resistant to plastic deformation during contact, as confirmed by scratch testing.     

Structure,gas-barrier properties and overall migration of poly(lactic acid) films coated with hydrogenated amorphous carbon layers

Hydrogenated amorphous carbon (a-C:H) films were grown on a poly(lactic acid) (PLA) substrate by means of a radiofrequency plasma-enhanced chemical vapour deposition (rf-PECVD) technique with different deposition times (5, 20 and 40 min). The main goal of this treatment was to increase the barrier properties of PLA, maintaining its original transparency and colour as well as controlling interactions with food simulants for packaging applications. Morphological, chemical, and mechanical properties of PLA/a-C:H systems were evaluated while permeability and overall migration tests were performed in order to determine the effect of the plasma treatment on the gas-barrier properties of PLA films and their application in food packaging. Morphological results suggested a good adhesion of the deposited layers onto the polymer surface and the samples treated for 5 and 20 min only slightly darkened the PLA film. X-ray photoelectron spectroscopy revealed that the structural properties of the carbon layer deposited onto the PLA film depend on the exposure time. PLA/a-C:H system treated for 5 min showed the highest barrier properties, while none of the studied samples exceeded the migration limit established by the current legislation, suggesting the suitability of these materials in packaging applications.     

Crystalline structures of carbon complexes in amorphous carbon films

Amorphous carbon (a-C) films, 20 nm thick, were deposited by sputtering on (001) Si substrates. A negative bias voltage was applied to the substrate during deposition to induce Ar⁺ ion bombardment with an energy of ∼230 eV. The film microstructure was investigated by conventional transmission electron microscopy as well as high-resolution electron microscopy. The films consist of an amorphous carbon matrix and crystallites with a platelet form. The crystallites are energetically metastable and easily degrade under electron beam irradiation. In addition, they are usually oriented along their sixfold or threefold axes, exhibiting lattice parameters larger than those of graphite and diamond. X-ray reflectivity density measurements and high-resolution electron microscopy observations indicate that these crystallites consist of packed complex carbon clusters. X-ray diffraction measurements in rocking curve geometry support the existence of oriented crystallites with interplanar spacings corresponding to those observed by transmission electron microscopy.