Influence of ion energy and substrate temperature on the optical and electronic properties of tetrahedral amorphous carbon (ta-C) films

The properties of amorphous carbon (a-C) deposited using a filtered cathodic vacuum arc as a function of the ion energy and substrate temperature are reported. The sp3 fraction was found to strongly depend on the ion energy, giving a highly sp3 bonded a-C denoted as tetrahedral amorphous carbon (ta-C) at ion energies around 100 eV. The optical band gap was found to follow similar trends to other diamondlike carbon films, varying almost linearly with sp2 fraction. The dependence of the electronic properties are discussed in terms of models of the electronic structure of a-C. The structure of ta-C was also strongly dependent on the deposition temperature, changing sharply to sp2 above a transition temperature, T1, of ≈200°C. Furthermore, T1 was found to decrease with increasing ion energy. Most film properties, such as compressive stress and plasmon energy, were correlated to the sp3 fraction. However, the optical and electrical properties were found to undergo a more gradual transition with the deposition temperature which we attribute to the medium range order of sp2 sites. We attribute the variation in film properties with the deposition temperature to diffusion of interstitials to the surface above T1 due to thermal activation, leading to the relaxation of density in context of a growth model. © 1997 American Institute of Physics.

High rate deposition of ta-C:H using an electron cyclotron wave resonance plasma source

A compact electron cyclotron wave resonance (ECWR) source has been developed for the high rate deposition of hydrogenated tetrahedral amorphous carbon (ta-C:H). The ECWR provides growth rates of up to 1.5 nm/s over a 4-inch diameter and an independent control of the deposition rate and ion energy. The ta-C:H was deposited using acetylene as the source gas and was characterized as having an sp3 content of up to 77%, plasmon energy of 27 eV, refractive index of 2.45, hydrogen content of about 30%, optical gap of up to 2.1 eV and RMS surface roughness of 0.04 nm. © 1999 Elsevier Science S.A. All rights reserved.

High rate deposition of Ta-C:H using an electron cyclotron wave resonance plasma source

A compact electron cyclotron wave resonance (ECWR) source has been developed for the high rate deposition of hydrogenated tetrahedral amorphous carbon (ta-C:H). The ECWR provides growth rates of up to 900 angstrom/min and an independent control of the deposition rate and ion energy. The ta-C:H was deposited using acetylene as the source gas and was characterized in terms of its bonding, stress and friction coefficient. The results indicated that the ta-C:H produced using this source fulfills the necessary requirements for applications requiring enhanced tribological performance.

Deposition of carbon nitride films using an electron cyclotron wave resonance plasma source

Hydrogenated amorphous carbon nitride (a-C:N:H) has been synthesized using a high plasma density electron cyclotron wave resonance (ECWR) technique using N2 and C2H2 as source gases, at different ratios and a fixed ion energy (80 eV). The composition, structure and bonding state of the films were investigated and related to their optical and electrical properties. The nitrogen content in the film rises rapidly until the N2/C2H2 gas ratio reaches 2 and then increases more gradually, while the deposition rate decreases steeply, placing an upper limit for the nitrogen incorporation at 30 at%. For nitrogen contents above 20 at%, the band gap and sp3-bonded carbon fraction decrease from 1.7 to 1.1 eV and approximately 65 to 40%, respectively. Films with higher nitrogen content are less dense than the original hydrogenated tetrahedral amorphous carbon (ta-C:H) film but, because they have a relatively high band gap (1.1 eV), high resistivity (109 Ω cm) and moderate sp3-bonded carbon fraction (40%), they should be classed as polymeric in nature.

Chemical sputtering of ta-C: Implications for the deposition of carbon nitride

The majority of attempts to synthesize the theoretically predicted superhard phase β-C3N4 have been driven towards the use of techniques which maximize both the carbon sp3 levels and the amount of nitrogen incorporated within the film. However, as yet no attempt has been made to understand the mechanism behind the resultant chemical sputter process and its obvious effect upon film growth. In this work, however, the chemical sputtering process has been investigated through the use of an as-deposited tetrahedrally bonded amorphous carbon film with a high density nitrogen plasma produced using an rf-based electron cyclotron wave resonance source. The results obtained suggested the presence of two distinct ion energy dependent regimes. The first, below 100 eV, involves the chemical sputtering of carbon from the surface, whereas the second at ion energies in excess of 100 eV exhibits a drop in sputter rate associated with the subplantation of nitrogen within the carbon matrix. Furthermore, as the sample temperature is increased there is a concomitant decrease in sputter rate suggesting that the rate is controlled by the adsorption and desorption of additional precursor species rather than the thermal desorption of CN. A simple empirical model has been developed in order to elucidate some of the primary reactions involved in the sputter process. Through the incorporation of various previously determined experimental parameters including electron temperature, ion current density, and nitrogen partial pressure the results indicated that molecular nitrogen physisorbed at the ta-C surface was the dominant precursor involved in the chemical sputter process. However, as the physisorption enthalpy of molecular nitrogen is low this suggests that activation of this molecular species takes place only through ion impact at the surface. The obtained results therefore provide important information for the modeling and growth of high density carbon nitride. © 2001 American Institute of Physics.

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.

Deposition of diamond-like carbon films by photon-enhanced chemical vapour deposition of methane using a windowless hydrogen lamp

Thin films of diamond-like carbon (DLC) have been deposited using a novel photon-enhanced chemical vapour deposition (photo-CVD) method. This low energy method may be a way to produce better interfaces in electronic devices by reducing damage due to ion bombardment. Methane requires high energy photons for photolysis to take place and these are not transmitted in most photo-CVD methods owing to the presence of a window between the lamp and the deposition environment. In our photo-CVD system there is no window and all the high energy photons are transmitted into the reaction gas. Initial work has proved promising and this paper presents recent results. Films have been characterized by measuring electron energy loss spectra, by ellipsometry and by fabricating and testing diode structures. Results indicate that the films are of a largely amorphous nature and are semiconducting. Diode structures have on/off current ratios of up to 106.

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.

Vertically aligned carbon nanotubes growth using self-assembled Ni nanoparticles produced by ion implantation

An alternative method for seeding catalyst nanoparticles for carbon nanotubes and nanowires growth is presented. Ni nanoparticles are formed inside a 450 nm SiO2 film on (100) Si wafers through the implantation of Ni ions at fluences of 7.5×1015 and 1.7×1016 ions.cm-2 and post-annealing treatments at 700, 900 and 1100°C. After exposed to the surface by HF dip etching, the Ni nanoparticles are used as catalyst for the growth of vertically aligned carbon nanotubes by direct current plasma enhanced chemical vapor deposition. © 2007 Materials Research Society.

How to achieve high mobility thin film transistors by direct deposition of silicon using 13.56 MHz RF PECVD?

CMOS nanocrystalline silicon thin film transistors with high field effect mobility are reported. The transistors were directly deposited by radio-frequency plasma enhanced chemical vapor deposition at 150°C The transistors show maximum field effect mobility of 450 cm2/V-s for electrons and 100 cm2/V-s for holes at room temperature. We attribute the high mobilities to a reduction of the oxygen content, which acts as an accidental donor. Indeed, secondary ion mass spectrometry measurements show that the impurity concentration in the nanocrystalline Si layer is comparable to, or lower than, the defect density in the material, which is already low thanks to hydrogen passivation.

Low temperature (< 100 °c) deposited P-type cuprous oxide thin films: Importance of controlled oxygen and deposition energy

With the emergence of transparent electronics, there has been considerable advancement in n-type transparent semiconducting oxide (TSO) materials, such as ZnO, InGaZnO, and InSnO. Comparatively, the availability of p-type TSO materials is more scarce and the available materials are less mature. The development of p-type semiconductors is one of the key technologies needed to push transparent electronics and systems to the next frontier, particularly for implementing p-n junctions for solar cells and p-type transistors for complementary logic/circuits applications. Cuprous oxide (Cu2O) is one of the most promising candidates for p-type TSO materials. This paper reports the deposition of Cu2O thin films without substrate heating using a high deposition rate reactive sputtering technique, called high target utilisation sputtering (HiTUS). This technique allows independent control of the remote plasma density and the ion energy, thus providing finer control of the film properties and microstructure as well as reducing film stress. The effect of deposition parameters, including oxygen flow rate, plasma power and target power, on the properties of Cu2O films are reported. It is known from previously published work that the formation of pure Cu2O film is often difficult, due to the more ready formation or co-formation of cupric oxide (CuO). From our investigation, we established two key concurrent criteria needed for attaining Cu2O thin films (as opposed to CuO or mixed phase CuO/Cu2O films). First, the oxygen flow rate must be kept low to avoid over-oxidation of Cu2O to CuO and to ensure a non-oxidised/non-poisoned metallic copper target in the reactive sputtering environment. Secondly, the energy of the sputtered copper species must be kept low as higher reaction energy tends to favour the formation of CuO. The unique design of the HiTUS system enables the provision of a high density of low energy sputtered copper radicals/ions, and when combined with a controlled amount of oxygen, can produce good quality p-type transparent Cu2O films with electrical resistivity ranging from 102 to 104 Ω-cm, hole mobility of 1-10 cm2/V-s, and optical band-gap of 2.0-2.6 eV. These material properties make this low temperature deposited HiTUS Cu 2O film suitable for fabrication of p-type metal oxide thin film transistors. Furthermore, the capability to deposit Cu2O films with low film stress at low temperatures on plastic substrates renders this approach favourable for fabrication of flexible p-n junction solar cells. © 2011 Elsevier B.V. All rights reserved.

Properties of tetrahedral amorphous carbon prepared by vacuum arc deposition

The structural, optical, electrical and physical properties of amorphous carbon deposited from the filtered plasma stream of a vacuum arc were investigated. The structure was determined by electron diffraction, neutron diffraction and energy loss spectroscopy and the tetrahedral coordination of the material was confirmed. The measurements gave a nearest neighbour distance of 1.53 Å, a bond angle of 110 and a coordination number of four. A model is proposed in which the compressive stress generated in the film by energetic ion impact produces pressure and temperature conditions lying well inside the region of the carbon phase diagram within which diamond is stable. The model is confirmed by measurements of stress and plasmon energy as a function of ion energy. The model also predicts the formation of sp2-rich materials on the surface owing to stress relaxation and this is confirmed by a study of the surface plasmon energy. Some nuclear magnetic resonance, infrared and optical properties are reported and the behaviour of diodes using tetrahedral amorphous carbon is discussed. © 1991.