Electrical conduction in plasma polymerized thin films of γ‐terpinene

Plasma polymerized γ‐terpinene (pp?GT) thin films are fabricated using RF plasma polymerization. MIM structures are fabricated and using the capacitive structures dielectric properties of the material is studied. The dielectric constant values are found to be in good agreement with those determined from ellipsometric data. At a frequency of 100 kHz, the dielectric constant varies with RF deposition power, from 3.69 (10 W) to 3.24 (75 W). The current density–voltage (J?V) characteristics of pp–GT thin films are investigated as a function of RF deposition power at room temperature to determine the resistivity and DC conduction mechanism of the films. At higher applied voltage region, Schottky conduction is the dominant DC conduction mechanism. The capacitance and the loss tangent are found to be frequency dependent. The conductivity of the pp?GT thin films is found to decrease from 1.39 × 10^?12 S/cm (10 W) to 1.02 × 10^?13 S/cm (75 W) and attributed to the change in the chemical composition and structure of the polymer. The breakdown field for pp–GT thin films increases from 1.48 MV/cm (10 W) to 2 MV/cm (75 W). A single broad relaxation peak is observed indicating the contribution of multiple relaxations to the dielectric response for temperature dependent J?V. The distribution of these relaxation times is determined through regularization methods. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42318.     

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.     

Dependence of the composition and bonding structure of carbon nitride films deposited by direct current plasma assisted pulsed laser ablation on the deposition temperature

Carbon nitride films were deposited by direct current plasma assisted pulsed laser ablation of a graphite target under nitrogen atmosphere. Atomic force microscopy (AFM), Fourier transform infrared (FTIR), Raman, and X-ray photoelectron spectroscopy (XPS) were used to characterize the surface morphology, bonding structure, and composition of the deposited films. The influence of deposition temperature in the range 25–400 °C on the composition and bonding structure of carbon nitride films was systematically studied. AFM images show that surface roughness and cluster size increase monotonically with deposition temperature. XPS, FTIR, and Raman spectra indicate directly the existence of CN, CN, and CN bonds in the deposited films. The increase of deposition temperature results in a drastic decrease in the N/C ratio, the content of CN bond and N atoms bonded to sp³ C atoms, in addition to the increase in the content of disorder sp² C atoms and N atoms bonded to sp² C atoms in the deposited films. Raman spectra show that the intensity ratio of D peak over G peak increases with increasing deposition temperature to 200 °C, then decreases with the further increase of deposition temperature, which results from the continuous growth of sp² cluster in the films.     

Scaling-down characteristics of nanoscale diamond-like carbon based resistive switching memories

A nonvolatile resistive switching random access memory (RRAM) device based on the diamond-like carbon (DLC) films and the inert metal electrodes was demonstrated. A typical unipolar resistive switching (RS) behavior without high voltage “forming process” is observed. It exhibits good scaling-down properties when negligible dependence upon the cell area is observed for V_SET and I_RESET decreases with the reduction of the cell area, which is suitable for practical nonvolatile memory applications. Investigations on the electron transport characteristics at HRS and LRS indicate that Frenkel–Poole emission and Ohmic Laws dominate the LRS and HRS states, respectively. Based on the conduction mechanism studies, the RS behavior is found to arise from the formation and rupture of conductive sp²-like graphitic filaments originating from the connection of conductive sp²-like carbon bonds in the predominantly sp³-like insulating carbon matrix through the electric field induced dielectric breakdown process and thermal fuse effects.     

Characterization of amorphous carbon films deposited by surface wave plasma CVD

Many dangling bonds in hydrogenated amorphous carbon (a-C:H) films are usually generated by bombardments of high-energy ion precursors in typical chemical vapor deposition (CVD). To generate low dangling bonds, a-C:H films should be deposited from low-energy radical species. Surface wave plasma (SWP) generates low-energy and high-density radicals. We prepare a-C:H films using SWP and investigate the relationship between the plasma characteristics and structures of a-C:H films. The microwave of the TM01 mode was introduced through the dielectric window and SWP generate under the dielectric window. An Ar and C₂H₂ plasma mixture mainly consists of neutral radical species, and the electron temperature is as low as 1 eV. Electron density significantly decreases with increasing distance from the dielectric window. The a-C:H films are prepared from these hydrocarbon and carbon low-energy radicals as main precursors. The sp² bonded network cluster size in a-C:H films increase with electron density in SWP. This structure change is the influence of the termination structure of clusters changing to CH from CH₃ and CH₂.     

Surface roughness evolution and growth mechanism of carbon films from hyperthermal species

The roughness evolution of carbon films deposited from hyperthermal species was investigated by AFM. 10 eV C deposition at normal incidence angle starts with formation of 10 nm high islands followed by continuous, sp² rich films at larger doses with essentially the same feature height and film roughness. 40 eV C deposition at normal incidence angle (0°) forms sp³ rich, atomically smooth films, which become sp² rich and rough at oblique angles (≥ 60°). The limitations of currently available molecular dynamic simulations prevent their use to describe the island formation during 10 eV C bombardment. Dedicated calculations probing the effect of incidence angle on 40 eV C deposition exhibit similar trends to the experimental data i.e. decrease of the sp³ fraction and increase of the roughness with increasing incidence angle. The results are in accord with the “subplantation” scheme, linking roughness and sp² bonding to surface entrapment. Implications on recent works discussing growth mechanisms or surface smoothening are given.     

Nitrogenated carbon films deposited using filtered cathodic arc

Nitrogenated carbon films were deposited on various substrates using filtered cathodic arc. Non-uniformity of the film thickness was less than 5% over a 15 cm diameter area. Mechanical, optical (refraction index, extinction coefficient versus wavelength) and electrical properties were investigated as a function of nitrogen flow rate. Deposited coatings demonstrated high hardness of 40–65 GPa, Young's modulus 200–285 GPa, excellent elastic recovery, high critical pressure for scratch formation, and surface smoothness. While the hardness showed a relatively small decrease with nitrogen flow increase, the stress decrease was more significant (8–3.8 GPa). Extremely low wear rates were observed, even at high contact pressures, and no substantial debris was detected indicating that carbon is oxidized during wear. Clear correlation was found between transparency, electrical resistivity and stress of the films. Transparency and resistivity showed a significant rise with an increase of stress. An explanation of the film properties is based on the assumption that the basic characteristics of the deposited films were determined by the relative proportion of two three dimensional complementary type of bonds; the tetrahedral sp³ bonds leading to stiff networks, and the trigonal sp² arrangments close to fullerene-like, or nanotube-like, structures.     

Microstructure of c-BN thin films deposited on diamond films

Diamond films were used as substrates for cubic boron nitride (c-BN) thin film deposition. The c-BN films were deposited by ion beam assisted deposition (IBAD) using a mixture of nitrogen and argon ions on diamond films. The diamond films exhibiting different values of surface roughness ranging from 16 to 200 nm (in R_rms) were deposited on Si substrates by plasma enhanced chemical vapor deposition. The microstructure of these c-BN films has been studied using in situ reflexion electron energy loss spectroscopy analyses at different primary energy values, Fourier transform infrared spectroscopy and high resolution transmission microscopy. The fraction of cubic phase in the c-BN films was depending on the roughness of the diamond surface. It was optimized in the case of the smooth surface presenting no particular geometrical effect for the incoming energetic nitrogen and argon ions during the deposition. The films showed a nanocrystalline cubic structure with columnar grains while the near surface region was sp² bonded. The films exhibit the commonly observed layered structure of c-BN films, that is, a well textured c-BN volume lying on a h-BN basal layer with the (00.2) planes perpendicular to the substrate. The formation mechanism of c-BN films by IBAD, still involving a h-BN basal sublayer, does not depend on the substrate nature.     

Embedded Capacitor Technology Using Aerosol Deposition

Embedded passives, which achieve miniaturization, cost reduction, and higher performance, are regarded as one of the most promising technologies for a future RF module substrate. Currently, a BaTiO₃/Polymer composite is being used for the embedded capacitors in printed wiring boards. One of the drawbacks of this composite is its relatively low dielectric constant, because the polymer component with a low dielectric constant suppresses the dielectric constant of the whole composite. We propose a resin build-up circuit board with passive functions embedded in a ceramic film without any polymer component for the next-generation low-cost RF modules. We have already manufactured a prototype board with ceramic capacitors embedded in an FR-4 substrate using a unique ceramic deposition technology: aerosol deposition (ASD) in which many kinds of ceramics can be deposited on a substrate at room temperature by making use of accelerated ceramic nanoparticle aerosol bombardment with a nozzle. In this study, first we examine the effects of the characteristics of raw ceramic powder on the crystal structure and the dielectric properties of ASD films. As a result, we confirmed that dense BaTiO₃ dielectric films can be deposited when raw powder without strain is used. From the resulting polarization versus electrical field (P–E curve), we confirmed that paraelectric was observed in the dense films, while the porous BaTiO₃ films deposited using milled powder exhibit a small hysteresis loop. We also clarified that dense BaTiO₃ dielectric films exhibit a nanostructure with a texture consisting of particles under 10 nm in diameter. We also examine the interfacial behavior between BaTiO₃ dielectric films and the Cu electrode, in order to investigate the deposition temperature and the reliability of a BaTiO₃ ASD film under high temperature (250°C), high humidity (100 Rh%), thermal cycle condition (−55°C to 150°C), and bias DC voltage (5 V). We clarified that the BaTiO₃ ASD film satisfies the criteria of reliability in the microelectronic packaging area.     

Corrosion and tribological properties of ultra-thin DLC films with different nitrogen contents in magnetic recording media

The corrosion spot density and contact–start–stop tribological properties that correlate to mechanical properties, electrical resistivity and lubricant bonded ratio of DLC overcoats on different disks of various surface roughness were investigated. DLC overcoats of hydrogenated carbon (CH) and nitrogenated carbon (CN) films were deposited by ion beam deposition (IBD) and sputter, respectively. Results show that the intensity ratio I(D)/I(G) increases with decreasing IBD-CH film thickness and increasing N₂ concentration of sputtered-CN layer, which implies that the films prepared at higher N₂ concentration contain a relatively lower sp³ bonded carbon. The composite hardness and Young's modulus of DLC films decrease with decreasing IBD-CH thickness and increasing N₂ concentration of sputtered-CN layers. Compared to disk overcoats deposited with only IBD-CH of comparable thickness, the lubricant bonded ratio is dramatically increased from 12 to 30% when the 0.5 nm CN is deposited on IBD-CH film. By increasing the N₂ concentration in the CN layer from 10 to 50 at.%, the electrical resistivity decreased from 3.6 to 0.8 kΩ and the lubricant bonded ratio increased from 30 to 46%. The corrosion spots density of sputtered-CN film surface decreases with increasing N₂ concentration. It is concluded that the dual layer of 1.5 nm IBD-CH/0.5 nm sputtered-CN with 30% N₂ deposition has the best integrated performance of corrosion resistance and CSS tribological properties.     

A correlation between the microstructure and optical properties of hydrogenated amorphous carbon films prepared by RF magnetron sputtering

Comparative and systematic studies of the effect of the radiofrequency (RF) bias on the microstructure and the optical properties of hydrogenated amorphous carbon (a-C:H) have been carried out on films deposited by RF magnetron sputtering under different RF power varying from 10 to 250 W applied to the graphite target, leading to a negative bias voltage at the target in the range of −60 to −600 V.A combination of infrared (IR) absorption experiments, which give information about the local microstructure (i.e. C–C and C–H bonding), and optical transmission measurements in the UV-visible and near IR, from which we determined the optical gap E₀₄ and the refractive index n, are applied to fully characterize the samples in their as-deposited state. The results show first that the films deposited at low RF power (i.e. low negative bias) exhibit a more open microstructure (polymeric character) with a lower density than those deposited at high RF power (i.e. high negative bias). They also indicate that the total bonded H content as well as the sp³/sp² ratio of carbon atoms bonded to H decrease with increasing RF power leading to the formation of higher proportions of C-sp² sites. The same tendency is observed for the optical gap E₀₄. On the contrary, the refractive index increases with increasing RF power, suggesting the densification of the films in going to a higher RF power.     

Enhanced cycling stability of Ni-MH battery by depositing amorphous carbon film on the Ti1.4V0.6Ni negative electrode

Amorphous carbon (a-C) films with various thicknesses depending on the reaction time are deposited on the surface of Ti_1.4V_0.6Ni alloy electrodes for Ni-MH (nickel-metal hydride) battery by radio frequency plasma enhanced chemical vapor deposition (RF-PECVD). With the increasing deposition time, the Raman spectra show a gradually disordered sp²-bonding change of the films and the changing trend of sp²/sp³ is obtained by X-ray photoelectron spectroscopy. The a-C film of depositing for 30 min with the thickness of 400 nm shows a favorable stability in alkaline electrolyte, the capacity is enhanced by 36.2% after 50 cycles than the bare electrode, and the charge voltage is 80 mV lower than the bare one. The a-C film with high sp²-bonded carbon content effectively reduces the charge transfer resistance, and as a coating layer, the dissolution of V of the alloy is also inhibited. In particular, to get a proper discharge voltage and a stable capacity simultaneously, covering completely and an appropriate thickness of the a-C film are crucial for an expected performance.     

Preparation and characterization of TiO2 thin films by PECVD on Si substrate

Titanium oxide thin films were prepared on p-Si(l00) substrate by plasma enhanced chemical vapor deposition using high purity titanium isopropoxide and oxygen. The deposition rate was little affected by oxygen flow rate, but significantly affected by RF power, substrate temperature, carrier gas flow rate, and chamber pressure. Morphology of the film became coarser with increasing deposition time and chamber pressure, and the film showed less uniformity at high deposition rates. It was also found that the overall deposition process is controlled by heterogeneous surface reaction below 200°C., but controlled by mass transfer of reactants at higher temperatures. TiO₂ films deposited at temperatures lower than 400°C was amorphous, but showed the anatase crystalline structure upon 400°C deposition. The dielectric constant was about 47 for the films post-treated by rapid-thermal annealing (RTA) at 800°C. The leakage current was about 2×10⁻⁵ A/cm² for the films deposited at 400°C and RTA-treated at 600°C. However, it was decreased to less than 3×10⁻⁷ A/cm² for the film RTA-treated at 800°C.     

Hydrogenated amorphous carbon films deposited on 316L stainless steel

Research on hydrogen amorphous carbon films (a-C:H), which possess the diamond-like characteristic, has been stimulated for many years by need to simultaneously optimizing the mechanical, optical and biological properties, and by challenges related to the deposition of a-C:H films on medical implants. In the present work, we investigate the structure, optical and mechanical properties (hardness, elastic modulus and stress) of a-C:H films deposited on 316L stainless steel substrate by the radio frequency plasma enhanced chemical vapor deposition (RF PECVD). The negative self-bias voltages significantly influence on temperature of steel substrates during the deposition process and films properties. Specifically, the high energetic deposition leads also to stabilization of the sp² content and thermally-activated relaxation in the stress of a-C:H films. Presented correlation between the obtained results and literature analysis let deem the Raman spectra as a good tool to control the properties of implants made of 316L stainless steel with a-C:H film for general use.     

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.     

Seed layer mediated growth of high dielectric and low leakage BaTiO3 thin film using two-step sputtering process

In this study, we demonstrated the seed layer mediated growth of high-quality BaTiO₃ (BTO) thin films using a two-step radio frequency (RF) magnetron sputtering process. Since the as-grown BTO thin films obtained by RF magnetron sputtering at the deposition temperatures of 300–500 °C were amorphous with a low dielectric constant of 20, it is necessary to develop a fabrication process for obtaining crystalline high-k BTO thin films without sacrificing other film properties such as morphology and leakage current. First, it was revealed that ex-situ post-deposition annealing (PDA) at high temperatures in the 700–800 °C range led to the crystallization of BTO films and a high dielectric constant of 121. However, the film morphology deteriorated significantly during PDA, and consequently, a high leakage current was observed due to the rough and discontinuous surface containing voids and micro-cracks. To achieve an excellent leakage current characteristic as well as a high dielectric constant for a crystalline BTO thin film, in-situ crystallization was carried out through local epitaxial growth using a crystalline seed layer. The crystalline BTO seed layer was formed by annealing a 5-nm-thick amorphous BTO film at 700 °C on which the in-situ crystallized BTO main layer was deposited at 500 °C. The in-situ crystallization method resulted in a smooth and uniform surface and a high dielectric constant of 113. In addition, the in-situ crystallized BTO film exhibited a low leakage current density of 10⁻⁶ A/cm² (at 0.8 V) displaying an improvement by a factor of 10³ compared to the ex-situ crystallized BTO film.     

Deposition of hard amorphous hydrogenated carbon films by radiofrequency parallel-plate hollow-cathode plasmas

Hard amorphous hydrogenated carbon (a-C:H) films were deposited by plasma decomposition of CH₄ gas in a RF parallel-plate hollow-cathode system. The deposition system was built by placing a metallic plate in parallel to and in electrical contact with an usual RF-PECVD planar cathode. Self-bias versus RF power curves were used to make an initial characterization of plasma discharges in nitrogen gas atmospheres, for pressures between 10 and 100 mTorr. The strongly increased power consumption to obtain the same self-bias in the hollow-cathode system evidenced an increase in plasma density. The a-C:H films were deposited onto Si single crystalline substrates, in the − 50 to − 500 V self-bias range, at 5, 10 and 50 mTorr deposition pressures. The film deposition rate was found to be about four times than that usually observed for single-cathode RF-PECVD-deposited films, under methane atmosphere, at similar pressure and self-bias conditions. Characterization of film structure was carried out by Raman spectroscopy on films deposited at 10 and 50 mTorr pressures. Gaussian deconvolution of the Raman spectra in its D and G bands shows a continuous increase in the I_D/I_G integrated band intensity ratio upon self-bias increase, obeying the expected increasing behavior of the sp² carbon atom fraction. The peak position of the G band was found to increase up to − 300 V self-bias, showing a nearly constant behavior for higher self-bias absolute values. On the other hand, the G band width showed a nearly constant behavior within the entire self-bias range. Nanohardness measurements have shown that films deposited with self-bias greater than 300 V are as hard as films obtained by the usual PECVD techniques, showing a maximum hardness of about 18 GPa. Films were also found to develop high internal compressive stress. The stress dependence on self-bias showed a strong maximum at about − 200 V self-bias, with a maximum stress value of about 5 GPa.     

Effect of deposition voltage on the microstructure of electrochemically deposited hydrogenated amorphous carbon films

Hydrogenated amorphous carbon (a-C:H) films were deposited on Si substrates by electrolysis in a methanol solution at ambient pressure and a low temperature (50 °C), using various deposition voltages. The influence of deposition voltage on the microstructure of the resulting films was analyzed by visible Raman spectroscopy at 514.5 nm and X-ray photoelectron spectroscopy (XPS). The contents of sp³ bonded carbon in the various films were obtained by the curve fitting technique to the C1s peak in the XPS spectra. The hardness and Young’s modulus of the a-C:H films were determined using a nanoindenter. The Raman characteristics suggest an increase of the ratio of sp³/sp² bonded carbon with increasing deposition voltage. The percentage of sp³-bonded carbon is determined as 33–55% obtained from XPS. Corresponding to the increase of sp³/sp², the hardness and Young’s modulus of the films both increase as the deposition voltage increases from 800 V to 1600 V.     

Microstructure,optical and electrical properties of sputtered HfTiO high-k gate dielectric thin films

The microstructure, optical and electrical properties of HfTiO high-k gate dielectric thin films deposited on Si substrate and quartz substrate by RF magnetron sputtering have been investigated. Based on analysis from x-ray diffraction (XRD) measurements, it has been found that the as-deposited HfTiO films remain amorphous regardless of the working gas pressure. Meanwhile, combined with characterization of ultraviolet-visible spectroscopy (UV–vis) and spectroscopy ellipsometry (SE), the deposition rate, band gap and optical properties of sputtered HfTiO gate dielectrics were determined. Besides, by means of the characteristic curves of high frequency capacitance–voltage (C–V) and leakage current density–voltage (J–V), the electrical parameters, such as permittivity, total positive charge density, border trap charge density, and leakage current density, have been obtained. The leakage current mechanisms are also discussed. The energy band gap of 3.70 eV, leakage current density of 1.39×10⁻⁵ A/cm² at bias voltage of 2 V, and total positive charge density and border trap charge density of 9.16×10¹¹ cm⁻² and 1.3×10¹¹ cm⁻², respectively render HfTiO thin films deposited at 0.6 Pa, potential high-k gate dielectrics in future CMOS devices.     

Diamond-like carbon (DLC) films as electrochemical electrodes

Amorphous carbon can be any mixture of carbon bonds of sp³, sp², and even sp¹, with the possible presence of hydrogen. The group of mixture, of which there is a high fraction of diamond-like (sp³) bonds, is named diamond-like carbon (DLC). Unlike the crystalline carbon materials: diamond, graphite, carbon nanotube, fullerene and graphene, DLC can be deposited at room temperature without catalyst or surface pretreatment. Furthermore, its properties can be tuned by changing the sp³ content, the organization of sp² sites and hydrogen content, and also by doping. This paper firstly reviewed the electrochemical properties of DLC films and their applications.