Carbon Thin Films Research Articles

Investigation of fundamental electrical and optoelectronic properties of an organic- and carbon-based MnPc/GC photodiode with high photosensitivity

The aim of this work is to provide an alternative to optoelectronic devices that use carbon and organic materials. To achieve this, we coated a modified MnPc organic semiconductor compound onto a graphite-like carbon (GC) thin film using the thermal evaporation technique, and fabricated an organic-based, highly light-sensitive MnPc/GC hybrid heterojunction. The heterojunction had a transmittance of approximately 60% in the visible region, an absorption coefficient of ∼106 m−1, and an energy band gap of 2.6 eV. Subsequently, Ag contacts were grown on the surface of each layer, and the Ag/MnPc/GC/Ag photodiode was subjected to fundamental electrical analysis at various light intensities and a ±3 V applied potential. Analysis in a dark environment revealed that the photodiode had a rectification ratio of 2.59 × 103, a series resistance of 28 Ω, and a shunt resistance of 4.17 × 104 Ω, as calculated from Ohm’s law. The diode ideality factor and barrier height of the photodiode were determined from thermionic emission theory to be 5.60 and 0.71 eV, respectively, and it was observed that these decreased with increasing light intensity. The photodetector parameters of the MnPc/GC hybrid photodiode were determined under positive and negative applied potentials at various light intensities. The highest photocurrent, photoconductive responsivity, photosensitivity, and specific detectivity were determined to be 1.512 × 10−1 A, 11.52 A.W−1, 9.83 × 105, and 2.48 × 1012 Jones, respectively, which were significantly higher than those reported in literature for organic and inorganic-based photodiodes. Based on the findings, it was concluded that the Ag/MnPc/GC/Ag photodiode holds promise as an alternative for sensors, solar cells, photodetectors, and optoelectronic communications applications.

Upcycling of surgical facemasks into carbon based thin film electrode for supercapacitor technology

Polypropylene (PP), a commonly used plastic, is used for making the outer layers of a surgical face mask. In 2020, around 3 billion surgical face masks were disposed into the environment, causing a huge threat to wildlife, aquatic life, and ecosystems. In this work, we have reported the sulfonation technique for stabilizing the surgical face masks and their conversion into carbon nanoparticles for application as a supercapacitor electrode. The electrode is fabricated by preparing a slurry paste of carbon nanoparticles and pasting it on a conductive wearable fabric. To investigate the performance of the carbon thin film electrode, electrochemical techniques are employed. The Cyclic Voltammetry (CV) analysis performed at different scan rates in a 6 molar KOH electrolyte reveals that the carbon thin film acts as a positive electrode. At 4 A g−1, the electrode shows a specific capacitance of 366.22 F g−1 and 100% retention of specific capacitance for 8000 cycles. A two-electrode asymmetric device is fabricated using carbon thin film as the positive electrode, NiO thin film as the negative electrode, and a KOH separator between two electrodes. The device shows a specific capacitance of 113.73 F g−1 at 1.3 A g−1 and glows a red LED for 6 min. This work is a step towards upcycling the waste produced from surgical face masks used during the COVID-19 pandemic and its application for energy storage.

Morphological changes of carbon thin films with nitrogen doping synthesized by microwave-excited surface wave plasma CVD

Nitrogen (N) doped graphene-based materials are of significant interest for various applications, such as, catalytic reactions, tribological energy generation, sensor devices and other electronic device applications. Most recently, the catalytic and noncatalytic growth of graphene structures at a low substrate temperature were explored by using the microwave-excited surface wave plasma (MW-SWP) chemical vapor deposition (CVD) technique. In this study, growth of carbon thin films is investigated by the MW-SWP CVD technique with nitrogen doping at various temperatures on the insulating substrates. It is obtained that partially graphitized carbon thin films can be obtained at a temperature as low as 150 °C on the quartz substrates. Interestingly, the morphological changes are observed with nitrogen doping and change in synthesis temperature for the carbon thin films grown by the MW-SWP CVD method. The partially graphitized carbon thin films form irregular morphologies at a lower temperature, while the morphology transforms with increase in temperature. At a certain growth temperature (500 and 700 °C), the carbon film shows granular morphology without addition of nitrogen, whereas the addition of nitrogen reduces the granular morphology and forming planar structures. Thus, these studies reveal the growth of carbon films with control morphology with respect to incorporation of nitrogen, which can be significant to develop carbon films and nanostructures for diverse fields of applications.

Highly effective Pt-free counter electrode constructed by break bone-like CoTe@graphite carbon thin films dye-synthesized solar cell

To boost the efficiency of dye-sensitized solar cells (DSSCs) at a cheaper cost than currently available counter electrodes, platinum (Pt)-based CEs are necessary. We demonstrate the creation of thin films with different aspect ratios made of molybdenum ditelluride (CoTe) combined with graphitic carbon nitrides (g-C3N4) using the chemical vapour deposition technique on an FTO glass substrate. According to XRD, Raman, SEM, and TEM examination, the 2D nanosheets of g-C3N4have a polycrystalline nature and uniform nanograins that break human bone like the morphology of CoTe. The optical band gap and charge transfer efficiency of the films was assessed using UV and PL spectroscopy. In experiments, the modification of DSSCs with g-C3N4 significantly increased their photoelectric conversion efficiency. The DSSC incorporating CoTe@g-C3N4CE achieved high-power conversion efficiency (PCE) of 8.52% compared to DSSC with bare CoTe CE (2.67%).Furthermore, the upgraded CoTe@g-C3N4CE exhibited improved electron lifetime compared to other CEs, significant reduction towards I3-, and good electrocatalytic activity. Additionally, CoTe@g-C3N4 shows excellent electrocatalytic activity and prolonged electron lifetime, which is supported by experimental work using Tafel polarisation, EIS, and CV.

Amorphous carbon thin films: Mechanisms of hydrogen incorporation during magnetron sputtering and consequences for the secondary electron emission

Amorphous carbon (a-C) films, having low secondary electron yield (SEY), are used at CERN to suppress electron multipacting in the beam pipes of particle accelerators. It was already demonstrated that hydrogen impurities increase the SEY of a-C films. In this work, a systematic characterization of a set of a-C coatings, deliberately contaminated by deuterium during the magnetron sputtering deposition, by scanning electron microscopy, ion beam analysis, secondary ion mass spectrometry, and optical absorption spectroscopy was performed to establish a correlation between the hydrogen content and the secondary electron emission properties. In parallel, the mechanisms of contamination were also investigated. Adding deuterium allows resolving the contributions of intentional and natural contamination. The results enabled us to quantify the relative deuterium/hydrogen (D/H) amounts and relate them with the maximum SEY (SEYmax). The first step of incorporation appears to be formation of D/H atoms in the discharge. An increase in both the flux of deposited carbon atoms and the discharge current with a D2 fraction in the gas discharge can be explained by target poisoning with deuterium species followed by etching of CxDy clusters, mainly by physical sputtering. For overall relative D/H amounts between 11% and 47% in the discharge gas, the SEYmax increases almost linearly from 0.99 to 1.38. An abrupt growth of SEYmax from 1.38 to 2.12 takes place in the narrow range of D/H relative content of 47%–54%, for which the nature of the deposited films changes to a polymer-like layer.

F2 Laser-Induced Micro-Reticulated Structural Changes of Amorphous Carbon Thin Films

Micro/nanoprocessing of materials using lasers is currently an active research topic. In that research, the choice of the laser to be used is critical, but the F2 laser, which has the shortest wavelength (157 nm) among commercially available lasers, has few research compared to its potential. In this paper, we discovered a new photochemical processing by using an F2 laser to irradiate an amorphous carbon thin film. The short wavelength and high photon energy of the F2 laser can photoexcite the surface of the thin film at high density and generate active oxygen atoms O(1D) by photodecomposition of atmospheric oxygen molecules. As a result, the optical change of the amorphous carbon thin film was induced without thickness reduction, and a micron-sized network-like, reticulated structural change was formed in the thin film surface after one month at the latest. The formed micron-sized reticulated structure was relatively swollen, and a graphitization occurred in the structure, observed by Raman spectroscopy. However, the structure was not observed when the laser irradiated area became smaller. This work has made it possible to form a micron-sized reticulated structure including carbon nanocrystals in an amorphous carbon, which is expected to further expand the applications of carbon materials.

Fabrication of plane-type axon guidance substrates by applying diamond-like carbon thin film deposition

This research aims to fabricate plane-type substrates for evaluating the axon behaviors of neuronal cells in vitro toward the development of brain-on-chip models by applying the functions of diamond-like carbon (DLC) thin film deposition, which helped to eliminate the costly and time-consuming lithography process by utilizing a shadow mask. The DLC thin films were partially deposited on stretched polydimethylsiloxane (PDMS) substrates covered with a metal mask by the plasma chemical vaper deposition method, and using the substrates culture teats with human neuroblastoma cells (SH-SY5Y) were performed. Three patterns of interconnection structures of axons were created on the substrates with disordered and regular linear wrinkle structures with several μm size formed by the depositions. The patterns were characterized by the structure that the aggregations of axons formed on the linear DLC thin film deposited areas were separately placed in regular intervals and connected each other by plenty of axons, which were individually taut in a straight line at about 100 to over 200 μm in length. The substrates expected of uses for evaluation of axon behaviors are available without fabricating guiding grooves by conventional soft lithographic methods requiring multiple stages and their treating times.

Electrical Properties of Silicon Oxide Layers Subjected to High-Temperature Treatment Reproducing the Growth Conditions for Thin Carbon Films

Electrical Properties of Silicon Oxide Layers Subjected to High-Temperature Treatment Reproducing the Growth Conditions for Thin Carbon Films

Large-Scale Moth-Eye-Structured Roll Mold Fabrication Using Sputtered Glassy Carbon Layer and Transferred Moth-Eye Film Characterization.

Currently, there is high demand for the development of a highly mass-producible technology for manufacturing moth-eye-structured films with an antireflection function. Conventional moth-eye-structured films have been produced by roll-to-roll (RTR) ultraviolet nanoimprint lithography (UV-NIL) using porous alumina, but the process of manufacturing the roll mold with aluminum is both complicated and time-consuming. To solve this problem, we proposed a sputtering process for forming a thin film of glassy carbon on a roll substrate and fabricated a moth-eye structure through the irradiation of oxygen plasma. A glassy carbon (GC) moth-eye-structure roll mold with a uniform reflectance of less than 0.1% over a length of 1560 mm was fabricated following this method. In addition, a superhydrophobic moth-eye-structured film was produced by RTR UV-NIL using the proposed roll mold, which exhibited a reflectance of 0.1%. In this study, a moth-eye-structure roll using porous alumina was compared with a film transferred from it. The GC moth-eye-structure roll mold was found to be superior in terms of antireflection, water repellency, and productivity. When the proposed large-area GC moth-eye-structured film was applied to window glass, significant anti-reflection and water-repellent functionalities were obtained.

Low temperature electrical transport in thin carbon films deposited on SiO2/Si substrates by pulsed laser deposition

In this paper electrical transport studies are performed on thin carbon films deposited on SiO2/Si substrates by pulsed laser deposition (PLD) applying laser ablation of micro-crystalline graphite target. Experiments were carried out on 320 - 420 nm thick SiO2 on Si substrates as well as on hydrogenated diamond-like carbon (DLC) films deposited on SiO2/Si. Structural studies by means of XPS, SEM and Raman spectroscopy revealed that the films can be characterized as nano-sized carbon phases possessing different phase composition (i.e. the ratio sp3/sp2 hybridized carbon, etc.). The electrical conductivity/resistivity of the films was measured in the temperature range 10 K < T < 300 K. Four-contact Van der Pauw method as well as two contact schemes have been applied. Some films have low room temperature resistivity in the range ρ = (0.1–1.5)×10-3 Ω.·m and consist predominantly of sp2 hybridized carbon with Raman spectra, which resemble that of nano-sized graphene depending on the deposition conditions and substrates used. The thinnest only 0.5 nm layer deposited directly on SiO2 exhibits relatively low specific resistance (~10-3 Ω. m), which can be taken as an indication of good deposition conditions of graphene-like layers. The current flow mechanism was explored at temperatures from 300 K down to 10K. The temperature dependence reveals non-metallic behavior - the conductivity decreases at decreasing temperature as opposed to typical metal behaviour. A model of variable range hopping (VRH) mechanism is applied to explain the low temperature conductivity drawn from transport in nanocrystalline disordered systems.

Anti-Stokes Raman spectroscopy for probing functional groups in amorphous carbon thin films

Ultra-thin amorphous carbon (a-C) films are well established protective coatings of optical fibers. These coatings allow one to prevent degradation of the SiO2 fiber, which occurs due to diffusion of the water and hydrogen molecules into cladding and core. The a-C films typically contain impurities, such as oxygen and hydrogen, which are attached to organic moieties via chemical bonding. The formation of hydrogen- and oxygen-containing functional groups reduces the hermeticity of a-C coatings, and therefore, monitoring these impurities is of great importance. In this work, we develop a method for probing O- and H- containing moieties based on resonance anti-Stokes Raman spectroscopy. We measured Raman spectra of a-C films and observed that anti-Stokes to Stokes ratios of Raman peaks differ from those predicted by Boltzmann law. This effect caused by resonance enhancement of the anti-Stokes Raman scattering in defects of graphite-like crystals. To quantify this effect, we used a resonance factor, which is defined as a ratio of the anti-Stokes and Stokes scattering cross sections. We show that this indicator can be used to assess degree of enrichment/depletion of a-C with O- and H- containing functional groups. Understanding the physical mechanisms of the anomalous anti-Stokes Raman scattering will improve Raman thermometry.

Influence of Fluorine Doping on Hardness and Compressive Stress of the Diamond-Like Carbon Thin Film

Influence of Fluorine Doping on Hardness and Compressive Stress of the Diamond-Like Carbon Thin Film

The Amorphous Carbon Thin Films Synthesized by Gas Injection Magnetron Sputtering Technique in Various Gas Atmospheres

This work presents the potential for using pulsed gas injection to produce amorphous carbon films. In this experiment, the frequency of injecting small amounts of gas was used to control the pressure amplitudes, thus achieving the conditions of plasma generation from stationary, through quasi-stationary, to pulsed oscillations of pressure. In addition, we used various gases and their mixtures, an alternative to argon. In the experiment, we studied the energy state of the plasma. The films were examined for phase and chemical composition, surface morphology, and optical and mechanical properties. We determined low-frequency pulsed gas injections to be conditions favorable for C(sp3)−C(sp3) bond formation. The plasma generated by gas injections is better ionized than that generated by static pressure. Pulsed conditions favor the plasma species to retain their kinetic energy, limiting the probability of intermolecular collision events. Since helium has a relatively high ionization energy, it is a practical addition to sputtering gas because of the increasing sp3 content in the films. The electrons created by helium ionization improve the plasma’s ionization degree.

Filtered cathodic vacuum arc deposition of tetrahedral amorphous carbon thin films on surgical blades and its corrosion resistance in phosphate buffer solution (PBS) at pH 7.4

Surgical blades are prone to corrosion in a body fluid environment, increasing the risk of surgical infection and inflammation. In this paper, the ta-C thin films was deposited on surgical blades by filtered cathode vacuum arc (FCVA) method. Modern analytical methods such as SEM, Raman, surface profiler and electrochemical corrosion were used for the test and analysis. The results show that the corrosion potential and corrosion current density of uncoated surgical blades are −507 mV and 2.43 μA/cm2 during surgery operation in a simulated human environment (pH 7.4 PBS solution), and the corrosion potential of the ta-C thin films surgical blades immersed in 0.25 h, 0.5 h and 1 h are −395 mV, −431 mV, −445 mV, and the corrosion current density are 1.11 μA/cm2, 1.46 μA/cm2, 1.58 μA/ cm2. The results show that the ta-C thin films surgical blades are excellent corrosion resistance during surgery operation in a simulated human environment. SEM shows that the ta-C thin films surgical blades have a smooth surface with a compact and uniform films structure, and the thicknesses of the ta-C thin films and Ti transition layer are 2.2 µm and 2.4 µm respectively. The surface profiler shows that the average roughness of the surgical blades and the ta-C thin films surgical blades are 295.979 nm and 477.417 nm. Raman shows that ta-C thin films is of high purity, without any impurity phase, and does not cause other adverse reactions during surgery operation.

Control of Microstructure in Iron–Carbon Thin Films by Means of Electromigration

Herein, it is demonstrated that high DC electric current densities can be used to tailor the microstructure of iron–carbon thin films. Specifically, elongated ferrite grains can be formed in a nanocrystalline matrix via a process involving electromigration‐induced carbide migration. Herein this article, the parameters that are required to produce and control elongated grain formation in the Fe(C) system are mapped out and they are interpreted in terms of carbon electromigration, and the flux divergences need to reach a critical carbon concentration for precipitate growth and migration. Possible approaches to allow more precise control of the elongated grains are discussed, as are the requirements for material systems where microstructure control through electromigration should be feasible.

The effect of coated diamond-like carbon thin films on polymer tooth based denture: Micro-morphology and fractal feature studies

To consider improving the micromorphology study of dentures combined with biocompatibility in recent years, we study hybrid organic–inorganic materials and diamond-like carbon coated on tooth-based dentures by the sol–gel and the RF sputtering method, respectively. Afterward, the effect of such material coating on the surface roughness and surface topography of dentures was evaluated. Aimed at this, 3D atomic force microscope images were analyzed via MountainsMap® Premium software, which divided the surface into peaks and pits through the watershed segmentation algorithm. This method made motif analysis possible by detecting the surface dimensions, curvature, volume, perimeters, shape, structure, etc., and the obtained statistics indicate interesting results for the regular and irregular topography and the surface of the prepared samples. In addition, the energy-dispersive x-ray spectrum illustrates the existence of N, C, O, Na, and Si in all samples, with the maximum value of C in the diamond-like carbon coated sample, which is because of the highest value of carbon in diamond-like carbon. Scanning electron microscope images also present a series of grooves on the surface with small randomly oriented cracks. The linear interpolation type shows that the surface of diamond-like carbon coated on the hybrid-control sample has the most irregular topography while the most regular topography was found in the hybrid coated control sample.

Nickel concentration dependent mechanical and tribological properties of subsurface layer of electrodeposited Ni-C nanocomposite thin films

Electrodeposited nickel- carbon (Ni-C) nanocomposite thin films are found to have varying mechanical and tribological properties. Ni-C nanocomposites thin films of varying nickel content were synthesized by a simple electrodeposition method. Annealed thin films possess a relatively hard and adherent subsurface layer. In order to have an understanding of the mechanical and tribological characteristics of the subsurface layer, the relatively soft and fragile outer layer of the thin films was removed by scraping. The sp2 and sp3 bondings of carbon atoms in the thin films were explored by Raman spectroscopy. The Fourier- transform infrared spectra of the diamond-like carbon (DLC) and Ni-C thin films also consist of sp2 and sp3 hybridized carbon bonds. Nanocrystalline nickel nanoparticles distributed in carbon matrix were observed in Transmission electron microscopy study of the films. Decrease in coefficient of friction of the films is observed with increase in nickel content in thin films having DLC structure. The highest nickel content Ni-C composite thin film shows the maximum hardness of 7.6 GPa while the amorphous DLC thin film possesses the least hardness of 2.19 GPa. The subsurface layers demonstrate a clear demarcation of mechanical properties with unmodified overlayer pointing towards an extra care must be exercised before applying these electrodeposited coating on technological appliances.

The Use of Sacrificial Graphite-like Coating to Improve Fusion Efficiency of Copper in Selective Laser Melting

Thin and ultrathin carbon films reduce the laser energy required for copper powder fusion in selective laser melting (SLM). The low absorption of infrared (IR) radiation and its excellent thermal conductivity leads to an intricate combination of processing parameters to obtain high-quality printed parts in SLM. Two carbon-based sacrificial thin films were deposited onto copper to facilitate light absorption into the copper substrates. Graphite-like (3.5 µm) and ultra-thin (25 nm) amorphous carbon films were deposited by aerosol spraying and direct current magnetron sputtering, respectively. The melting was analyzed for several IR (1.06 µm) laser powers in order to observe the coating influence on the energy absorption. Scanning electron microscopy showed the topography and cross-section of the thermally affected area, electron backscatter diffraction provided the surface chemical composition of the films, and glow-discharge optical emission spectroscopy (GDOES) allowed the tracking of the in-deep chemical composition of the 3D printed parts using carbon film-covered copper. Ultra-thin films of a few tens of nanometers could reduce fusion energy by about 40%, enhanced by interferences phenomena. Despite the lower energy required, the melting maintained good quality and high wettability when using top carbon coatings. A copper part was SLM printed and associated with 25 nm of carbon deposition between two copper layers. The chemical composition analysis demonstrated that the carbon was intrinsically removed during the fusion process, preserving the high purity of the copper part.

Optical and structural properties of nitrogen incorporated Ni doped diamond-like carbon thin films

Optical and structural properties of nitrogen incorporated Ni doped diamond-like carbon thin films

Semiconductor process fabrication of multiscale porous carbon thin films for energy storage devices

Semiconductor process fabrication of multiscale porous carbon thin films for energy storage devices