Overcoming the quality–quantity tradeoff in dispersion and printing of carbon nanotubes by a repetitive dispersion–extraction process

Dispersion-printing processes are essential for the fabrication of various devices using carbon nanotubes (CNTs). Insufficient dispersion results in CNT aggregates, while excessive dispersion results in the shortening of individual CNTs. To overcome this tradeoff, we propose here a repetitive dispersion–extraction process for CNTs. Long-duration ultrasonication (for 100 min) produced an aqueous dispersion of CNTs with sodium dodecylbenzene sulfonate with a high yield of 64%, but with short CNT lengths (a few μm), and poor conductivity in the printed films (∼450 S cm⁻¹). Short-duration ultrasonication (for 3 min) yielded a CNT dispersion with a very small yield of 2.4%, but with long CNTs (up to 20–40 μm), and improved conductivity in the printed films (2200 S cm⁻¹). The remaining sediment was used for the next cycle after the addition of the surfactant solution. 90% of the CNT aggregates were converted into conductive CNT films within 13 cycles (i.e., within 39 min), demonstrating the improved conductivity and reduced energy/time requirements for ultrasonication. CNT lines with conductivities of 1400–2300 S cm⁻¹ without doping and sub-100 μm width, and uniform CNT films with 80% optical transmittance and 50 Ω/sq sheet resistance with nitric acid doping were obtained on polyethylene terephthalate films.     

Preparation by tape casting and hot pressing of copper carbon composites films

During this last decade, the use of metal matrix composites (MMCs) such as AlSiC or CuW for heat dissipation in microelectronic devices has been leading to the improvement of the reliability of electronic power modules. Today, the continuous increasing complexity, miniaturization and density of components in modern devices requires new heat dissipating films with high thermal conductivity, low coefficient of thermal expansion (CTE), and good machinability. This article presents the original use of copper carbon composites, made by tape casting and hot pressing, as heat dissipation materials. The tape casting process and the sintering have been adapted and optimised to obtain near fully dense, flat and homogeneous Cu/C composites.A good electrical contact between carbon fibres and copper matrix and a low porosity at matrix/copper interfaces allow obtaining a low electrical resistivity of 3.8 μΩ cm⁻¹ for 35 vol.% carbon fibre (electrical resistivity of copper = 1.7 μΩ cm⁻¹). The CTE and the thermal conductivity are strongly anisotropic due to the preferential orientation of carbon fibres in the plan of laminated sheets. Values in the parallel plan are, respectively, 9 × 10⁻⁶ °C⁻¹ and 160–210 W m⁻¹ K⁻¹ for 40 vol.% fibres. These CTE and thermal conductivity values are in agreement with the thermo-elastic Kerner's model and with the Hashin and Shtrikman model, respectively.     

Preparation and characterization of transparent indium- doped TiO2 films deposited by MOCVD

Titanium dioxide (TiO₂) films doped with different indium (In) concentrations have been prepared on SrTiO₃ (STO) substrates by high vacuum metalorganic chemical vapor deposition (MOCVD). X-ray diffraction (XRD) analyses revealed the TiO₂ films doped with low In concentrations to be [001] oriented anatase phase and the films with high In concentrations to present polycrystalline structures. The 1.8% In-doped TiO₂ film exhibited the best electrical conductivity properties with the lowest resistivity of 8.68×10⁻² Ω cm, a Hall mobility of 10.9 cm² V⁻¹ s⁻¹ and a carrier concentration of 6.5×10¹⁸ cm⁻³. The films showed excellent transparency with average transmittances of over 85% in the visible range.     

Room-temperature UV-ozone assisted solution process for zirconium oxide films with high dielectric properties

A facile, low-cost, and room-temperature UV-ozone (UVO) assisted solution process was employed to prepare zirconium oxide (ZrO_x) films with high dielectric properties. ZrO_x films were deposited by a simple spin-coating of zirconium acetylacetonate (ZrAcAc) precursor in the environment-friendly solvent of ethanol. The smooth and amorphous ZrO_x films by UVO exhibit average visible transmittances over 90% and energy bandgap of 5.7 eV. Low leakage current of 6.0 × 10⁻⁸ A/cm² at 3 MV/cm and high dielectric constant of 13 (100 Hz) were achieved for ZrO_x dielectrics at the nearly room temperature. Moreover, a fully room-temperature solution-processed oxide thin films transistor (TFT) with UVO assisted ZrO_x dielectric films achieved acceptable performances, such as a low operating voltage of 3 V, high carrier mobility of 1.65 cm² V⁻¹ s⁻¹, and on/off current ratio about 10⁴–10⁵. Our work indicates that simple room-temperature UVO is highly potential for low-temperature, solution-processed and high-performance oxide films and devices.     

Influence of sintering aids and excess Lithium on the conductivity of perovskite-type Li3/8Sr7/16Zr1/4Nb3/4O3 solid electrolyte

Perovskite-structured Li_3/8Sr_7/16Zr_1/4Nb_3/4O₃ solid-state Lithium-conductors were prepared by conventional solid-state reaction method. Influence of sintering aids (Al₂O₃, B₂O₃) and excess Lithium on structure and electrical properties of Li_3/8Sr_7/16Zr_1/4Nb_3/4O₃ (LSNZ) has been investigated. Their crystal structure and microstructure were characterized by X-ray diffraction analysis and scanning electron microscope, respectively. The conductivity and electronic conductivity were evaluated by AC-impedance spectra and potentiostatic polarization experiment. All sintered compounds are cubic perovskite structure. Optimal amount of excess Li₂CO₃ was chosen as 20 wt% because of the total conductivity of LSNZ-20% was as high as 1.6×10⁻⁵ S cm⁻¹ at 30 °C and 1.1×10⁻⁴ S cm⁻¹ at 100 °C, respectively. Electronic conductivity of LSNZ-20% is 2.93×10⁻⁸ S cm⁻¹, nearly 3 orders of magnitude lower than ionic conductivity. The density of solid electrolytes appears to be increased by the addition of sintering aids. The addition of B₂O₃ leads to a considerable increase of the total conductivity and the enhancement of conductivity is attributed to the decrease of grain-boundary resistance. Among these compounds, LSNZ-1 wt%B₂O₃ has lower activation energy of 0.34 eV and the highest conductivity of 1.98×10⁻⁵ S cm⁻¹ at 30 °C.     

Preparation-microstructure-property relationships in double-walled carbon nanotubes/alumina composites

Double-walled carbon nanotube/alumina composite powders with low carbon contents (2–3 wt.%) are prepared using three different methods and densified by spark plasma sintering. The mechanical properties and electrical conductivity are investigated and correlated with the microstructure of the dense materials. Samples prepared by in situ synthesis of carbon nanotubes (CNTs) in impregnated submicronic alumina are highly homogeneous and present the higher electrical conductivity (2.2–3.5 S cm⁻¹) but carbon films at grain boundaries induce a poor cohesion of the materials. Composites prepared by mixing using moderate sonication of as-prepared double-walled CNTs and lyophilisation, with little damage to the CNTs, have a fracture strength higher (+30%) and a fracture toughness similar (5.6 vs 5.4   MPa m^1/2) to alumina with a similar submicronic grain size. This is correlated with crack-bridging by CNTs on a large scale, despite a lack of homogeneity of the CNT distribution.     

High density carbon nanotube growth using a plasma pretreated catalyst

We have developed a direct current plasma pretreatment of the Fe catalyst to increase the area density of vertically-aligned carbon nanotube forests. The carbon wall density of the double- and multi-walled nanotubes reaches 4.8 × 10¹² cm⁻², with a 40% volume occupancy and a mass density of ∼0.4 g cm⁻³. The plasma pretreatment works by reducing the sintering of the catalyst nanoparticles during growth. This treatment increases the forest density by 8 times compared to the standard growth conditions.     

Electrical contacts to nitrogen incorporated nanocrystalline diamond films

The effect of surface plasma treatment on the nature of the electrical contact to the nitrogen incorporated nanocrystalline diamond (n-NCD) films is reported. Nitrogen incorporated NCD films were grown in a microwave plasma enhanced chemical vapor deposition (MPECVD) reactor using CH₄ (1%)/N₂ (20%)/Ar (79%) gas chemistry. Raman spectra of the films showed features at ∼ 1140 cm^− 1, 1350 cm^− 1(D-band) and 1560 cm^− 1(G-band) respectively with changes in the bonding configuration of G-band after the plasma treatment. Electrical contacts to both untreated and surface plasma treated films are formed by sputtering and patterning Ti/Au metal electrodes. Ohmic nature of these contacts on the untreated films has changed to non-ohmic type after the hydrogen plasma treatment. The linear current–voltage characteristics could not be obtained even after annealing the contacts. The nature of the electrical contacts to these films depends on the surface conditions and the presence of defects and sp² carbon.     

Dense carbon monoliths for supercapacitors with outstanding volumetric capacitances

A commercially available dense carbon monolith (CM) and four carbon monoliths obtained from it have been studied as electrochemical capacitor electrodes in a two-electrode cell. CM has: (i) very high density (1.17 g cm⁻³), (ii) high electrical conductivity (9.3 S cm⁻¹), (iii) well-compacted and interconnected carbon spheres, (iv) homogeneous microporous structure and (v) apparent BET surface area of 957 m²g⁻¹. It presents interesting electrochemical behaviors (e.g., excellent gravimetric capacitance and outstanding volumetric capacitance). The textural characteristics of CM (porosity and surface chemistry) have been modified by means of different treatments. The electrochemical performances of the starting and treated monoliths have been analyzed as a function of their porous textures and surface chemistry, both on gravimetric and volumetric basis. The monoliths present high specific and volumetric capacitances (292 F g⁻¹ and 342 F cm⁻³), high energy densities (38 Wh kg⁻¹ and 44 Wh L⁻¹), and high power densities (176 W kg⁻¹ and 183 W L⁻¹). The specific and volumetric capacitances, especially the volumetric capacitance, are the highest ever reported for carbon monoliths. The high values are achieved due to a suitable combination of density, electrical conductivity, porosity and oxygen surface content.     

Effects of plasma treatments on the nitrogen incorporated nanocrystalline diamond films

The nitrogen incorporated nanocrystalline diamond (NCD) films were grown on n-silicon (100) substrates by microwave plasma enhanced chemical vapor deposition (MPECVD) using CH₄/Ar/N₂ gas chemistry. The effect of surface passivation on the properties of NCD films was investigated by hydrogen and nitrogen-plasma treatments. The crystallinity of the NCD films reduced due to the damage induced by the plasma treatments. From the crystallographic data, it was observed that the intensity of (111) peak of the diamond lattice reduced after the films were exposed to the nitrogen plasma. From Raman spectra, it was observed that the relative intensity of the features associated with the transpolyacetylene (TPA) states decreased after hydrogen-plasma treatment, while such change was not observed after nitrogen-plasma treatment. The hydrogen-plasma treatment has reduced the sp²/sp³ ratio due to preferential etching of the graphitic carbon, while this ratio remained same in both as-grown and nitrogen-plasma treated films. The electrical contacts of the as-grown films changed from ohmic to near Schottky after the plasma treatment. The electrical conductivity reduced from ~ 84 ohm^– 1 cm^− 1 (as-grown) to ~ 10 ohm^– 1 cm^− 1 after hydrogen-plasma treatment, while the change in the conductivity was insignificant after nitrogen-plasma treatment.     

Electrical characterization of La9.33Si2Ge4O26 oxyapatite for prospective intermediate-temperature solid oxide fuel cells

La_9.33Si₂Ge₄O₂₆ materials have been fabricated from La₂O₃, SiO₂ and GeO₂ powders by high speed mechanical alloying followed by conventional and microwave hybrid sintering at different temperatures and holding times. XRD data showed that the apatite phase is formed after 1 h of mechanical alloying at 850 rpm. This phase remained stable after conventional sintering in an electric furnace with density increasing as sintering temperatures and holding times were increased. However, the highest density was achieved for samples sintered in the microwave furnace (5.44 g cm⁻³), corresponding to a relative density of 98%. The electrical conductivity of the samples microwave sintered at 700 and 800 ºC are 4.72×10⁻³ and 1.93×10⁻² S.cm⁻¹, respectively, with a correspondent activation energy of 0.952 eV.     

Enhanced thermoelectric properties of carbon fiber reinforced cement composites

Thermoelectric properties of carbon fiber reinforced cement composites (CFRCs) have attracted relevant interest in recent years, due to their fascinating ability for harvesting ambient energy in urban areas and roads, and to the widespread use of cement-based materials in modern society. The enhanced effect of the thin pyrolytic carbon layer (formed at the carbon fiber/cement interface) on transport and thermoelectric properties of CFRCs has been studied. It has been demonstrated that it can enhance the electrical conduction and Seebeck coefficient of CFRCs greatly, resulting in higher power factor 2.08 µW m⁻¹ K⁻² and higher thermoelectric figure of merit 3.11×10⁻³, compared to those reported in the literature and comparable to oxide thermoelectric materials. All CFRCs with pyrolytic carbon layer, exhibit typical semiconductor behavior with activation energy of electrical conduction of 0.228-0.407 eV together with a high Seebeck coefficient. The calculation through Mott’s formula indicates the charge carrier density of CFRCs (10¹⁴–10¹⁶ cm⁻³) to be much smaller than that of typical thermoelectric materials and to increase with the carbon layer thickness. CFRCs thermal conductivity is dominated by phonon thermal conductivity, which is kept at a low level by high density of micro/nano-sized defects in the cement matrix that scatter phonons and shorten their mean free path. The appropriate carrier density and mobility induced by the amorphous structure of pyrolytic carbon is primarily responsible for the high thermoelectric figure of merit.     

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.     

Synthesis and properties of an atomically thin carbon nanosheet similar to graphene and its promising use as an organic thin film transistor

We synthesize an atomically thin carbon nanosheet (CNS) analogous to graphene with properties suitable for an organic thin film transistor (OTFT). The synthesis of graphene by chemical vapor deposition has serious drawbacks such as wrinkles, grain boundaries, and defects due to catalyst removal and transfer process. Here the CNS is directly synthesized on a silicon wafer by heat-treatment of spin-coated polyacrylonitrile and shows a higher electrical conductivity (>1600 S cm⁻¹) than that of chemically converted graphene. The CNS on glass, transferred from a silicon wafer, exhibits approximately 92% optical transmittance. We have used our CNS as the electrodes of OTFTs, and recorded a mobility (0.25–0.35 cm² V⁻¹ s⁻¹) that exceeds that of gold electrodes (0.2–0.25 cm² V⁻¹ s⁻¹).     

Large-area reduced graphene oxide thin film with excellent thermal conductivity and electromagnetic interference shielding effectiveness

In this work, we fabricated reduced large-area graphene oxide (rLGO) with maximum surface area of 1592 μm² through a cost-effective chemical reduction process at low temperature. The product revealed large electrical conductivity of 243 ± 12 S cm⁻¹ and thermal conductivity of 1390 ± 65 W m⁻¹ K⁻¹, values much superior to those of a conventional reduced small-area graphene oxide (with electrical conductivity of 152 ± 7.5 S cm⁻¹ and thermal conductivity of 900 ± 45 W m⁻¹ K⁻¹). The rLGO thin film also exhibited not only excellent stiffness and flexibility with Young’s modulus of 6.3 GPa and tensile strength of 77.7 MPa, but also an efficient electromagnetic interference (EMI) shielding effectiveness of ∼20 dB at 1 GHz. The excellent performance of rLGO is attributed to the fact that the larger area LGO sheets include much fewer defects that are mostly caused by the damage of graphene sp² structure around edge boundaries, resulting in large electrical conductivity. The manufacturing process of rLGO is an economical and facile approach for the large scale production of highly thermally conducting graphene thin films with efficient EMI shielding properties, greatly desirable for future portable electronic devices.     

Contribution of sp3 clusters in films and fibers obtained from camphor

Considerable attention has been focused on the growth of carbon-based films or fibers by various methods. Diamond-like carbon (DLC) films may be of greater importance in some specific electronic applications such as flat panel displays, which represent a very large market. In this study, carbon-based thin films and fibers obtained from doped camphor soot were studied by confocal microRaman spectroscopy at 632.8 nm.Different contributions were identified between 1000 and 1650 cm⁻¹ in the Raman spectra of the as-grown and laser-annealed films and fibers. The contributions were the D-like and G-like peaks of polycrystalline graphite at about 1345 and 1530 cm⁻¹, respectively, with a FWHM value about 5 times larger than in a:C. It is now well established from correlation between Raman signature and grain size measurements that the width of the Raman line is a decreasing function of the graphite grain size. From these results, one can estimate that the grain size of this polycrystalline graphitic phase was small. An additional feature is observed at about 1240 cm⁻¹ which could be due to sp³-bonded carbon clusters.     

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.     

Fabrication of highly efficient TiO2/Ag/TiO2 multilayer transparent conducting electrode with N ion implantation for optoelectronic applications

Fabrication of highly conductive and transparent TiO₂/Ag/TiO₂ (referred hereafter as TAT) multilayer films with nitrogen implantation is reported. In the present work, TAT films were fabricated with a total thickness of 100 nm by sputtering on glass substrates at room temperature. The as-deposited films were implanted with 40 keV N ions for different fluences (1×10¹⁴, 5×10¹⁴, 1×10¹⁵, 5×10¹⁵ and 1×10¹⁶ ions/cm²). The objective of this study was to investigate the effect of N⁺ implantation on the optical and electrical properties of TAT multilayer films. X-ray diffraction of TAT films shows an amorphous TiO₂ film with a crystalline peak assigned to Ag (111) diffraction plane. The surface morphology studied by atomic force microscopy (AFM) and field emission scanning electron microscope (FESEM) revealed smooth and uniform top layer of the sandwich structure. The surface roughness of pristine film was 1.7 nm which increases to 2.34 nm on implantation for 1×10¹⁴ ions/cm² fluence. Beyond this fluence, the roughness decreases. The oxide/metal/oxide structure exhibits an average transmittance ~80% for pristine and ~70% for the implanted film at fluence of 1×10¹⁶ ions/cm² in the visible region. The electrical resistivity of the pristine sample was obtained as 2.04×10⁻⁴ Ω cm which is minimized to 9.62×10⁻⁵ Ω cm at highest fluence. Sheet resistance of TAT films decreased from 20.4 to 9.62 Ω/□ with an increase in fluence. Electrical and optical parameters such as carrier concentration, carrier mobility, absorption coefficient, band gap, refractive index and extinction coefficient have been calculated for the pristine and implanted films to assess the performance of films. The TAT multilayer film with fluence of 1×10¹⁶ ions/cm² showed maximum Haacke figure of merit (FOM) of 5.7×10⁻³ Ω⁻¹. X-ray photoelectron spectroscopy (XPS) analysis of N 1s and Ti 2p spectra revealed that substitutional implantation of nitrogen into the TiO₂ lattice added new electronic states just above the valence band which is responsible for the narrowing of band gap resulting in the enhancement in electrical conductivity. This study reports that fabrication of multilayer transparent conducting electrode with nitrogen implantation that exhibits superior electrical and optical properties and hence can be an alternative to indium tin oxide (ITO) for futuristic TCE applications in optoelectronic devices.     

Effect of moisture on the thermoelectric properties in expanded graphite/carbon fiber cement composites

A kind of dry mixing and pressing process was introduced to prepare expanded graphite/carbon fiber cement composites (EG-CFRC). Significant effect of moisture on the thermoelectric properties of EG-CFRC was observed. The higher the moisture content is, the greater the absolute Seebeck coefficient. The maximum of absolute Seebeck coefficient 11.59 μV/°C was obtained with moisture of 14.98% at 33 °C. Simultaneously, the maximum of electrical conductivity 0.78 S cm⁻¹ was got with moisture of 11.44%. Furthermore, the largest power factor 7.85×10⁻⁴ µW m⁻¹ K⁻² was calculated at 33 °C with moisture of 11.44%. The carrier scattering, polarization effects and high density defects interface of EG-CFRC are attributed to the enhancement of thermoelectric properties in the case of higher moisture content.     

Submicrometric NASICON ceramics with improved electrical conductivity obtained from mechanically activated precursors

Na₃Si₂Zr_1.88Y_0.12PO_11.94 was for the first time synthesised using mechanically activated mixtures of (ZrO₂)_0.97(Y₂O₃)_0.03, Na₃PO₄·12H₂O and SiO₂ aiming to lower the sintering temperature thus improving chemical homogeneity. The best result was obtained with powder mixtures activated in Teflon containers with partial amorphisation of the reactants attained after milling for 70 h at a maximum of 300 rpm, without significant contamination. The microstructure consists of 300–500 nm agglomerates of smaller grains with size in the range 50–100 nm. Dense, single phase ceramics with submicrometric grain size were obtained from the activated mixture after sintering at 1050 °C for 10 h. The ionic conductivity of these ceramics is 2.5×10⁻³ S cm⁻¹ at room temperature, and 0.24 S cm⁻¹ at 300 °C. These values are higher than those obtained with non-activated solid state reaction samples and amongst the highest reported in the literature.