Electro-optical characteristics and field-emission properties of reactive DC-sputtered p-CuAlO2+x thin films

P-type transparent-conducting CuAlO_2+x thin films were deposited on silicon and glass substrates by reactive direct current sputtering of a prefabricated metal powder target having 1:1 atomic ratio of Cu and Al in oxygen-diluted argon atmosphere. XRD spectrum confirmed the proper phase formation of the material. UV-Vis-NIR spectrophotometric measurements showed high transparency of the films in the visible region with direct and indirect band gap values around 3.90 and 1.89 eV, respectively. The room temperature conductivity of the film was of the order of 0.22 S cm⁻¹ and the activation energy was 0.25 eV. Seebeck coefficient at room temperature showed a value of +115 μV/K confirming the p-type nature of the film. Room temperature Hall effect measurement also indicated positive value of Hall coefficient with a carrier concentration 4.4×10¹⁷ cm⁻³. We have also observed the low macroscopic field emission, from the wide band gap p-CuAlO_2+x thin film deposited on glass substrate. The emission properties have been studied for different anode-sample spacing. The threshold field was found to be as low as around 0.5–1.1 V/μm. This low threshold is attributed primarily to the internal nanostructure of the thin film, which causes considerable geometrical field enhancement inside the film as well as at the film/vacuum interface.     

Study of effects of Mn in CdS nanocrystals

Mn²⁺-doped CdS nanocrystals have been synthesized by adopting an aqueous solution precipitation method. These nanocrystals have been studied using X-ray diffraction (XRD), X-ray fluorescence (XRF), optical absorbance, photoluminescence (PL), DC electrical conductivity measurements and positron annihilation lifetime spectroscopy (PALS). The system has been found to be in the hexagonal phase. PL spectra have been studied on most prominent exciton peaks within the wavelength range (586–731 nm). The emission intensity is found to increase on increasing Mn²⁺ ion concentration (0–5%). Electrical conductivity lies within 0.819×10⁻⁶ to 1.69×10⁻⁶ Ω⁻¹ m⁻¹ and the system shows power law dependence for n=3–3.77. The Cd vacancies concentration has been found to decrease on increasing Mn%.     

Thermal stability of ultrathin amorphous carbon films synthesized by plasma-enhanced chemical vapor deposition and filtered cathodic vacuum arc

Abstract

Ultrathin hydrogenated amorphous carbon (a-C:H) films deposited by plasma-enhanced chemical vapor deposition (PECVD) and hydrogen-free amorphous carbon (a-C) films of similar thickness deposited by filtered cathodic vacuum arc (FCVA) were subjected to rapid thermal annealing (RTA). Cross-sectional transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS) were used to study the structural stability of the films. While RTA increased the thickness of the intermixing layer and decreased the sp³ content of the a-C:H films, it did not affect the thickness or the sp³ content of the a-C films. The superior structural stability of the FCVA a-C films compared with PECVD a-C:H films, demonstrated by the TEM and EELS results of this study, illustrates the high potential of these films as protective overcoats in applications where rapid heating is critical to the device functionality and performance, such as heat-assisted magnetic recording.     

Surface energy and hybridization studies of amorphous carbon surfaces

Surface properties of a large number of amorphous carbon (a-C) films have been investigated using contact angle measurements and X-ray photoelectron spectroscopy (XPS). Dense a-C surfaces with variable sp³/(sp² + sp³) average hybridization were grown using sputtering or pulsed laser deposition (PLD) and were further chemically modified by thermal annealing, ion bombardment or covalent grafting of organic monolayers. The average carbon hybridization, impurity level and mass density, were deduced from XPS and photoelectron energy loss spectroscopy (PEELS). The depth sensitivity of the dispersive (Lifshitz–van der Waals) interaction, estimated at 1–2 nm from the dependence of γ^LW on the grafted perflorodecene molecule coverage, is much better than XPS which probes a 3–5 nm depth. The observation of a non-monotonic behavior in the correlation between surface hybridization and electron donor component of surface energy reveals that the average carbon hybridization alone does not describe the entire surface energy physics. The role of π bond clustering in the polar interactions is thus considered and some implications on surface reactivity and mutual interactions with molecular or biomolecular species are discussed.     

Nanomechanical probing of microbubbles using the atomic force microscope

Atomic force microscopy (AFM) is a versatile mechanical nanosensor that can be used to quantify the mechanical properties of microbubbles (MBs) and the adhesion mechanisms of targeted MBs.

Mechanical properties were investigated using AFM tipless cantilevers to microcompress the MBs. The range of compressive stiffness for biSphere^® was found to be between 1 and 10 N m⁻¹ using a cantilever with a spring constant of 0.6 N m⁻¹. This stiffness was shown to decrease with the MB size in a non-linear fashion. It is also possible to calculate a theoretical Young’s modulus of the shell.

The adhesion properties of targeted lipid based MBs that use avidin–biotin chemistry for the attachment of targeting ligands were also studied. The MBs were attached to poly-l-lysine treated tipless cantilevers with spring constants ranging from 0.03 to 0.1 N m⁻¹. This system interrogated individual cells with pulling cantilever distance of 15 μm, and scan rate at 0.2 Hz. The depth of contact was not larger than 0.4 μm. The targeted MBs provided a significantly larger adhesion to the cells compared to control ones. Average adhesion force was dependent on depth of contact. Analysis of the data demonstrated a single distribution of adhesion events with median at 89 pN, which is in agreement with the literature for such interactions.

The nanointerrogation of MBs using AFM provides new insight into their mechanical properties, and should be of assistance to MB design and manufacture.     

Chemically deposited copper oxide thin films: structural, optical and electrical characteristics

Thin films of copper oxide with thickness ranging from 0.05–0.45 μm were deposited on microscope glass slides by successively dipping them for 20 s each in a solution of 1 M NaOH and then in a solution of copper complex. Temperature of the NaOH solution was varied from 50–90°C, while that of the copper solution was maintained at room temperature. X-ray diffraction patterns showed that the films, as prepared, are of cuprite structure with composition Cu₂O. Annealing the films in air at 350°C converts these films to CuO. This conversion is accompanied by a shift in the optical band gap from 2.1 eV (direct) to 1.75 eV (direct). The films show p-type conductivity, 5×10⁻⁴ Ω⁻¹ cm⁻¹ for a film of thickness 0.15 μm. Electrical conductivity of this film increases by a factor of 3 when illuminated with 1 kW m⁻² tungsten halogen radiation. Annealing in a nitrogen atmosphere at temperatures up to 400°C does not change the composition of the films. However, the conductivity in the dark as well as the photoconductivity of the film increases by an order of magnitude. The electrical conductivity of the CuO thin films produced by air annealing at 400°C, is high, 7×10⁻³ Ω⁻¹ cm⁻¹. These films are also photoconductive.     

Increased surface roughness by oxygen plasma treatment of graphite/polymer composite

The technology of selective plasma etching was applied to increase the surface roughness of graphite/polymer composite. Etching was performed with a low pressure weakly ionised oxygen plasma created with a RF generator of the output power of 200 W and frequency of 27.12 MHz. The density of charged particles, density of neutral oxygen atoms and the electron temperature was about 1×10¹⁶ m⁻³, 4×10²¹ m⁻³, and 5 eV, respectively. The effects of plasma treatment were observed by scanning electron microscope (SEM), electron microprobe (EMPA) and Talysurf. It was found that the surface roughness was increased by approximately 15 times, from a virgin sample at the roughness of R_a=0.27 μm to a very rough surface with R_a=4 μm. The roughness increased with increasing plasma exposure time. The EMPA results showed that the amount of sulphur in the surface layer decreased with increasing etching time indicating that PPS polymer was the material etched preferentially.     

Effect of heat-pretreatment of the graphite rod on the quality of SWCNTs by arc discharge

Single-walled carbon nanotubes (SWCNTs) have been synthesized in high yield by the dc arc discharge technique under heat-pretreatment of the graphite rod conditions. Before executing arc discharge, the graphite rods containing the catalysts were heat treated at 600, 700, 800 and 900 °C for 1–3 h, respectively. Effects of heat-pretreatment of the graphite rod on the quality of SWCNTs by arc discharge were investigated. The heat-treatment temperature and time were found to be crucial for a high yield of high-purity SWCNTs. Optimum parameter was found to be at the heat-treatment temperature of 800 °C for 2 h. The SWCNTs synthesized under the optimum condition have better field-emission characteristics. The turn-on field needed to produce a current density of 10 μA/cm² is found to be 1.9 V/μm and the threshold field where current density reaches 10 mA/cm² is 3.9 V/μm.     

Femtosecond laser micro-structuring of aluminium under helium

The interaction of 180 fs, 775 nm laser pulses with aluminium under a flowing stream of helium at ambient pressure have been used to study the material re-deposition, ablation rate and residual surface roughness. Threshold fluence F_th0.4 J cm⁻² and the volume ablation rate was measured to be 30<V<450 μm³ per pulse in the fluence range 1.4<F<21 J cm⁻². The presence of helium avoids gas breakdown above the substrate and leads to improved surface micro-structure by minimising surface oxidation and debris re-deposition. At 1 kHz rep. rate, with fluence F>7 J cm⁻² and >85 W cm⁻² average power density, residual thermal effects result in melt and debris formation producing poor surface micro-structure. On the contrary, surface micro-machining at low fluence F1.4 J cm⁻² with low power density, 3 W cm⁻² produces much superior surface micro-structuring with minimum melt and measured surface roughness R_a1.1±0.1 μm at a depth D50 μm. By varying the combination of fluence/scan speed during ultra-fast ablation of aluminium at 1 kHz rep. rate, results suggest that maintaining average scanned power density to <5 W cm⁻² combined with single pulse fluence <4 J cm⁻² produces near optimum micro-structuring. The debris under these conditions contains pure aluminium nanoparticles carried with the helium stream.     

Domain wall pinning in polycrystalline perovskite La0.7Sr0.3MnO3

Reversible and irreversible domain wall (DW) motions have been investigated in La_0.7Sr_0.3MnO₃ ceramic samples using frequency-response complex permeability with various amplitudes of AC field. We also examine the effects of temperature in the range from 293 to 368 K and transverse DC magnetic field with a maximum of 4.40×10⁵ A/m on the real part of permeability (μ′). Two relaxations corresponding to reversible wall motions and domain rotations occur in low and high frequency regions, respectively. The irreversible DW displacements can be activated as the amplitude larger than the pinning field of 3 A/m, leading to an increase in μ′. The μ′ obeys a Rayleigh law at the temperature below 343 K or under DC field of less than 4.22×10⁴ A/m. The Rayleigh constant η increases from 5.45×10⁻² to 1.54×10⁻¹ (A/m)⁻¹ as the temperature rises from 293 to 343 K, and η decreases from 5.58×10⁻² to 3.67×10⁻² (A/m)⁻¹ with increasing DC field from 1.99×10³ to 4.22×10⁴ A/m.     

Structural and electrical properties of crystalline (1−x)Ta2O5−xTiO2 thin films fabricated by metalorganic decomposition

Polycrystalline (1−x)Ta₂O₅−xTiO₂ thin films were formed on Si by metalorganic decomposition (MOD) and annealed at various temperatures. As-deposited films were in the amorphous state and were completely transformed to crystalline after annealing above 600 °C. During crystallization, a thin interfacial SiO₂ layer was formed at the (1−x)Ta₂O₅−xTiO₂/Si interface. Thin films with 0.92Ta₂O₅–0.08TiO₂ composition exhibited superior insulating properties. The measured dielectric constant and dissipation factor at 1 MHz were 9 and 0.015, respectively, for films annealed at 900 °C. The interface trap density was 2.5×10¹¹ cm⁻² eV⁻¹, and flatband voltage was −0.38 V. A charge storage density of 22.8 fC/μm² was obtained at an applied electric field of 3 MV/cm. The leakage current density was lower than 4×10⁻⁹ A/cm² up to an applied electric field of 6 MV/cm.     

Properties of boron and phosphorous incorporated tetrahedral amorphous carbon films grown using filtered cathodic vacuum arc process

This paper reports the electrical, mechanical, structural and field emission properties of as grown and also boron and phosphorous incorporated tetrahedral amorphous carbon (ta-C) films, deposited using a filtered cathodic vacuum arc process. The effect of varying boron and phosphorous content (up to 2.0 at.% in to ta-C) on the conductivity (σ_D), activation energy (ΔE₁), hardness, microstructure, emission threshold (E_turn-ON) and emission current density (J) at 12.5 V/μm of ta-C: B and ta-C: P films deposited at a high negative substrate bias of −300 V are reported. It is observed that both boron and phosphorous incorporation leads to a nearly an order increase in σ_D and corresponding decrease in ΔE₁ and a slight increase in hardness as compared to as grown ta-C films. In the case of field assisted electron emission, it is observed that E_turn-ON increases and J decreases. The changes are attributed to the changes in the sp³/sp² ratio of the films due to boron and phosphorous incorporation. The effect of boron on ta-C is to give a p-type effect whereas the effect of phosphorous gives n-type doping effect.     

Microstructured silicon surfaces for field emission devices

Enhanced field emission of electrons from silicon surfaces was obtained by surface microstructuring, by means of electrochemical oxidation in organic solutions containing HF. Morphological characterisations showed the formation of cylindrical rods, randomly distributed with relative spacing of a few microns. They are originated at the top of silicon pyramids and have typical diameter in the 100 nm range. Variable length in the 1–50 μm range was obtained, by adjusting the process parameters. Electron field emission properties were characterised for several samples, prepared in different conditions: the emission threshold was found to be strongly correlated with the overall charge exchanged during electrochemical oxidation. In the most favourable conditions, the threshold field for the emission of an electron current I_th = 10⁻¹⁰ A was 11.1 V/μm.     

Detection, dosimetry and microdosimetry using high energy C beams

Samples of polyallyldiglycolcarbonate (PADC) track etch detectors (TED) were exposed to high energy ¹²C nuclei at the particle beam of the Dubna synchrophasotron. The energy of ¹²C nuclei varied between 0.1 and 1.5 GeV per amu.

At the low studied energies the linear energy transfer (LET) of these nuclei is higher than the detector threshold value. Then, the primary particle tracks are directly etched in the detector surface. The detection efficiency approaches to 100% at perpendicular incidence. Their LET has been established by means of standard authomatized procedure recently developed. The LET values found here are in good agreement with theoretical ones.

At 1.5 GeV per amu (LET 8.4 KeV μm⁻¹) the secondary particle tracks were evaluated in all the exposed detectors. The energy deposited by these particles was compared to the energy deposited through primary ionization losses. It was found out that its contribution to the total dose is relatively lower than for protons of comparable energies. In some of these samples even the tracks of the primary nuclei were observed. It follows that the detection threshold of the developed LET spectrometer should be below 10 keV μm⁻¹.     

Effects of substitution of Ti for Fe in BiFeO3 films prepared by sol–gel process

Ti substituted BiFe_1−xTi_xO_3+δ films have been prepared on indium–tin oxide (ITO)/glass substrates by the sol–gel process. The films with x=0.00–0.20 were prepared at an annealing temperature of 600 °C. X-ray diffraction patterns indicate that all films adopt R3m structure and the films with x=0 and 0.10 show pure perovskite phase. Cross-section scanning shows the thickness of the films is about 300 nm. Through 0.05 Ti substitution, the 2P_r increases to 8.30 μC/cm² from 2.12 μC/cm² of the un-substituted BiFeO₃ film and show enhanced ferroelectricity at room temperature. The 2P_r values are 2.63 and 0.44 μC/cm² for the films with x=0.01 and 0.2, respectively. Moreover, the films with x=0.05 and 0.10 show enhanced dielectric property since the permittivity increases near 150 at the same measuring frequency. Through the substitution of Ti, the leakage conduction is reduced for the films with x=0.05–0.20.     

Transmission of 1.6 J Er:YAG laser light by ZnS-coated silver hollow waveguides

A maximum energy of 1.6 J at 5 pps of Er:YAG laser light has been transmitted through a flexible ZnS-coated silver hollow waveguide which has an inner diameter of 800 μm and is 116 cm long. The straight waveguide loss is 0.6 dB m⁻¹ and no significant loss and mechanical changes have been found after an endurance test of 10000 pulse transmissions and bending 400 times with a bending radius of 30 cm.     

The preparation and evaluation of graded multilayer ta-C films deposited by FCVA method

In this study, a series of graded multilayer ta-C films were investigated by varying their sublayer thickness ratios, in which each film sublayer was prepared at different substrate bias by filtered cathode vacuum arc (FCVA) method. The experimental results show that the graded multilayer film structure can effectively decrease the internal stress level of deposited ta-C film, and meanwhile the graded multilayer ta-C films still have high sp³ fractions. The applied substrate bias voltage and sublayer thickness ratio can apparently influence the microstructure characteristics and internal stress of the graded multilayer ta-C films. The graded multilayer ta-C film has larger sp³ fraction when applying a larger negative substrate bias voltage and having a thicker outer sublayer during the film deposition process. However, the internal stress in the as-deposited film also increases with larger thickness of the outer sublayer, and the optimal ratio of sublayer thicknesses is 1:1:1:1 for graded ta-C film with four sublayers.     

Field emission from self-assembly structure of carbon-nanotube films

Chemical vapor deposited (CVD) carbon nanotube (CNT) arrays were immersed in ethanol to make shrunk structures with separate nanotube “walls” for better field emission properties, such structures decreased the screening effects and reduced the turn-on electric field at 10 μA/cm² from 1.68 to 1.23 V/μm. The field enhancement factor was calculated to increase by 23% according to Fowler–Nordheim (F–N) equation. The number of emission sites also increased and their distribution was more uniform.     

Preparation and characterization of a novel Si-incorporated ceramic film on pure titanium by plasma electrolytic oxidation

A Si-incorporated bioactive ceramic film was prepared on pure titanium by plasma electrolytic oxidation (PEO) in a new bath containing Ca²⁺, H₂PO₄⁻ and SiO₃²⁻. The film was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscope (XPS). The apatite-induced ability of PEO film was evaluated by soaking in a simulated body fluid (SBF) for various periods. The results showed that Si-incorporated PEO film present a porous microstructure, the pore size is around 1–5 μm. The film mainly consists of anatase and rutile and a small amount of CaHPO₄ and CaO, besides, bioactive compounds such as CaSiO₃ and SiO₂, also exist in the Si-incorporated PEO film. After immersion in SBF for 28 days, not only the surface layer but also the pores inside the Si-incorporated PEO film were completely filled by apatite crystals, whereas on the surface of a benchmark PEO film free of Si just present small piles of apatite crystals. Silicon incorporated into the PEO film provided more heterogeneous nucleation sites for apatite deposition and hence increased remarkably bioactivity of the PEO film.     

非晶金刚石薄膜的X射线反射研究

利用过滤阴极真空电弧系统制备了不同衬底偏压下非晶金刚石薄膜,分别采用X射线反射法测定了相应的非晶金刚石膜密度,分析了薄膜密度与沉积能量之间的变化规律．建立了薄膜密度随衬底偏压的变化曲线。研究发现在-80V时非晶金刚石膜密度存在最大值3．26g／cm^2,随着偏压的增大和减小,薄膜的密度都相应的下降;当衬底偏压加到-2000V时,密度减小到2．63g／cm^2,相对于密度的最大值变化较小。通过薄膜sp^3能态杂化含量与密度的简单比例关系,近似推算出非晶金刚石膜中sp^3能态的含量最高可达80％以上。