Pulsed laser deposition of nanostructured Ag films

Ultra-thin (0.5-5 nm) films of Ag have been prepared by pulsed laser deposition in vacuum using a 26 ns KrF excimer laser at 1 J cm⁻². The deposition was controlled using a Langmuir ion probe and a quartz crystal thickness monitor. Transmission electron microscopy showed that the films are not continuous, but are structured on nanometer size scales. Optical absorption spectra showed the expected surface plasmon resonance feature, which shifted to longer wavelength and increased in strength as the equivalent film thickness was increased. It is shown that Maxwell Garnett effective medium theory can be used to calculate the main features of optical absorption spectra.     

Influence of deposition conditions on nanostructured InSe thin films

In this study, nanostructured indium selenide (InSe) thin films were deposited on Indium tin oxide (ITO)-coated glass substrate using electrochemical deposition (ECD) from aqueous solution containing In(SO₄)₃.H₂O and SeO₂. The effects of deposition potential (−0.70 to −1.35 V), time (30-3600 s), temperature (25-80 °C) and pH (2.58 for A samples; 2 for B samples and 1.45 for C samples) on growth of the InSe thin films were examined in terms of their structural, morphological and optical properties. X-ray diffraction (XRD) analysis confirmed that the InSe thin films are in polycrystalline structure. It was found that the values of grain size decreased and the full width half maximum (FWHM) values increased with the increasing deposition potential. According to the absorption measurements, optical properties of the thin films varied with changes in deposition conditions. Based on the atomic force microscopy (AFM) and the scanning electron microscopy (SEM) images, surface morphology of the thin films was influenced by deposition potential and pH of the electrolyte, and non-homogeneous depositions distributed across the entire surface were observed. In addition, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and fourier transform infrared spectroscopy (FT-IR) analyses were used to further examine crystal quality, vibration, chemical binding conditions, In/Se orientation and structure of the prepared InSe thin films. When Raman results are examined, the B12 sample shows a more intensity and narrow peak at 248 cm⁻¹. XPS measurements sowed that A6 sample exhibited more growth in low potential for a long time and better film stoichiometry compared to the other three samples. Also, FT-IR studies prove the presence of InSe. According to the results, the film did not form at low temperatures and short times. However, the film formation began with the increasing deposition temperature and time at the low potential value of −0.730 V. But, it is clear that a high quality film can be obtained in cathodic potential with −1.3 V and shorter deposition time with 300 s at room temperature respectively. Overall results showed that the high quality thin films can be obtained by the ECD technique. However, deposition conditions must be sensitively adjusted to control morphology of the electrodeposited nanoparticles.     

Titanium oxide nanostructured films by reactive pulsed laser deposition

Nanostructured titanium oxide thin films have been grown by nanosecond UV pulsed laser deposition (PLD) performed in a reactive background atmosphere. We exploited laser ablation of a Ti target at different pressures of pure oxygen and Ar:O₂ mixtures to show that film growth can be tuned at the nanoscale from compact and dense to columnar and to porous, leading to different morphology, density and structure (oxidized fraction and degree of crystallinity). We observed that the position of the substrate relative to the time integrated visible plume front is fundamental in the determination of film structure and morphology. Film growth and film properties can be related to a non-dimensional parameter L which is the ratio between the target-to-substrate distance and the visible plume length. In particular, surface morphology and degree of structural order are strictly related to L irrespective of the oxygen content, while the latter mainly affects the oxidized fraction in the film.     

Femtosecond pulsed laser deposition of nanostructured TiO2 films

Nanostructured deposits of TiO₂ were grown on Si (1 0 0) substrates by laser ablating a TiO₂ sintered target in vacuum or in oxygen using a Ti:sapphire laser delivering 80 fs pulses. The effect of the laser irradiation wavelength on the obtained nanostructures, was investigated using 800, 400 and 266 nm at different substrate temperatures and pressures of oxygen. The composition of the deposits was characterized using X-ray photoelectron spectroscopy (XPS) and the surface morphology was studied by environmental scanning electron microscopy (ESEM) and atomic force microscopy (AFM). Deposits are absent of microscopic droplets in all conditions explored. The best deposits, constituted by nanoparticles of an average diameter of 30 nm with a narrow size distribution, were obtained at the shorter laser wavelength of 266 nm under vacuum at substrate room temperature.     

Thermal expansion of nanostructured PbS films and anharmonicity of atomic vibrations

The dependences of the coherent scattering region size and thermal expansion coefficient α of a PbS nanofilm on the annealing temperature in the range of 293–473 K and on the duration of annealing at a constant temperature of 423 K have been measured. It has been found that the thermal expansion coefficient α of the PbS nanofilm is almost twice as much as the coefficient α of coarse-grained lead sulfide. It has been shown that the large difference in the coefficients α is associated with the small size of particles in the film, which leads to an increase in the anharmonicity of atomic vibrations. The contribution from the small size of particles to the thermal expansion coefficient of the PbS nanofilm has been evaluated theoretically.     

Synthesis and characterization of permalloy nanostructured films by deposition of laser ablated nanoparticles

A permalloy (Ni₈₁Fe₁₉; at%) microparticle (MP) aerosol was ablated to produce a nanoparticle (NP) aerosol that was then impacted at high velocity onto a substrate to produce porous thick films. The structure of the NPs was analyzed by transmission electron microscopy and the morphologies of the NPs and the nanostructured films were studied using high-resolution transmission electron microscopy and scanning electron microscopy. These analyses showed that the original composition and structure of the MPs were preserved in the NPs and films. The majority of NPs that were produced ranged in size between 2 and 15 nm with some larger particles present. Magnetization-temperature curves showed that the films consisted of a mixture of small superparamagnetic NPs and larger ferromagnetic NPs. A high saturation magnetization of 62.3 emu/g at 300 K was retained in the films indicating that they remained free of significant oxidation.     

Radio-frequency assisted pulsed laser deposition of nanostructured WOx films

The synthesis of tungsten oxide films with large surface area is promising for gas sensing applications. Thin WO_x films were obtained by radio-frequency assisted pulsed laser deposition (RF-PLD). A tungsten target was ablated at 700 and 900 Pa in reactive oxygen, or in a 50% mixed oxygen-helium atmosphere at the same total pressure values. Corning glass was used as substrate, at temperatures including 673, 773 and 873 K. Other deposition parameters such as laser fluence (4.5 J cm⁻²), laser wavelength (355 nm), radiofrequency power (150 W), target to substrate distance (4 cm), laser spot area (0.7 mm²), and number of laser shots (12,000) were kept fixed. The sensitivity on the deposition conditions of morphology, nanostructure, bond coordination, and roughness of the obtained films were analyzed by scanning and transmission electron microscopy, micro-Raman spectroscopy, and atomic force microscopy.     

Photocatalytic activity of nanostructured TiO2 films produced by supersonic cluster beam deposition

The photocatalytic activity of thin, nanostructured films of titanium dioxide, synthesized by supersonic cluster beam deposition (SCBD) from the gas phase, has been investigated employing the photodegradation of salicylic acid as test reaction. Because of the low deposition energy, the so-deposited highly porous TiO₂ films are composed of nanoparticles maintaining their original properties in the film, which can be fully controlled by tuning the deposition and post-deposition treatment conditions. A systematic investigation on the evolution of light absorption properties and photoactivity of the films in relation to their morphology, determined by AFM analysis, and phase composition, determined by Raman spectroscopy, has been performed. The absorption and photocatalytic activity of the nanostructured films in the visible region could be enhanced either through post-deposition annealing treatment in ammonia containing atmosphere or employing mild oxidation conditions, followed by annealing in N₂ at 600 °C.     

Artificially nanostructured Cu:Al2O3 films produced by pulsed laser deposition

The processes leading to the formation of Cu:Al₂O₃ composite films on Si (001) with a well defined nanostructure by alternate pulsed laser deposition (a-PLD) in vacuum are investigated. Alternately amorphous Al₂O₃ layers and Cu nanocrystals nucleated on the Al₂O₃ surface are formed, according to the PLD sequence. The Al₂O₃ deposited on the Cu nanocrystals fills in the space between them until they are completely buried, and subsequently, a continuous dense layer with a very flat surface (within 1 nm) is developed. The nucleation process of the nanocrystals and their resulting oblate ellipsoidal shape are discussed in terms of the role of the energetic species involved in the PLD process and the metal–oxide interface energy. Received: 4 July 2000 / Accepted: 5 July 2000 / Published online: 13 September 2000     

Electrical conduction in nanostructured carbon and carbon-metal films grown by supersonic cluster beam deposition

We have studied the electrical conduction in nanostructured carbon (ns-C) films produced by deposition of a supersonic beam of neutral carbon clusters. The d.c. conduction properties of these films have been measured in situ during the deposition process and ex situ as a function of the temperature in vacuum and in ambient of different gases (H₂, N₂, CH₄, He). The ns-C films exhibit an ohmic behavior with a room temperature resistivity in the range of 10⁷-10⁹ W{\rm\Omega} cm depending on the growth and storage conditions. Conductivity vs. temperature measured in vacuum in the range 290-400 K is characterized by activation energies in the range of 0.3-1.7 eV, the current response does not differ significantly in gas atmosphere. Nanocomposite carbon-metal films have been obtained by adding small amounts of metallorganic precursors containing molybdenum and cobalt during the formation of carbon clusters prior to deposition. The films are characterized by porous carbon networks containing small metal and metal carbide clusters. Electrical transport properties of these films have been studied as a function of temperature, gas pressure and relative humidity. In particular, the electrical conductivity of the sample produced with molybdenum showed to be much sensitive to changes in gas pressure and relative humidity, being characterised by fast and reversible responses.     

Preparation and characterizations of amorphous nanostructured SiC thin films by low energy pulsed laser deposition

Amorphous silicon carbide (SiC) thin films were deposited on silicon substrates by pulsed laser ablation at room temperature. Thicknesses and surface morphology of the thin films were characterized using optical profilers, atomic force and field emission scanning electron microscopy. Nanohardnes, modulus and scratch resistance properties were determined using XP nanoindenter. The results show that crack free, smooth and nanostructured thin films can be deposited using low laser energy densities.     

Supersonic cluster beam deposition of nanostructured titania

Nanostructured titanium dioxide films have been deposited by supersonic cluster beam deposition (CBD). Nanoparticles are produced by a pulsed microplasma cluster source (PMCS) and selected by aerodynamic separation effects. The as-deposited film is a complex mixture where amorphous material coexists, at the nanoscale, with anatase and rutile crystal phases. The nanocrystalline fraction of the film is characterized by crystal size ranging from 100 nm to less than 5 nm. We have characterized the film structure by transmission electron microscopy, Raman spectromicroscopy, X-ray diffraction, and UV-visible spectroscopy showing that correlations exist between cluster size and film properties. In particular if very small clusters are deposited, the film shows a predominant rutile phase whereas larger clusters form films with mainly anatase structure. Our observations suggest that phonon confinement effects are responsible for a significant shift and broadening observed for the Raman peaks. In addition, optical gap tuning is provided by mass selection: large clusters assembling generates a film with 3.22 eV optical gap, while smallest clusters 3.52 eV.     

Hysteretic properties of nanostructured terbium films

The hysteretic properties of terbium films subjected to layered structuring by introducing nonmagnetic Ti and Si layers of a fixed thickness (2 nm) are studied in the temperature range 2–230 K. It is found that the variation of the Tb layer thickness in the range 1.5–360 nm and the nonmagnetic layer material leads to substantial changes in the magnetic hysteresis of the films and its temperature behavior. These changes are related to a change in the structural composition of the films, which consists of nanocrystalline, granulated, and amorphous Tb phases.     

采用空心阴极放电等离子体化学气相沉积方法制备a-CH薄膜

研究了不同衬底-阴极距离、直流电压和H2流量对a-CH薄膜沉积速率的影响。结果表明：衬底-阴极距离必须大于0.5cm,随着该距离的增加,薄膜的沉积速率减少;直流电压达550V时沉积速率最大;随着H2含量的增加,CH4含量相对减少,沉积速率随之降低。用AFM观察了以该方法制得的448.4nm CH薄膜的表面形貌,表面粗糙度约为10nm。最后测出了不同条件下CH薄膜的UV-VIS谱,由此可以计算得到薄膜的禁带宽度及折射率。     

电感耦合等离子体CVD低温生长硅薄膜过程中的铝诱导晶化

利用电感耦合等离子体CVD方法在350℃的低温下在镀Al玻璃衬底上制备出具有良好结晶性的Si薄膜.利用x射线衍射、紫外-可见分光椭圆偏振谱、原子力显微镜及x射线光电子谱等研究了薄膜的结构、表面形貌和成分分布等.结果表明，用这种方法制备的Si薄膜不但晶化程度高，而且具有良好的（111）结晶取向性，晶粒尺寸大于300nm，样品中无Al的残留.结合电感耦合等离子体的高电子密度特征讨论了低温生长过程中Al诱导Si薄膜晶化的机理. 关键词： 电感耦合等离子体CVD Al诱导晶化 Si薄膜 低温生长     

Characterization of BCN films synthesized by radiofrequency plasma enhanced chemical vapor deposition

Boron carbonitride (BCN) films have been synthesized on Si(1 0 0) substrate by radio frequency plasma enhanced chemical vapor deposition using tris-(dimethylamino)borane (TDMAB) as a precursor. The deposition was performed at the different RF powers of 400-800 W, at the working pressure of 2×10⁻¹ Torr. The formation of the sp²-bonded BCN phase was confirmed by Fourier transform infrared spectroscopy. X-ray photoelectron spectroscopy measurements showed that B atoms were bonded to C and N atoms to form the BCN atomic hybrid configurations with the chemical compositions of B₅₂C₁₂N₃₆ (sample 1; prepared at the RF power of 400 W), B₅₂C₁₀N₃₈ (sample 2; at 500 W) and B₄₆C₁₈N₃₆ (sample 3; at 800 W), respectively. Near-edge X-ray absorption fine structure (NEXAFS) measurements indicated that B atoms were bonded not only to N atoms but also to C atoms to form various configurations of sp²-BCN atomic hybrids. The polarization dependence of NEXAFS suggested that the predominant hybrid configuration of sp²-BCN films oriented in the direction perpendicular to the Si substrate.     

采用空心阴极放电等离子体化学气相沉积方法制备a-CH薄膜

 研究了不同衬底-阴极距离、直流电压和H₂流量对a-CH薄膜沉积速率的影响。结果表明：衬底-阴极距离必须大于0.5cm，随着该距离的增加，薄膜的沉积速率减少；直流电压达550V时沉积速率最大；随着H2含量的增加，CH₄含量相对减少，沉积速率随之降低。用AFM观察了以该方法制得的448.4nm CH薄膜的表面形貌，表面粗糙度约为10nm。最后测出了不同条件下CH薄膜的UV-VIS谱，由此可以计算得到薄膜的禁带宽度及折射率。     

Surface-plasmon vortices in nanostructured metallic films

Light scattering by a small protrusion on a metal surface is analyzed within the framework of perturbation theory. Upon normal incidence of a linearly polarized monochromatic wave, slight deviations of the protrusion’s shape from a circularly symmetric one lead to the formation of optical vortices in the near-field region due to resonant excitation of circular surface plasmons. This agrees with the results of scanning near-field optical microscopy experiments revealing distinct spiral patterns in the in-plane near-field intensity distribution for metallized nanostructured polymer substrates.     

Thermal and chemical passivation of gallium-arsenide films deposited from ablation plasma

The electric and photoelectric properties of gallium-arsenide films deposited on a polycrystalline corundum substrate from the ablation plasma formed by a high-power ion beam are investigated. It is ascertained that vacuum and air annealing (in the former case, P = 10^?2 Pa and T = 300–1200 K) and sulfide chemical passivation in an alcoholic solution affect the characteristics of the dark conductivity and photo-conductivity of the film surfaces. The optimal conditions for thermal and chemical treatment, at which the most stable changes in film the properties are attained, are determined. Enhancement in the stability of the electrical and photoelectric characteristics of films, which is achieved after thermal treatment, arises from the annealing of defects and their clusterization. Sulfide passivation leads to changes in the characteristics and increases the stability of properties under air oxidation.