Structure of a-Si:H/a-Si1-xCx:H multilayers deposited in a reactor with automated substrate holder

This paper deals with the structural properties of a-Si:H/a-Si1-xCx: H multilayers deposited by glow-discharge decomposition of SiH4 and SiH4 and CH4 mixtures. The main feature of the rf plasma reactor is an automated substrate holder. The plasma stabilization time and its influence on the multilayer obtained is discussed. A series of a-Si:H/a-Si1-xCx: H multilayers has been deposited and characterized by secondary ion mass spectrometry (SIMS), X-ray diffraction (XRD) and transmission electron microscopy (TEM). No asymmetry between the two types of interface has been observed. The results show that the multilayers present a very good periodicity and low roughness. The difficulty of determining the abruptness of the multilayer at the nanometer scale is discussed.

Efficiency and reliability enhancement of silicon nanocrystal field-effect luminescence from nitride-oxide gate stacks

We report on a field-effect light emitting device based on silicon nanocrystals in silicon oxide deposited by plasma-enhanced chemical vapor deposition. The device shows high power efficiency and long lifetime. The power efficiency is enhanced up to 0.1 %25 by the presence of a silicon nitride control layer. The leakage current reduction induced by this nitride buffer effectively increases the power efficiency two orders of magnitude with regard to similarly processed devices with solely oxide. In addition, the nitride cools down the electrons that reach the polycrystalline silicon gate lowering the formation of defects, which significantly reduces the device degradation.

Technological solution for the automatic replacement of the catalytic filaments in HWCVD

The degradation of the catalytic filaments is the main factor limiting the industrial implementation of the hot wire chemical vapor deposition (HWCVD) technique. Up to now, no solution has been found to protect the catalytic filaments used in HWCVD without compromising their catalytic activity. Probably, the definitive solution relies on the automatic replacement of the catalytic filaments. In this work, the results of the validation tests of a new apparatus for the automatic replacement of the catalytic filaments are reported. The functionalities of the different parts have been validated using a 0.2 mm diameter tungsten filament under uc-Si:H deposition conditions.

Degradation of thin tungsten filaments at high temperature in HWCVD

The degradation of the filaments is usually studied by checking the silicidation or carbonization status of the refractory metal used as catalysts, and their effects on the structural stability of the filaments. In this paper, it will be shown that the catalytic stability of a filament heated at high temperature is much shorter than its structural lifetime. The electrical resistance of a thin tungsten filament and the deposition rate of the deposited thin film have been monitored during the filament aging. It has been found that the deposition rate drops drastically once the quantity of dissolved silicon in the tungsten reaches the solubility limit and the silicides start precipitating. This manuscript concludes that the catalytic stability is only guaranteed for a short time and that for sufficiently thick filaments it does not depend on the filament radius.

Anisotropic surface properties of micro/nanostructured a-C:H:F thin films with self-assembly applications

The singular properties of hydrogenated amorphous carbon (a-C:H) thin filmsdeposited by pulsed DC plasma enhanced chemical vapor deposition (PECVD), such as hardness and wear resistance, make it suitable as protective coating with low surface energy for self-assembly applications. In this paper, we designed fluorine-containing a-C:H (a-C:H:F) nanostructured surfaces and we characterized them for self-assembly applications. Sub-micron patterns were generated on silicon through laser lithography while contact angle measurements, nanotribometer, atomic force microscopy (AFM), and scanning electron microscopy (SEM) were used to characterize the surface. a-C:H:F properties on lithographied surfaces such as hydrophobicity and friction were improved with the proper relative quantity of CH4 and CHF3 during deposition, resulting in ultrahydrophobic samples and low friction coefficients. Furthermore, these properties were enhanced along the direction of the lithographypatterns (in-plane anisotropy). Finally, self-assembly properties were tested with silicananoparticles, which were successfully assembled in linear arrays following the generated patterns. Among the main applications, these surfaces could be suitable as particle filter selector and cell colony substrate.

Filmes de diamante CVD dopado com boro. Parte I . Histórico, produção e caracterização

This review presents a brief account concerning the production, characterization and evolution of the knowledge in the area of diamond and boron-doped diamond films. The most important methods used for the growth of these films, such as chemical vapor deposition and high pressure/high temperature systems, as well as the several kinds of reactors which can be employed are reviewed. However, larger emphasis is given to the CVD method. Morphological, structural and electric properties of these films, as well as their role in the performance of voltammetric electrodes for electrochemistry and electroanalytical chemistry are also discussed.

Calorimetry of hydrogen desorption from ɑ-Si nanoparticles

The process of hydrogen desorption from amorphous silicon (ɑ-Si) nanoparticles grown by plasmaenhanced chemical vapor deposition (PECVD) has been analyzed by differential scanning calorimetry (DSC), mass spectrometry, and infrared spectroscopy, with the aim of quantifying the energy exchanged. Two exothermic peaks centered at 330 and 410 °C have been detected with energies per H atom of about 50 meV. This value has been compared with the results of theoretical calculations and is found to agree with the dissociation energy of Si-H groups of about 3.25 eV per H atom, provided that the formation energy per dangling bond in ɑ-Si is about 1.15 eV. It is shown that this result is valid for ɑ-Si:H films, too

Reducing contact resistance in graphene devices

In this thesis, the contact resistance of graphene devices was investigated because high contact resistance is detrimental to the performance of graphene field-effect transistors (GFET). Method for increasing so-called edge-contact area was applied in device fabrication process, as few nanometers thick Ni layer was used as a catalytic etchant during the annealing process. Finally, Ni was also used as a metal for contact. GFETs were fabricated using electron beam lithography using graphene fabricated by chemical vapor deposition (CVD). Critical part of the fabrication process was to preserve the high quality of the graphene channel while etching the graphene at contact areas with Ni during the annealing. This was achieved by optimizing the combination of temperature and gas flows. The structural properties of graphene were studied using scanning electron microscopy, scanning confocal μ-Raman spectroscopy and optical microscopy. Evaluation of electric transport properties including contact resistance was carried out by transmission line method and four-probe method. The lowest contact resistance found was about at 350 Ωμm. In addition, different methods to transfer CVD graphene synthesized on copper were studied. Typical method using PMMA as a supporting layer leaves some residues after its removal, thus effecting on the performance of a graphene devices. In a metal assisted transfer method, metal is used as an interfacial layer between PMMA and graphene. This allows more effective removal of PMMA. However, Raman spectra of graphene transferred by metal assisted method showed somewhat lower quality than the PMMA assisted method

Young’s modulus of silicon nitride used in scanning force microscope cantilevers

The Young’s modulus and Poisson’s ratio of high-quality silicon nitride films with 800 nm thickness, grown on silicon substrates by low-pressure chemical vapor deposition, were determined by measuring the dispersion of laser-induced surface acoustic waves. The Young’s modulus was also measured by mechanical tuning of commercially available silicon nitride cantilevers, manufactured from the same material, using the tapping mode of a scanning force microscope. For this experiment, an expression for the oscillation frequencies of two-media beam systems is derived. Both methods yield a Young’s modulus of 280–290 GPa for amorphous silicon nitride, which is substantially higher than previously reported (E5146 GPa). For Poisson’s ratio, a value of n 50.20 was obtained. These values are relevant for the determination of the spring constant of the cantilever and the effective tip–sample stiffness

Calorimetry of hydrogen desorption from a-Si nanoparticles

The process of hydrogen desorption from amorphous silicon (a-Si) nanoparticles grown by plasma-enhanced chemical vapor deposition (PECVD) has been analyzed by differential scanning calorimetry (DSC), mass spectrometry, and infrared spectroscopy, with the aim of quantifying the energy exchanged. Two exothermic peaks centered at 330 and 410 C have been detected with energies per H atom of about 50 meV. This value has been compared with the results of theoretical calculations and is found to agree with the dissociation energy of Si-H groups of about 3.25 eV per H atom, provided that the formation energy per dangling bond in a-Si is about 1.15 eV. It is shown that this result is valid for a-Si:H films, too.

Structural, electrical and electrochemical characterization of high frequency magnetron sputtered spinel oxide cathode films for lithium ion battery applications

The main challenges in the deposition of cathode materials in thin film form are the reproduction of stoichiometry close to the bulk material and attaining higher rates of deposition and excellent crystallinity at comparatively lower annealing temperatures. There are several methods available to develop stoichiometric thin film cathode materials including pulsed laser deposition; plasma enhanced chemical vapor deposition, electron beam evaporation, electrostatic spray deposition and RF magnetron sputtering. Among them the most versatile method is the sputtering technique, owing to its suitability for micro-fabricating the thin film batteries directly on chips in any shape or size, and on flexible substrates, with good capacity and cycle life. The main drawback of the conventional sputtering technique using RF frequency of 13.56MHz is its lower rate of deposition, compared to other deposition techniques A typical cathode layer for a thin film battery requires a thickness around one micron. To deposit such thick layers using convention RF sputtering, longer time of deposition is required, since the deposition rate is very low, which is typically 10-20 Å/min. This makes the conventional RF sputtering technique a less viable option for mass production in an economical way. There exists a host of theoretical and experimental evidences and results that higher excitation frequency can be efficiently used to deposit good quality films at higher deposition rates with glow discharge plasma. The effect of frequencies higher than the conventional one (13.56MHz) on the RF magnetron sputtering process has not been subjected to detailed investigations. Attempts have been made in the present work, to sputter deposit spinel oxide cathode films, using high frequency RF excitation source. Most importantly, the major challenge faced by the thin film battery based on the LiMn2O4 cathode material is the poor capacity retention during charge discharge cycling. The major causes for the capacity fading reported in LiMn2O4cathode materials are due to, Jahn-Teller distortion, Mn2+ dissolution into the electrolyte and oxygen loss in cathode material during cycling. The work discussed in this thesis is an attempt on overcoming the above said challenges and developing a high capacity thin film cathode material.

Production of carbon nanotubes by PECVD and their applications to supercapacitors

Màster en Nanociència i Nanotecnologia

On the synthesis and magnetic properties of multiwall carbon nanotube– superparamagnetic iron oxide nanoparticle nanocomposites

Multiwall carbon nanotubes (MWCNTs) possessing an average inner diameter of 150 nm were synthesized by template assisted chemical vapor deposition over an alumina template. Aqueous ferrofluid based on superparamagnetic iron oxide nanoparticles (SPIONs) was prepared by a controlled co-precipitation technique, and this ferrofluid was used to fill the MWCNTs by nanocapillarity. The filling of nanotubes with iron oxide nanoparticles was confirmed by electron microscopy. Selected area electron diffraction indicated the presence of iron oxide and graphitic carbon from MWCNTs. The magnetic phase transition during cooling of the MWCNT–SPION composite was investigated by low temperature magnetization studies and zero field cooled (ZFC) and field cooled experiments. The ZFC curve exhibited a blocking at ∼110 K. A peculiar ferromagnetic ordering exhibited by the MWCNT–SPION composite above room temperature is because of the ferromagnetic interaction emanating from the clustering of superparamagnetic particles in the constrained volume of an MWCNT. This kind of MWCNT–SPION composite can be envisaged as a good agent for various biomedical applications

Low-Cost Micromechanically Tunable Optical Devices: Strained Resonator Engineering, Technological Implementation and Characterization

The rapid growth of the optical communication branches and the enormous demand for more bandwidth require novel networks such as dense wavelength division multiplexing (DWDM). These networks enable higher bitrate transmission using the existing optical fibers. Micromechanically tunable optical microcavity devices like VCSELs, Fabry-Pérot filters and photodetectors are core components of these novel DWDM systems. Several air-gap based tunable devices were successfully implemented in the last years. Even though these concepts are very promising, two main disadvantages are still remaining. On the one hand, the high fabrication and integration cost and on the other hand the undesired adverse buckling of the suspended membranes. This thesis addresses these two problems and consists of two main parts: • PECVD dielectric material investigation and stress control resulting in membranes shape engineering. • Implementation and characterization of novel tunable optical devices with tailored shapes of the suspended membranes. For this purposes, low-cost PECVD technology is investigated and developed in detail. The macro- and microstress of silicon nitride and silicon dioxide are controlled over a wide range. Furthermore, the effect of stress on the optical and mechanical properties of the suspended membranes and on the microcavities is evaluated. Various membrane shapes (concave, convex and planar) with several radii of curvature are fabricated. Using this resonator shape engineering, microcavity devices such as non tunable and tunable Fabry-Pérot filters, VCSELs and PIN photodetectors are succesfully implemented. The fabricated Fabry-Pérot filters cover a spectral range of over 200nm and show resonance linewidths down to 1.5nm. By varying the stress distribution across the vertical direction within a DBR, the shape and the radius of curvature of the top membrane are explicitely tailored. By adjusting the incoming light beam waist to the curvature, the fundamental resonant mode is supported and the higher order ones are suppressed. For instance, a tunable VCSEL with 26 nm tuning range, 400µW maximal output power, 47nm free spectral range and over 57dB side mode suppresion ratio (SMSR) is demonstrated. Other technologies, such as introducing light emitting organic materials in microcavities are also investigated.

Development of hybrid UV VCSEL with organic active material and dielectric DBR mirrors for medical, sensoric and data storage applications

Lasers play an important role for medical, sensoric and data storage devices. This thesis is focused on design, technology development, fabrication and characterization of hybrid ultraviolet Vertical-Cavity Surface-Emitting Lasers (UV VCSEL) with organic laser-active material and inorganic distributed Bragg reflectors (DBR). Multilayer structures with different layer thicknesses, refractive indices and absorption coefficients of the inorganic materials were studied using theoretical model calculations. During the simulations the structure parameters such as materials and thicknesses have been varied. This procedure was repeated several times during the design optimization process including also the feedback from technology and characterization. Two types of VCSEL devices were investigated. The first is an index coupled structure consisting of bottom and top DBR dielectric mirrors. In the space in between them is the cavity, which includes active region and defines the spectral gain profile. In this configuration the maximum electrical field is concentrated in the cavity and can destroy the chemical structure of the active material. The second type of laser is a so called complex coupled VCSEL. In this structure the active material is placed not only in the cavity but also in parts of the DBR structure. The simulations show that such a distribution of the active material reduces the required pumping power for reaching lasing threshold. High efficiency is achieved by substituting the dielectric material with high refractive index for the periods closer to the cavity. The inorganic materials for the DBR mirrors have been deposited by Plasma- Enhanced Chemical Vapor Deposition (PECVD) and Dual Ion Beam Sputtering (DIBS) machines. Extended optimizations of the technological processes have been performed. All the processes are carried out in a clean room Class 1 and Class 10000. The optical properties and the thicknesses of the layers are measured in-situ by spectroscopic ellipsometry and spectroscopic reflectometry. The surface roughness is analyzed by atomic force microscopy (AFM) and images of the devices are taken with scanning electron microscope (SEM). The silicon dioxide (SiO2) and silicon nitride (Si3N4) layers deposited by the PECVD machine show defects of the material structure and have higher absorption in the ultra violet range compared to ion beam deposition (IBD). This results in low reflectivity of the DBR mirrors and also reduces the optical properties of the VCSEL devices. However PECVD has the advantage that the stress in the layers can be tuned and compensated, in contrast to IBD at the moment. A sputtering machine Ionsys 1000 produced by Roth&Rau company, is used for the deposition of silicon dioxide (SiO2), silicon nitride (Si3N4), aluminum oxide (Al2O3) and zirconium dioxide (ZrO2). The chamber is equipped with main (sputter) and assisted ion sources. The dielectric materials were optimized by introducing additional oxygen and nitrogen into the chamber. DBR mirrors with different material combinations were deposited. The measured optical properties of the fabricated multilayer structures show an excellent agreement with the results of theoretical model calculations. The layers deposited by puttering show high compressive stress. As an active region a novel organic material with spiro-linked molecules is used. Two different materials have been evaporated by utilizing a dye evaporation machine in the clean room of the department Makromolekulare Chemie und Molekulare Materialien (mmCmm). The Spiro-Octopus-1 organic material has a maximum emission at the wavelength λemission = 395 nm and the Spiro-Pphenal has a maximum emission at the wavelength λemission = 418 nm. Both of them have high refractive index and can be combined with low refractive index materials like silicon dioxide (SiO2). The sputtering method shows excellent optical quality of the deposited materials and high reflection of the multilayer structures. The bottom DBR mirrors for all VCSEL devices were deposited by the DIBS machine, whereas the top DBR mirror deposited either by PECVD or by combination of PECVD and DIBS. The fabricated VCSEL structures were optically pumped by nitrogen laser at wavelength λpumping = 337 nm. The emission was measured by spectrometer. A radiation of the VCSEL structure at wavelength 392 nm and 420 nm is observed.