HMDSO plasma polymerization and thin film optical properties

Thin films were deposited from hexamethyldisiloxane (HMDSO) in a glow discharge supplied with radiofrequency (rf) power. Actino-metric optical emission spectroscopy was used to follow trends in the plasma concentrations of the species SiH (414.2 nm), CH (431.4 nm), CO (520.0 nm), and H (656.3 nm) as a function of the applied rf power (range 5 to 35 W). Transmission infrared spectroscopy (IRS) was employed to characterize the molecular structure of the polymer, showing the presence of Si-H, Si-O-Si, Si-O-C and C-H groups. The deposition rate, determined by optical interferometry, ranged from 60 to 130 nm/min. Optical properties were determined from transmission ultra violet-visible spectroscopy (UVS) data. The absorption coefficient α, the refractive index n, and the optical gap E04 of the polymer films were calculated as a function of the applied power. The refractive index at a photon energy of 1 eV varied from 1.45 to 1.55, depending on the rf power used for the deposition. The absorption coefficient showed an absorption edge similar to other non-crystalline materials, amorphous hydrogenated carbon, and semiconductors. For our samples, we define as an optical gap, the photon energy E04 corresponding to the energy at an absorption of 104 cm-1. The values of E04 decreased from 5.3 to 4.6 as the rf power was increased from 5 to 35 W. © 1995.

An optical fibre based evanescent wave sensor to monitor the deposition rate of thin films

A novel fibre optic sensor for the in situ measurement of the rate of deposition of thin films has been developed. Evanescent wave in the uncladded portion of a multimode fibre is utilised for this sensor development. In the present paper we demonstrate how this sensor is useful for the monitoring of the deposition rate of polypyrrole thin films, deposited by an AC plasma polymerisation method. This technique is simple, accurate and highly sensitive compared with existing techniques.

Mechanism of electrical conduction in plasma polymerized furfural thin films

Polyfurfural thin films lying in the thickness range of 1300–2000 A˚ were prepared by ac plasma polymerization technique. The current–voltage characteristics in symmetric and asymmetric electrode configuration were studied with a view to determining the dominant conduction mechanism.It was found that the Schottky conduction mechanism is dominant in plasma polymerized furfural thin films.The predominance of Schottky mechanism was further confirmed based on the thermally stimulated current measurements.

Improvements of plasma immersion ion implantation (PIII) and deposition (PIII&D) processing for materials surface modification

Plasma immersion ion implantation (PIII) process is a three dimensional surface modification method that is quite mature and well known to the surface engineering community nowadays, especially to those working in the field of plasma-materials interaction, aiming at both industrial and academic applications. More recently, deposition methods have been added to PIII, the PIII&D, opening possibilities of broader range of applications of these techniques. So, PIII&D is becoming a routine method of surface modification, with the advantage of pushing up the retained dose levels limited by the sputtering due to ion implantation. Therefore, well adherent, thick, three-dimensional films without stress are possible to be achieved, at relatively low cost, using PIII&D. In this paper, we will discuss about a few PIII and PIII&D experiments that have been performed recently to achieve surface improvements in different materials: 1 - high temperature nitrogen PIII in Ti6Al4V alloy in which a deep nitrogen rich treated layer resulted in surface improvements as increase of hardness, corrosion resistance and resistance to wear of the Ti alloy; 2 - nanostructures in ZnO films, obtained by PIII&D of vaporized & ionized Zn source; 3 - combined implantation and deposition of calcium for biomaterial activity of Ti alloy (PIII&D), allowing the growth of hydroxyapatite in a body solution; 4 - magnetron sputtering deposition of Cr that was enhanced by the glow discharge Ar plasma to allow implantation and deposition of Cr on SAE 1070 steel (PIII&D) resulting in surfaces with high resistance to corrosion; and 5 - implantation of nitrogen by ordinary PIII into this Cr film, which improved resistance to corrosion, while keeping the tribological properties as good as for the SAE 1070 steel surface. © 2012 Elsevier B.V.

Plasma diagnostics and ITO film deposition by RF-assisted closed-field dual magnetron system

Deposition of indium tin oxide (ITO) among various transparent conductive materials on flexible organic substrates has been intensively investigated among academics and industrials for a whole new array of imaginative optoelectronic products. One critical challenge coming with the organic materials is their poor thermal endurances, considering that the process currently used to produce industry-standard ITO usually involves relatively high substrate temperature in excess of 200°C and post-annealing. A lower processing temperature is thus demanded, among other desires of high deposition rate, large substrate area, good uniformity, and high quality of the deposited materials. For this purpose, we developed an RF-assisted closed-field dual magnetron sputtering system. The “prototype” system consists of a 3-inch unbalanced dual magnetron operated at a closed-field configuration. An RF coil was fabricated and placed between the two magnetron cathodes to initiate a secondary plasma. The concept is to increase the ionization faction with the RF enhancement and utilize the ion energy instead of thermal energy to facilitate the ITO film growth. The closed-field unbalanced magnetrons create a plasma in the intervening region rather than confine it near the target, thus achieving a large-area processing capability. An RF-compensated Langmuir probe was used to characterize and compare the plasmas in mirrored balanced and closed-field unbalanced magnetron configurations. The spatial distributions of the electron density ne and electron temperature Te were measured. The density profiles reflect the shapes of the plasma. Rather than intensively concentrated to the targets/cathodes in the balanced magnetrons, the plasma is more dispersive in the closed-field mode with a twice higher electron density in the substrate region. The RF assistance significantly enhances ne by one or two orders of magnitude higher. The effect of various other parameters, such as pressure, on the plasma was also studied. The ionization fractions of the sputtered atoms were measured using a gridded energy analyzer (GEA) combined with a quartz crystal microbalance (QCM). The presence of the RF plasma effectively increases the ITO ionization fraction to around 80% in both the balanced and closed-field unbalanced configurations. The ionization fraction also varies with pressure, maximizing at 5-10 mTorr. The study of the ionization not only facilitates understanding the plasma behaviors in the RF-assisted magnetron sputtering, but also provides a criterion for optimizing the film deposition process. ITO films were deposited on both glass and plastic (PET) substrates in the 3-inch RF-assisted closed-field magnetrons. The electrical resistivity and optical transmission transparency of the ITO films were measured. Appropriate RF assistance was shown to dramatically reduce the electrical resistivity. An ITO film with a resistivity of 1.2×10-3 Ω-cm and a visible light transmittance of 91% was obtained with a 225 W RF enhancement, while the substrate temperature was monitored as below 110°C. X-ray photoelectron spectroscopy (XPS) was employed to confirm the ITO film stoichiometry. The surface morphology of the ITO films and its effect on the film properties were studied using atomic force microscopy (AFM). The prototype of RF-assisted closed-field magnetron was further extended to a larger rectangular shaped dual magnetron in a flat panel display manufacturing system. Similar improvement of the ITO film conductivities by the auxiliary RF was observed on the large-area PET substrates. Meanwhile, significant deposition rates of 25-42 nm/min were achieved.

A high voltage pulse power supply for metal plasma immersion ion implantation and deposition

We describe the design and implementation of a high voltage pulse power supply (pulser) that supports the operation of a repetitively pulsed filtered vacuum arc plasma deposition facility in plasma immersion ion implantation and deposition (Mepiiid) mode. Negative pulses (micropulses) of up to 20 kV in magnitude and 20 A peak current are provided in gated pulse packets (macropulses) over a broad range of possible pulse width and duty cycle. Application of the system consisting of filtered vacuum arc and high voltage pulser is demonstrated by forming diamond-like carbon (DLC) thin films with and without substrate bias provided by the pulser. Significantly enhanced film/substrate adhesion is observed when the pulser is used to induce interface mixing between the DLC film and the underlying Si substrate. (C) 2010 American Institute of Physics. [doi:10.1063/1.3518969]

Involvement of Dab1 in APP processing and [beta]-amyloid deposition in sporadic Creutzfeldt-Jakob patients.

Alzheimer"s disease and prion pathologies (e.g., Creutzfeldt-Jakob disease) display profound neural lesions associated with aberrant protein processing and extracellular amyloid deposits. For APP processing, emerging data suggest that the adaptor protein Dab1 plays a relevant role in regulating its intracellular trafficking and secretase-mediated proteolysis. Although some data have been presented, a putative relationship between human prion diseases and Dab1/APP interactions is lacking. Therefore, we have studied the putative relation between Dab1, APP processing and Aβ deposition, targets in sCJD cases. Our biochemical results categorized two groups of sCJD cases, which also correlated with PrPsc types 1 and 2 respectively. One group, with PrPsc type 1 showed increased Dab1 phosphorylation, and lower βCTF production with an absence of Aβ deposition. The second sCJD group, which carried PrPsc type 2, showed lower levels of Dab1 phosphorylation and βCTF production, similar to control cases. Relevant Aβ deposition in the second sCJD group was measured. Thus, a direct correlation between Dab1 phosphorylation, Aβ deposition and PrPsc type in human sCJD is presented for the first time.

APP processing and b-amyloid deposition in sporadic Creutzfeldt-Jakob patients is dependent on Dab1.

Alzheimer"s disease and prion pathologies (e.g., Creutzfeldt-Jakob disease (CJD)) display profound neural lesions associated with aberrant protein processing and extracellular amyloid deposits. Dab1 has been implicated in the regulation of Amyloid Precursor Protein (APP), but a direct link between human prion diseases and Dab1/APP interactions has not been published. Here we examined this putative relationship in seventeen cases of sporadic CJD (sCJD) post mortem. Biochemical analyses of brain tissue revealed two groups, which also correlated with PrPsc types 1 and 2. One group, with PrPsc type 1 showed increased Dab1 phosphorylation, and lower CTF production with an absence of A deposition. The second sCJD group, which carried PrPsc type 2, showed lower levels of Dab1 phosphorylation and CTF production, and A deposition. Thus, the present observations suggest a correlation between Dab1-phosphorylation, A deposition and PrPsc type in sCJD.

Effect of collection, transport, processing and storage of blood specimens on the activity of lysosomal enzymes in plasma and leukocytes

This study was designed to evaluate the effect of different conditions of collection, transport and storage on the quality of blood samples from normal individuals in terms of the activity of the enzymes ß-glucuronidase, total hexosaminidase, hexosaminidase A, arylsulfatase A and ß-galactosidase. The enzyme activities were not affected by the different materials used for collection (plastic syringes or vacuum glass tubes). In the evaluation of different heparin concentrations (10% heparin, 5% heparin, and heparinized syringe) in the syringes, it was observed that higher doses resulted in an increase of at least 1-fold in the activities of ß-galactosidase, total hexosaminidase and hexosaminidase A in leukocytes, and ß-glucuronidase in plasma. When the effects of time and means of transportation were studied, samples that had been kept at room temperature showed higher deterioration with time (72 and 96 h) before processing, and in this case it was impossible to isolate leukocytes from most samples. Comparison of heparin and acid citrate-dextrose (ACD) as anticoagulants revealed that ß-glucuronidase and hexosaminidase activities in plasma reached levels near the lower normal limits when ACD was used. In conclusion, we observed that heparin should be used as the preferable anticoagulant when measuring these lysosomal enzyme activities, and we recommend that, when transport time is more than 24 h, samples should be shipped by air in a styrofoam box containing wet ice.

Chemical bonding and composition of silicon nitride films prepared by inductively coupled plasma chemical vapor deposition

Thin silicon nitride films were prepared at 350 degrees C by inductively coupled plasma chemical vapor deposition on Si(100) substrates under different NH(3)/SiH(4) or N(2)/SiH(4) gas mixture. The chemical composition and bonding structure of the deposited films were investigated as a function of the process parameters, such as the gas flow ratio NH(3)/SiH(4) or N(2)/SiH(4) and the RF power, using X-ray photoelectron spectroscopy (XPS). The gas flow ratio was 1.4, 4.3, 7.2 or 9.5 and the RF power, 50 or 100 W. Decomposition results of Si 2p XPS spectra indicated the presence of bulk Si, under-stoichiometric nitride, stoichiometric nitride Si(3)N(4), oxynitride SiN(x)O(y), and stoichiometric oxide SiO(2), and the amounts of these compounds were strongly influenced by the two process parameters. These results were consistent with those obtained from N 1s XPS spectra. The chemical composition ratio N/Si in the film increased with increasing the gas flow ratio until the gas flow ratio reached 4.3, reflecting the high reactivity of nitrogen, and stayed almost constant for further increase in gas flow ratio, the excess nitrogen being rejected from the growing film. A considerable and unexpected incorporation of contaminant oxygen and carbon into the depositing film was observed and attributed to their high chemical reactivity. (C) 2010 Elsevier B.V. All rights reserved.

Amorphous carbon nitrogenated films prepared by plasma immersion ion implantation and deposition

In this work, an investigation was conducted on amorphous hydrogenated-nitrogenated carbon films prepared by plasma immersion ion implantation and deposition. Glow discharge was excited by radiofrequency power (13.56 MHz, 40 W) whereas the substrate-holder was biased with 25 kV negative pulses. The films were deposited from benzene, nitrogen and argon mixtures. The proportion of nitrogen in the chamber feed (R-N) was varied against that of argon, while keeping the total pressure constant (1.3 Pa). From infrared reflectance-absorbance spectroscopy it was observed that the molecular structure of the benzene is not preserved in the film. Nitrogen was incorporated from the plasma while oxygen arose as a contaminant. X-ray photoelectron spectroscopy revealed that N/C and O/C atomic ratios change slightly with R-N. Water wettability decreased as the proportion of N in the gas phase increased while surface toughness underwent just small changes. Nanoindentation measurements showed that film deposition by means of ion bombardment was beneficial to the mechanical properties of the film-substrate interface. The intensity of the modifications correlates well with the degree of ion bombardment. (c) 2006 Elsevier B.V. All rights reserved.

Thin polymer films prepared by plasma immersion ion implantation and deposition

This work describes an investigation of the properties of polymer films prepared by plasma immersion ion implantation and deposition. Films were synthesized from low pressure benzene glow discharges, biasing the samples with 25 W negative pulses. The total energy deposited in the growing layer was varied tailoring simultaneously pulse frequency and duty cycle. The effect of the pulse characteristics on the chemical composition and mechanical properties of the films was studied by X-ray photoelectron spectroscopy (XPS) and nanoindentation, respectively. Analysis of the deconvoluted C 1s XPS peaks demonstrated that oxygen was incorporated in all the samples. The chemical modifications induced structural reorganization, characterized by chain cross-linking and unsaturation, affecting material properties. Hardness and plastic resistance parameter increased under certain bombardment conditions. An interpretation is proposed in terms of the total energy delivered to the growing layer. (C) 2004 Elsevier B.V. All rights reserved.

Thin films generated by plasma immersion ion implantation and deposition of hexamethyldisilazane mixed with nitrogen in different proportions

In this work, it was used a plasma system composed of a cylindrical stainless steel reactor, a radio-frequency (13.56MHz) power source fixed at either 25 W or 70 W, a power source with a negative bias of 10kV and a 100Hz pulse. The system worked at an operational pressure of 80mTorr which consisted of varying concentrations of the monomer HMDSN and gaseous nitrogen in ratios: HMDSN (mTorr)/nitrogen (mTorr) from 70/10 to 20/60 in terms of operational pressure. The structural characterization of the films was done by FTIR spectroscopy. Absorptions were observed between 3500 cm(-1) to 3200 cm(-1), 3000 cm(-1) to 2900 cm(-1), 2500 cm(-1) to 2000 cm(-1), 1500 cm(-1) to 700 cm(-1), corresponding, respectively, to OH radicals, C-H stretching bonds in CH2 and CH3 molecules, C-N bonds, and finally, strain C-H bonds, Si-CH3 and Si-N groups, for both the 70 W and the 25 W. The contact angle for water was approximately 100 degrees and the surface energy is near 25mJ/m(2) which represents a hydrophobic surface, measured by goniometric method. The aging of the film was also analyzed by measuring the contact angle over a period of time. The stabilization was observed after 4 weeks. The refractive index of these materials presents values from 1.73 to 1.65 measured by ultraviolet-visible technique.

Diverse Amorphous Carbonaceous Thin Films Obtained by Plasma Enhanced Chemical Vapor Deposition and Plasma Immersion Ion Implantation and Deposition

Diverse amorphous hydrogenated carbon and similar films containing additional elements were produced by Plasma Enhanced Chemical Vapor Deposition (PECVD) and by Plasma Immersion Ion Implantation and Deposition (PIIID). Thus a-C:H, a-C:H:F, a-C:H:N, a-C:H:Cl and a-C:H:O:Si were obtained, starting from the same feed gases, using both techniques. The same deposition system supplied with radiofrequency (RF) power was used to produce all the films. A cylindrical stainless steel chamber equipped with circular electrodes mounted horizontally was employed. RF power was fed to the upper electrode; substrates were placed on the lower electrode. For PIIID negative high tension pulses were also applied to the lower electrode. Raman spectroscopy confirmed that all the films are amorphous. Chemical characterization of each pair of films was undertaken using Infrared Reflection Absorption Spectroscopy and X-ray Photoelectron Spectroscopy. The former revealed the presence of specific structures, such as C-H, C-O, O-H. The latter allowed calculation of the ratio of hetero-atoms to carbon atoms in the films, e. g. F:C, N:C, and Si:C. Only relatively small differences in elemental composition were detected between films produced by the two methods. The deposition rate in PIIID is generally reduced in relation to that of PECVD; for a-C:H:Cl films the reduction factor is almost four.

The improvement of thin polymer film properties through plasma immersion ion implantation and deposition technique

Thin polymer films were deposited from acetylene and argon mixtures by plasma immersion ion implantation and deposition. The effect of the pulse frequency, v, on molecular structure, optical gap, contact angle and hardness of the films was investigated. It was observed progressive dehydrogenation of the samples and increment in the concentration of unsaturated carbon bonds as the pulse frequency was increased. Film hardness and contact angle increased and optical gap decreased with v. These results are interpreted in terms of the chain unsaturation and crosslinking.