Produção e análise do desempenho óptico e elétrico de filmes finos de SnO2:F para aplicações fotovoltaicas

Conselho Nacional de Desenvolvimento Científico e Tecnológico - CNPq

Construção, caracterização e aplicação de eletrodos para descarga por arco de cátodo oco

The system built to characterize electrodes and, consequently, deposited fine films are constituted by a hollow cathode that works to discharges and low pressures (approximately 10-3 to 5 mbar), a source DC (0 to 1200 V), a cylindrical camera of closed borossilicato for flanges of stainless steel with an association of vacuum bombs mechanical and spread. In the upper flange it is connected the system of hollow cathode, which possesses an entrance of gas and two entrances for its refrigeration, the same is electrically isolated of the rest of the equipment and it is polarized negatively. In front of the system of hollow cathode there is a movable sample in stainless steel with possibility of moving in the horizontal and vertical. In the vertical, the sample can vary its distance between 0 and 70 mm and, in the horizontal, can leave completely from the front of the hollow cathode. The sample and also the cathode hollow are equipped with cromel-alumel termopares with simultaneous reading of the temperatures during the time of treatment. In this work copper electrodes, bronze, titanium, iron, stainless steel, powder of titanium, powder of titanium and silício, glass and ceramic were used. The electrodes were investigated relating their geometry change and behavior of the plasma of the cavity of hollow cathode and channel of the gas. As the cavity of hollow cathode, the analyzed aspects were the diameter and depth. With the channel of the gas, we verified the diameter. In the two situations, we investigated parameters as flow of the gas, pressure, current and applied tension in the electrode, temperature, loss of mass of the electrode with relationship at the time of use. The flow of gas investigated in the electrodes it was fastened in a work strip from 15 to 6 sccm, the constant pressure of work was among 2.7 to 8 x 10-2 mbar. The applied current was among a strip of work from 0,8 to 0,4 A, and their respective tensions were in a strip from 400 to 220 V. Fixing the value of the current, it was possible to lift the curve of the behavior of the tension with the time of use. That curves esteem in that time of use of the electrode to its efficiency is maximum. The temperatures of the electrodes were in the dependence of that curves showing a maximum temperature when the tension was maximum, yet the measured temperatures in the samples showed to be sensitive the variation of the temperature in the electrodes. An accompaniment of the loss of mass of the electrode relating to its time of use showed that the electrodes that appeared the spherical cavities lost more mass in comparison with the electrodes in that didn't appear. That phenomenon is only seen for pressures of 10-2 mbar, in these conditions a plasma column is formed inside of the channel of the gas and in certain points it is concentrated in form of spheres. Those spherical cavities develop inside of the channel of the gas spreading during the whole extension of the channel of the gas. The used electrodes were cut after they could not be more used, however among those electrodes, films that were deposited in alternate times and the electrodes that were used to deposit films in same times, those films were deposited in the glass substrata, alumina, stainless steel 420, stainless steel 316, silício and steel M2. As the eletros used to deposit films in alternate time as the ones that they were used to deposit in same times, the behavior of the thickness of the film obeyed the curve of the tension with relationship the time of use of the electrode, that is, when the tension was maximum, the thickness of the film was also maximum and when the tension was minimum, the thickness was minimum and in the case where the value of the tension was constant, the thickness of the film tends to be constant. The fine films that were produced they had applications with nano stick, bio-compatibility, cellular growth, inhibition of bacterias, cut tool, metallic leagues, brasagem, pineapple fiber and ornamental. In those films it was investigated the thickness, the adherence and the uniformity characterized by sweeping electronic microscopy. Another technique developed to assist the production and characterization of the films produced in that work was the caloteste. It uses a sphere and abrasive to mark the sample with a cap impression, with that cap form it is possible to calculate the thickness of the film. Through the time of life of the cathode, it was possible to evaluate the rate of waste of its material for the different work conditions. Values of waste rate up to 3,2 x 10-6 g/s were verified. For a distance of the substratum of 11 mm, the deposited film was limited to a circular area of 22 mm diameter mm for high pressures and a circular area of 75 mm for pressure strip. The obtained films presented thickness around 2,1 µm, showing that the discharge of arch of hollow cathode in argon obeys a curve characteristic of the tension with the time of life of the eletrodo. The deposition rate obtained in this system it is of approximately 0,18 µm/min

Comparação entre técnicas de nitretação em cátodo oco e gaiola catódica na deposição de TiN

The plasma nitriding has been used in industrial and technological applications for large-scale show an improvement in the mechanical, tribological, among others. In order to solve problems arising in the conventional nitriding, for example, rings constraint (edge effect) techniques have been developed with different cathodes. In this work, we studied surfaces of commercially pure titanium (Grade II), modified by plasma nitriding treatment through different settings cathodes (hollow cathode, cathodic cage with a cage and cathodic cage with two cages) varying the temperature 350, 400 and 430oC, with the goal of obtaining a surface optimization for technological applications, evaluating which treatment generally showed better results under the substrate. The samples were characterized by the techniques of testing for Atomic Force Microscopy (AFM), Raman spectroscopy, microhardness, X-ray diffraction (XRD), and a macroscopic analysis. Thus, we were able to evaluate the processing properties, such as roughness, topography, the presence of interstitial elements, hardness, homogeneity, uniformity and thickness of the nitrided layer. It was observed that all samples were exposed to nitriding modified relative to the control sample (no treatment) thus having increased surface hardness, the presence of TiN observed by XRD as per both Raman and a significant change in the roughness of the treated samples . It was found that treatment in hollow cathode, despite having the lowest value of microhardness between treated samples, was presented the lowest surface roughness, although this configuration samples suffer greater physical aggressiveness of treatment

Construção, caracterização e aplicação de eletrodos para descarga por arco de cátodo oco

The system built to characterize electrodes and, consequently, deposited fine films are constituted by a hollow cathode that works to discharges and low pressures (approximately 10-3 to 5 mbar), a source DC (0 to 1200 V), a cylindrical camera of closed borossilicato for flanges of stainless steel with an association of vacuum bombs mechanical and spread. In the upper flange it is connected the system of hollow cathode, which possesses an entrance of gas and two entrances for its refrigeration, the same is electrically isolated of the rest of the equipment and it is polarized negatively. In front of the system of hollow cathode there is a movable sample in stainless steel with possibility of moving in the horizontal and vertical. In the vertical, the sample can vary its distance between 0 and 70 mm and, in the horizontal, can leave completely from the front of the hollow cathode. The sample and also the cathode hollow are equipped with cromel-alumel termopares with simultaneous reading of the temperatures during the time of treatment. In this work copper electrodes, bronze, titanium, iron, stainless steel, powder of titanium, powder of titanium and silício, glass and ceramic were used. The electrodes were investigated relating their geometry change and behavior of the plasma of the cavity of hollow cathode and channel of the gas. As the cavity of hollow cathode, the analyzed aspects were the diameter and depth. With the channel of the gas, we verified the diameter. In the two situations, we investigated parameters as flow of the gas, pressure, current and applied tension in the electrode, temperature, loss of mass of the electrode with relationship at the time of use. The flow of gas investigated in the electrodes it was fastened in a work strip from 15 to 6 sccm, the constant pressure of work was among 2.7 to 8 x 10-2 mbar. The applied current was among a strip of work from 0,8 to 0,4 A, and their respective tensions were in a strip from 400 to 220 V. Fixing the value of the current, it was possible to lift the curve of the behavior of the tension with the time of use. That curves esteem in that time of use of the electrode to its efficiency is maximum. The temperatures of the electrodes were in the dependence of that curves showing a maximum temperature when the tension was maximum, yet the measured temperatures in the samples showed to be sensitive the variation of the temperature in the electrodes. An accompaniment of the loss of mass of the electrode relating to its time of use showed that the electrodes that appeared the spherical cavities lost more mass in comparison with the electrodes in that didn't appear. That phenomenon is only seen for pressures of 10-2 mbar, in these conditions a plasma column is formed inside of the channel of the gas and in certain points it is concentrated in form of spheres. Those spherical cavities develop inside of the channel of the gas spreading during the whole extension of the channel of the gas. The used electrodes were cut after they could not be more used, however among those electrodes, films that were deposited in alternate times and the electrodes that were used to deposit films in same times, those films were deposited in the glass substrata, alumina, stainless steel 420, stainless steel 316, silício and steel M2. As the eletros used to deposit films in alternate time as the ones that they were used to deposit in same times, the behavior of the thickness of the film obeyed the curve of the tension with relationship the time of use of the electrode, that is, when the tension was maximum, the thickness of the film was also maximum and when the tension was minimum, the thickness was minimum and in the case where the value of the tension was constant, the thickness of the film tends to be constant. The fine films that were produced they had applications with nano stick, bio-compatibility, cellular growth, inhibition of bacterias, cut tool, metallic leagues, brasagem, pineapple fiber and ornamental. In those films it was investigated the thickness, the adherence and the uniformity characterized by sweeping electronic microscopy. Another technique developed to assist the production and characterization of the films produced in that work was the caloteste. It uses a sphere and abrasive to mark the sample with a cap impression, with that cap form it is possible to calculate the thickness of the film. Through the time of life of the cathode, it was possible to evaluate the rate of waste of its material for the different work conditions. Values of waste rate up to 3,2 x 10-6 g/s were verified. For a distance of the substratum of 11 mm, the deposited film was limited to a circular area of 22 mm diameter mm for high pressures and a circular area of 75 mm for pressure strip. The obtained films presented thickness around 2,1 µm, showing that the discharge of arch of hollow cathode in argon obeys a curve characteristic of the tension with the time of life of the eletrodo. The deposition rate obtained in this system it is of approximately 0,18 µm/min

Nitretação em plasma com gaiola catódica: investigação do mecanismo e estudo comparativo com a nitretação em plasma de tensão contínua

The ionic plasma nitriding is one of the most important plasma assisted treatment technique for surface modification, but it presents some inherent problems mainly in nitriding pieces with complex geometries. In the last four years has appeared a plasma nitriding technique, named ASPN (Active Screen Plasma Nitriding) in which the samples and the workload are surrounded by a metal screen on which the cathodic potential is applied. This new technique makes possible to obtain a perfect uniform nitrided layer apart from the shape of the samples. The present work is based on the development of a new nitriding plasma technique named CCPN (Cathodic Cage Plasma Nitriding) Patent PI 0603213-3 derived from ASPN, but utilizes the hollow cathode effect to increase the nitriding process efficiency. That technique has shown great improvement on the treatment of several types of steels under different process conditions, producing thicker and harder layers when compared with both, ASPN and ionic plasma nitriding, besides eliminating problems associated with the later technique. The best obtained results are due to the hollow cathode effect on the cage holes. Moreover, characteristic problems of ionic plasma nitriding are eliminated due to the fact that the luminescent discharge acts on the cage wall instead of on the samples surface, which remains under a floating potential. In this work the enhancement of the cathodic cage nitriding layers proprieties, under several conditions for some types of steels was investigated, besides the mechanism for nitrides deposition on glass substrate, concluding that the CCPN is both a diffusion and a deposition process at the same time

Nitretação iônica sem efeito de borda :desenvolvimento e avaliação de uma nova técnica

The ionic nitriding process presents some limitations related with the control of the thickness of the layer and its uniformity. Those limitations that happen during the process, are produced due to edge effects, damage caused by arcing arc and hollow cathode, mainly in pieces with complex geometry and under pressures in excess of 1 mbar. A new technique, denominated ASPN (active screen shapes nitriding) it has been used as alternative, for offering many advantages with respect to dc plasma conventional. The developed system presents a configuration in that the samples treated are surrounded by a large metal screen at high voltage cathodic potencials, (varying between 0 and 1200V) and currents up to 1 A. The sample is placed in floting potential or polarized at relatively lower bias voltages by an auxiliary source. As the plasma is not formed directly in the sample surface but in the metal screen, the mentioned effects are eliminated. This mechanism allows investigate ion of the transfer of nitrogen to the substrate. Optical and electronic microscopy are used to exam morphology and structure at the layer. X-ray difration for phase identification and microhardness to evaluate the efficiency of this process with respect to dc conventional nitriding

Diagnóstico de plasma de cátodo oco: análise da ação de plasma de argônio e Ar-H2 para a deposição de filmes finos de titânio em pós-descarga

Plasma DC hollow cathode has been used for film deposition by sputtering with release of neutral atoms from the cathode. The DC Plasma Ar-H2 hollow cathode currently used in the industry has proven to be effective in cleaning surfaces and thin film deposition when compared to argon plasma. When we wish to avoid the effects of ion bombardment on the substrate discharge, it uses the post-discharge region. Were generated by discharge plasma of argon and hydrogen hollow cathode deposition of thin films of titanium on glass substrate. The optical emission spectroscopy was used for the post-discharge diagnosis. The films formed were analyzed by mechanical profilometry technique. It was observed that in the spectrum of the excitation lines of argon occurred species. There are variations in the rate of deposition of titanium on the glass substrate for different process parameters such as deposition time, distance and discharge working gases. It was noted an increase in intensity of the lines of argon compared with the lines of titanium. Deposition with argon and hydrogen in glass sample observed a higher rate deposition of titanium as more closer the sample was in the discharge

Desenvolvimento de um sistema a jato de plasma obtido em cátodo oco para deposição de filmes finos

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior

Desenvolvimento e caracterização de dispositivos para reposição de filmes finos por descarga em cátodo oco

In the present work we use a plasma jet system with a hollow cathode to deposit thin TiO2 films on silicon substrates as alternative at sol-gel, PECVD, dip-coating e magnetron sputtering techniques. The cylindrical cathode, made from pure titanium, can be negatively polarized between 0 e 1200 V and supports an electrical current of up to 1 A. An Ar/O2 mixture, with a total flux of 20 sccm and an O2 percentage ranging between 0 and 30%, is passed through a cylindrical hole machined in the cathode. The plasma parameters and your influence on the properties of deposited TiO2 films and their deposition rate was studied. When discharge occurs, titanium atoms are sputtered/evaporated. They are transported by the jet and deposited on the Si substrates located on the substrate holder facing the plasma jet system at a distance ranging between10 and 50 mm from the cathode. The working pressure was 10-3 mbar and the deposition time was 10 -60 min. Deposited films were characterized by scanning electron microscopy and atomic force microscopy to check the film uniformity and morphology and by X-ray diffraction to analyze qualitatively the phases present. Also it is presented the new dispositive denominate ionizing cage, derived from the active screen plasma nitriding (ASPN), but based in hollow cathode effect, recently developed. In this process, the sample was involved in a cage, in which the cathodic potential was applied. The samples were placed on an insulator substrate holder, remaining in a floating potential, and then it was treated in reactive plasma in hollow cathode regime. Moreover, the edge effect was completely eliminated, since the plasma was formed on the cage and not directly onto the samples and uniformity layer was getting in all sampl

Nitretação em plasma com gaiola catódica: investigação do mecanismo e estudo comparativo com a nitretação em plasma de tensão contínua

The ionic plasma nitriding is one of the most important plasma assisted treatment technique for surface modification, but it presents some inherent problems mainly in nitriding pieces with complex geometries. In the last four years has appeared a plasma nitriding technique, named ASPN (Active Screen Plasma Nitriding) in which the samples and the workload are surrounded by a metal screen on which the cathodic potential is applied. This new technique makes possible to obtain a perfect uniform nitrided layer apart from the shape of the samples. The present work is based on the development of a new nitriding plasma technique named CCPN (Cathodic Cage Plasma Nitriding) Patent PI 0603213-3 derived from ASPN, but utilizes the hollow cathode effect to increase the nitriding process efficiency. That technique has shown great improvement on the treatment of several types of steels under different process conditions, producing thicker and harder layers when compared with both, ASPN and ionic plasma nitriding, besides eliminating problems associated with the later technique. The best obtained results are due to the hollow cathode effect on the cage holes. Moreover, characteristic problems of ionic plasma nitriding are eliminated due to the fact that the luminescent discharge acts on the cage wall instead of on the samples surface, which remains under a floating potential. In this work the enhancement of the cathodic cage nitriding layers proprieties, under several conditions for some types of steels was investigated, besides the mechanism for nitrides deposition on glass substrate, concluding that the CCPN is both a diffusion and a deposition process at the same time

Nitretação iônica sem efeito de borda :desenvolvimento e avaliação de uma nova técnica

The ionic nitriding process presents some limitations related with the control of the thickness of the layer and its uniformity. Those limitations that happen during the process, are produced due to edge effects, damage caused by arcing arc and hollow cathode, mainly in pieces with complex geometry and under pressures in excess of 1 mbar. A new technique, denominated ASPN (active screen shapes nitriding) it has been used as alternative, for offering many advantages with respect to dc plasma conventional. The developed system presents a configuration in that the samples treated are surrounded by a large metal screen at high voltage cathodic potencials, (varying between 0 and 1200V) and currents up to 1 A. The sample is placed in floting potential or polarized at relatively lower bias voltages by an auxiliary source. As the plasma is not formed directly in the sample surface but in the metal screen, the mentioned effects are eliminated. This mechanism allows investigate ion of the transfer of nitrogen to the substrate. Optical and electronic microscopy are used to exam morphology and structure at the layer. X-ray difration for phase identification and microhardness to evaluate the efficiency of this process with respect to dc conventional nitriding

Análise por meio de espectroscopia de emissão óptica das espécies ativas em nitretação iônica e gaiola catódica

Plasma process like ionic nitriding and cathodic cage plasma nitriding are utilized in order to become hard surface of steels. The ionic nitriding is already accepted in the industry while cathodic cage plasma nitriding process is in industrial implementation stage. Those process depend of plasma parameters like electronic and ionic temperature (Te, Ti), species density (ne, ni) and of distribution function of these species. In the present work, the plasma used to those two processes has been observed through Optical Emission Spectroscopy OES technique in order to identify presents species in the treatment ambient and relatively quantify them. So plasma of typical mixtures like N2 H2 has been monitored through in order to study evolution of those species during the process. Moreover, it has been realized a systematic study about leaks, also thought OES, that accomplish the evolution of contaminant species arising because there is flux of atmosphere to inside nitriding chamber and in what conditions the species are sufficiently reduced. Finally, to describe the physic mechanism that acts on both coating techniques ionic nitriding and cathodic cage plasma nitriding

Avaliação do desempenho do aço D6 tratado termicamente e netretado em plasma com gaiola catódica visando aplicação industrial

In this research there was an evaluation of the best conditions of nitriding in plasma within a cathodic cage at an atmosphere of 80% N2-20%H2 in samples of tool manganese steel AISI D6, cold working, treated thermally in the following conditions: tension relief, treated thermally to temperature of maximum heat, temperate heat and temperate and temperate heat. A pressure of 2.5mbar and temperatures of 400 and 300ºC com treatment time of two and three hours were used to evaluate its performance as cutting tool (punch) of bicycle backs. Hardness, micro-structural aspects (layer thickness, interface, grain size etc), and crystal phases on the surface were appraised. When treated to tension relief, thermally treated to maximum heat temperature, temperature and temperate heat, the samples presented hardness levels of 243HV, 231HV, 832HV, and 653HV, respectively. The best nitrification conditions were: four hours and 300ºC for heat samples. A superficial hardness of 1000HV and a 108µm thickness for the nitrided layer were found in these samples

Avaliação do desempenho do aço AISI D2 tratado termicamente e nitretado em plasma com gaiola catódica visando aplicação industrial

In the research, steel samples tool AISI D2, treated thermally, in the conditions: relief of tension, when maximum, seasoned and seasoned was treated thermally in the temperature of revenimento and revenida had been nitrited in plasma with cathodic cage, in atmosphere of 80%N2:20%H2. One used pressure of 2,5 mbar, 400 and 480°C temperatures with treatment time of 3 and 4 hours, with the objective to evaluate its performance in pipes cut tool. It was compared that the performance of the same steel when only thermally treated, both with tension relief. It was evaluated its hardness. Microstructural aspects (the layer thickness, interface, graisn size, etc) and crystalline phases on the surface. Besides, it was verified accomplishment possibility of nitriding simultaneous to annealing treatment. The tempering samples had presented hardness levels of 600 HV, while in nitrited samples these values had been 1100 HV

Influência dos parâmetros de processo na deposição de nitreto de titânio por plasma em gaiola catódica

Titanium nitride films were grown on glass using the Cathodic Cage Plasma Deposition technique in order to verify the influence of process parameters in optical and structural properties of the films. The plasma atmosphere used was a mixture of Ar, N2 and H2, setting the Ar and N2 gas flows at 4 and 3 sccm, respectively and H2 gas flow varied from 0, 1 to 2 sccm. The deposition process was monitored by Optical Emission Spectroscopy (OES) to investigate the influence of the active species in plasma. It was observed that increasing the H2 gas flow into the plasma the luminescent intensities associated to the species changed. In this case, the luminescence of N2 (391,4nm) species was not proportional to the increasing of the H2 gas into the reactor. Other parameters investigated were diameter and number of holes in the cage. The analysis by Grazing Incidence X-Ray Diffraction (GIXRD) confirmed that the obtained films are composed by TiN and they may have variations in the nitrogen amount into the crystal and in the crystallite size. The optical microscopy images provided information about the homogeneity of the films. The atomic force microscopy (AFM) results revealed some microstructural characteristics and surface roughness. The thickness was measured by ellipsometry. The optical properties such as transmittance and reflectance (they were measured by spectrophotometry) are very sensitive to changes in the crystal lattice of the material, chemical composition and film thicknesses. Therefore, such properties are appropriate tools for verification of this process control. In general, films obtained at 0 sccm of H2 gas flow present a higher transmittance. It can be attributed to the smaller crystalline size due to a higher amount of nitrogen in the TiN lattice. The films obtained at 1 and 2 sccm of H2 gas flow have a golden appearance and XRD pattern showed peaks characteristics of TiN with higher intensity and smaller FWHM (Full Width at Half Maximum) parameter. It suggests that the hydrogen presence in the plasma makes the films more stoichiometric and becomes it more crystalline. It was observed that with higher number of holes in the lid of the cage, close to the region between the lid and the sample and the smaller diameter of the hole, the deposited film is thicker, which is justified by the most probability of plasma species reach effectively the sample and it promotes the growth of the film