Made available in DSpace on 2017-07-24T19:37:58Z (GMT). No. of bitstreams: 1 cintiafav.pdf: 4767448 bytes, checksum: 5cb193787f5e0c0461b164eb3079f888 (MD5) Previous issue date: 2008-08-06 / Thin films of tin dioxide (SnO2) with the addition of doping are widely used because its various applications, so develop a search on this subject is of great value technology, since many different forms of doping, formulation and preparation, can be made and modified, intended to improve this material according to their physical and chemical properties. This paper used for niobium oxide (Nb2O5) as doping, an important factor in the formulation, since Brazil has the largest reserves of natural element, found in various forms of ore. The preparation of thin films is a process that requires great care and high quality control. However, care is not sufficient to avoid the appearance of defects in his deposition, and subsequent calcination, as broken, deterioration, poor adhesion to the substrate, which are considered problems, undermining the efficiency of the material and its applicability. The addition of self assembled monolayers (SAM) on thin films of SnO2 aimed to reduce or correct this type of defect. Different techniques were used experimentally, as: X-ray diffraction, fotochronoamperometric, eletrochemical impedance spectroscopy, electrochemistry, measures of potential open circuit, optical microscopy optical, scanning electron microscopy and Infrared. The results of the measures to density of current and electrochemical impedance of samples of thin films of SnO2 containing SAM showed positive results, confirming that the SAM not only improved the structure of films about the electrochemical properties and photovoltaic, but also corrected the defects caused existing surface the techniques for the generation thin film. The efficiency of photosensitive films studied increased in the following sequence: SnO2 + SAM < SnO2:Nb2O5(0.1) + SAM SnO2:Nb2O5(0.3) + SAM. The electrochemical impedance spectroscopy, showed that the addition of SAM to thin films studied in this work is diminishing Rtc, minimizing the resistance. The film of SnO2 containing 0.3 Nb2O5 + SAM presents a resistance around 1000 Wcm-1 less than the film containing 0.1 Nb2O5. The thin films containing SAM showed that when immersed in the electrolyte solution, extending the capacitance of double layer electrical probably due to accumulation of cargo between the surface of films. The scanning electron microscopy showed that the nucleation of SAM has a higher incidence of disruptions in the regions (of higher energy) in the form of needles and often mixed, needles and mushrooms, as observed for the film: SnO2: Nb2O5 (0.3 ) + SAM. / Filmes finos de dióxido de estanho (SnO2) com adição de dopantes são muito utilizados devido as suas diversas aplicações, assim o desenvolver de uma pesquisa sobre este tema é de grande valia tecnológica, já que muitas formas diferentes de dopagem, formulação e preparação, podem ser feitas e modificadas, visando o melhoramento deste material em função de suas propriedades físicas e químicas. Neste trabalho foi utilizado óxido de nióbio (Nb2O5) como dopante, um fator importante na formulação, já que o Brasil possui a maior reserva natural deste elemento, encontrado em várias formas de minérios. A preparação de filmes finos é um processo que exige muito cuidado e alto controle de qualidade. Porém, cuidados não são suficientes para evitar o aparecimento de defeitos em sua deposição e, posterior calcinação, como trincas, deteriorização, baixa aderência ao substrato, que são considerados problemas, comprometendo a eficiência do material e sua aplicabilidade. A adição de moléculas auto-organizáveis (SAM) em filmes finos de SnO2 teve como objetivo reduzir ou corrigir este tipo de defeito. Diferentes técnicas foram utilizadas experimentalmente, tais como: difração de raios X, fotocronoamperometria, espectroscopia de impedância eletroquímica, medidas de potencial de circuito aberto, micrografia óptica, microscopia eletrônica de varredura e Infravermelha. Os resultados das medidas de densidade de corrente e impedância eletroquímica das amostras dos filmes finos de SnO2 contendo SAM mostraram resultados positivos, confirmando que a SAM não só melhorou a estrutura dos filmes quanto às propriedades eletroquímicas e fotovoltaicas, como também corrigiu os defeitos superficiais existentes provocados pelas técnicas de geração do filme fino. A eficiência fotossensível dos filmes estudados aumentou na seguinte seqüência: SnO2 + SAM < SnO2:Nb2O5 (0,1) + SAM < SnO2:Nb2O5 (0,3) + SAM. A espectroscopia de impedância eletroquímica mostrou que a adição de SAM aos filmes finos estudados neste trabalho diminui a Rtc, minimizando a resistência do mesmo. O filme de SnO2 contendo 0,3 Nb2O5 + SAM apresenta uma resistência aproximadamente 1000 Wcm-1 menor do que o filme contendo 0,1 Nb2O5. Os filmes finos contendo SAM mostraram que ao serem imersos na solução eletrolítica, ampliaram a capacitância da dupla camada elétrica devido provavelmente ao acúmulo de carga entre a superfície dos filmes. A microscopia eletrônica de varredura mostrou que a nucleação da SAM tem maior incidência nas regiões de rupturas (de maior energia) em forma de agulhas e muitas vezes mista, agulhas e cogumelos, como observado para o filme: SnO2:Nb2O5 (0,3) + SAM.

<p>Thin films of metals and compounds have a very wide range of applications today. Many of the deposition methods used for the production of such films utilize plasma to support the growth the film, e.g. by the supply of energy and the enhancement of reactivity. This thesis focuses on the physical vapor deposition (PVD) of thin films by high density plasma sources based on hollow cathodes and aims to increase the understanding of the deposition process and its influence on the film properties.</p><p>Titanium nitride films reactively deposited by the low-pressure hybrid plasma (HYP LP) source exhibited excellent properties and was deposited at considerable higher rates than films deposited by conventional methods.</p><p>An original finding in this work is the influence of substrate material on the deposition process and consequently on the properties of the deposited film. In the deposition of TiN films by the HYP LP source it was found that the substrate temperature was higher for Si substrates than for steel substrates due to a more efficient absorption of microwave power in Si than in steel. Further, it was found that ferromagnetic substrates influence the film growth in magnetized plasma systems. An effect of the ferromagnetic substrates is the enhancement of ion bombardment that increases the growth temperature and affects the texture and morphology of the growing films. It was also found that a DC bias can change the TiN film properties considerably and compensate the effect of ferromagnetic substrates.</p><p>High rate depositions of chromium and chromium nitride films by the RF hollow cathode plasma jet (RHCPJ) source were studied. The performance of the reactive diffuse arc process and the CrN film properties indicates that the process can be transferred from small cylindrical cathodes to linear magnetized hollow cathodes which allow deposition on considerable larger areas and this is important for industrial applications.</p>

Thin films of metals and compounds have a very wide range of applications today. Many of the deposition methods used for the production of such films utilize plasma to support the growth the film, e.g. by the supply of energy and the enhancement of reactivity. This thesis focuses on the physical vapor deposition (PVD) of thin films by high density plasma sources based on hollow cathodes and aims to increase the understanding of the deposition process and its influence on the film properties. Titanium nitride films reactively deposited by the low-pressure hybrid plasma (HYP LP) source exhibited excellent properties and was deposited at considerable higher rates than films deposited by conventional methods. An original finding in this work is the influence of substrate material on the deposition process and consequently on the properties of the deposited film. In the deposition of TiN films by the HYP LP source it was found that the substrate temperature was higher for Si substrates than for steel substrates due to a more efficient absorption of microwave power in Si than in steel. Further, it was found that ferromagnetic substrates influence the film growth in magnetized plasma systems. An effect of the ferromagnetic substrates is the enhancement of ion bombardment that increases the growth temperature and affects the texture and morphology of the growing films. It was also found that a DC bias can change the TiN film properties considerably and compensate the effect of ferromagnetic substrates. High rate depositions of chromium and chromium nitride films by the RF hollow cathode plasma jet (RHCPJ) source were studied. The performance of the reactive diffuse arc process and the CrN film properties indicates that the process can be transferred from small cylindrical cathodes to linear magnetized hollow cathodes which allow deposition on considerable larger areas and this is important for industrial applications.

The broad theme of the present research investigation is Ion Assisted Deposition of thin films and its effect on the properties of thin films. Though this activity has been of interest to researchers for more than a decade, the development of different types of ion sources with control over the ion flux and energy, makes it a current topic of interest. Ion assisted deposition was successful in depositing thin films of many material with desired qualities, however, there are certain class of materials whose deposition has been rather difficult. This has mainly been attributed to higher energies and low ion flux of conventional ion sources. The advent of ECR ion sources for thin film deposition has given impetus to the deposition of such materials. This is due to the low energy high-density plasma generated in this type of sources. Hitherto, these sources were widely used in PECVD techniques and only recently the importance of ECR sources in PVD techniques has been realized. This thesis is on the development of ECR plasma source for ion assisted deposition of thin films using PVD techniques. This thesis is organized into six chapters. The first chapter gives an introduction on the ion assisted growth of thin films and the importance of ECR plasma. A detailed discussion on various aspects of ECR sources has been included. The design details on the development of ECR source have been discussed in the second chapter. The performance of ECR source as analyzed by the Langmuir probe are also discussed. Variation of plasma parameters like ion density, electron temperature, plasma potential and floating potential as a function of pressure and microwave power have been studied using Langmuir probe analysis. An ion density of the order of 1011/cm3 was measured at a distance of 8 cm from the plasma source with a microwave power of 400 watts. This was comparable to the ion density reported in downstream plasma of ECR sources. The behavior of plasma parameters with variation in microwave power and pressure was explained on the basis of microwave transmission above critical ion density and the microwave power absorption. The uniformity of the plasma parameters at the substrate position (29 cm from the ECR source) was found to be ± 2% over a diameter of 12 cm, which makes the ion source suitable for ion assisted deposition. The third chapter deals with the simulation and experimental study of the ECR sputtering process. ECR sputter type sources are equipped with cylindrical targets. The sputtered flux distribution on the substrate depends on target geometry, sputtering pressure and target-substrate distance. The effect of cylindrical geometry on the distribution of sputtered flux has been simulated by Monte Carlo methods. It is found that the sputtered flux distribution at different pressures and target-substrate distances in ECR sputter type source differs from the conventional glow discharge sputtering system equipped with planar targets. The simulated results are compared with the experimental results. The simulated data agree very well with the experimental data. The deposition and characterization of the TiN thin films for diffusion barrier applications in copper metallization have been discussed in the fourth chapter. Titanium nitride films are prepared by ECR sputtering. The effect of high density ion bombardment on the morphology, orientation and resistivity of the films was studied. It was observed that films with atomic smoothness could be prepared by ECR sputtering. Also the high density ion bombardment has been found to be effective for the film growth in (100) orientation. The behavior of TiN films deposited by this method as a diffusion barrier in copper metallization has been investigated. The resistivity measurements and RBS depth profile studies showed that up to 700°C there is no diffusion of copper into silicon. This shows that ECR sputtered TiN can be used as an effective diffusion barrier in copper metallization. The fifth chapter contains investigations on the ECR assisted growth of silicon nitride films. The films are characterized for composition, morphology and chemical bonding using AES, RBS, AFM, XPS and FTIR. AFM studies revealed that ion bombardment results in the reduction of surface roughness, which indicates dense film growth. The effect of ion assistance on the optical and electrical properties is studied in detail. Films prepared with microwave power ranging from 100 to 200 watts are having bandgap and refractive index of 4.9 eV and 1.92 respectively. Interface state density of silicon nitride films prepared in the above mentioned range was found to be 5x10 10 eVcm2. These films exhibited a resistivity of 10 13 Ω, cm and critical field of 4 MV/cm. The electrical conductivity in these films has been explained on the basis of Poole and Frenkel conduction. The low value of interface state density, higher resistivity, and critical field show that good quality SiN4 films can be deposited with low energy high density ECR plasma. A detailed summary of this research investigation has been discussed in the last chapter. The thesis is concluded with a discussion on the need of focused ECR source to establish ECR assisted deposition as a versatile technique for the growth of thin films.

<p>Stress relaxation in tin films can result in microstructural changes visible on the surface, referred to as “surface defects,” and can include whisker and hillock formation, cracking, nucleation of new grains, and grain growth. Sn whiskers are of particular concern for microelectronics reliability in which Sn whiskers growing from component surface and cause catastrophic short-circuiting. While prior research has identified the conditions and mechanisms for surface defect evolution during aging and thermal cycling, the response of tin films due to mechanical stress, especially high frequency vibration, is not fully understood. In practical terms, high frequency vibration is an important source of mechanical stress generation in microelectronics for automotive and aerospace applications. This research, based on high frequency vibration of cantilevers, adds to the existing mechanisms for stress relaxation process in metal thin films, not just for tin films, as well as proposed new mechanisms for such processes.</p> <p>In the first study, the piezoelectric drive of small atomic force microscopy (AFM) cantilevers vibrated at resonance are used for high frequency cyclic bending experiments. Intermetallic (IMC) formation as well as initial film morphology and thickness (corresponding to surface grain size) all influence the response of tin films for cyclic bending. A laser doppler vibrometer (LDV) system was used to identify the real-time strain along the cantilever during cycling, suggesting that the small strains are responsible for the limited nucleation and growth for defects though the defect density increases with the number of cycles and strain distribution along the cantilever.</p> <p>In the second study, the effect of larger strains on defect evolution was determined using vibration of larger cantilevers at resonance as a function of number of cycles, frequency, temperature, and whether the vibration was continuous or interrupted for SEM characterization of defect type and density. In addition to typical micro-sized whiskers and hillocks, intragranular breakup (IGB) with intrusions and extrusions and nanowhiskers (NWs) with diameters < 1 𝜇m were observed. Both increasing number of cycles and strain amplitude/rate promote defect formation for a fixed frequency, with the defect density being strongly frequency dependent.Vibration at low temperature and interrupting measurements for SEM characterization affected the relative densities. The density of larger surface defects is strongly influenced by interruptions while NW density is almost unaffected. </p><p>Both low resonant frequency and low T (223 K) promote IGB formation during cyclic bending due to large maximum strain amplitude and slower diffusion/creep at low T, respectively. Though the overall defect density for low T is smaller than that at room temperature (RT), the response of films is similar to that at RT, indicating the same mechanisms. The defect density decrease at low T is mainly determined by NW formation, and there is a transition from micro-sized surface defects to IGBs for cyclic bending at low T.</p><p>This research demonstrated that cyclic bending of cantilevers can be used to quantify the stress relaxation of tin films in an important stress regime for microelectronics and to develop defect mitigation strategies to improve the reliability of interconnects in electronic applications.</p>