Plasma induced damage of ultra low-k (ULK) dielectrics is a common phenomenon in BEOL interconnects. The damage leads to an increase in k-value, which raises the RC delay, leading to increased power consumption and cross talk noise. Therefore, diverse repair and post etch treatments (PET) have been proposed to restore or reduce the ULK damage. However, current repair processes are usually based on non-plasma silylation, which suffers from limited chemistry diffusion into the ULK. Moreover, the conventional PET based on anisotropic plasma results in bottom vs. sidewall inhomogeneities of the structures (e.g. via and trench). To reduce these drawbacks, an organosilane downstream -plasma (DSP) was applied. This new application resulted in an increased resistance to ULK removal by fluorinated wet clean chemistries, preserving the ULK hydrophobicity, keeping its carbon content relatively high. The effective RC measured on 28 nm node patterned wafers treated with a DSP PET remains nevertheless comparable to the process of record (POR).

The objective of this study was to increase the bond strength at the surface interface of a thin stainless-steel panel for structural bonding on a helicopter. To achieve this objective, six activation methods for applying the coating to the panel in the surface preparation process are presented and explored. Adhesion and roughness tests were conducted to determine which method consistently initiates the etch and improves the bond at the surface. Based on the test results, three methods proved to be effective in initiating the etch. Of the three effective methods, only one method exhibited significantly improved bond strength at the surface interface as well as consistently initiated the etch in solution. The applicability of this method is discussed, and recommendations are presented for further study.

Fabrication of current generation integrated circuits involves the creation of multilevel copper/low-k dielectric structures during the back end of line processing. This is done by plasma etching of low-k dielectric layers to form vias and trenches, and this process typically leaves behind polymer-like post etch residues (PER) containing copper oxides, copper fluorides and fluoro carbons, on underlying copper and sidewalls of low-k dielectrics. Effective removal of PER is crucial for achieving good adhesion and low contact resistance in the interconnect structure, and this is accomplished using wet cleaning and rinsing steps. Currently, the removal of PER is carried out using semi-aqueous fluoride based formulations. To reduce the environmental burden and meet the semiconductor industry's environmental health and safety requirements, there is a desire to completely eliminate solvents in the cleaning formulations and explore the use of organic solvent-free formulations.The main objective of this work is to investigate the selective removal of PER over copper and low-k (Coral and Black Diamond®) dielectrics using all-aqueous dilute HF (DHF) solutions and choline chloride (CC) - urea (U) based deep eutectic solvent (DES) system. Initial investigations were performed on plasma oxidized copper films. Copper oxide and copper fluoride based PER films representative of etch products were prepared by ashing g-line and deep UV photoresist films coated on copper in CF4/O2 plasma. PER removal process was characterized using scanning electron microscopy and X-ray photoelectron spectroscopy and verified using electrochemical impedance spectroscopy measurements.A PER removal rate of ~60 Å/min was obtained using a 0.2 vol% HF (pH 2.8). Deaeration of DHF solutions improved the selectivity of PER over Cu mainly due to reduced Cu removal rate. A PER/Cu selectivity of ~20:1 was observed in a 0.05 vol% deaerated HF (pH 3). DES systems containing 2:1 U/CC removed PER at a rate of ~10 and ~20 Å/min at 40 and 70oC respectively. A mixture of 10-90 vol% de-ionized water (W) with 2:1 U/CC in the temperature range of 20 to 40oC also effectively removed PER. Importantly, etch rate of copper and low-k dielectric in DES formulations were lower than that in conventional DHF cleaning solutions.

Os estudos sobre contaminação apresentam difícil comparação devido a variedade dos delineamentos experimentais como o tipo de substrato testado, o momento na sequência do procedimento adesivo em que a contaminação acontece e a forma como essa contaminação é tratada de maneira a limpar este campo operatório. Assim, novos estudos fazem-se necessários para investigar com maior profundidade as condições já descritas na literatura e assim, obter um protocolo de conduta mais seguro para lidar com a contaminação. Esse estudo objetivou analisar,através de Microscopia Eletronica de Varredura (MEV), a interface adesiva de restaurações realizadas com sistema adesivo autocondicionante de dois passos (Clearfill SE Bond Kuraray), contaminadas por sangue em dois momentos diferentes, recebendo essa contaminaçao dois tratamento distintos. Para tanto foram selecionados 15 molares humanos que foram divididos em 5 grupos experimentais (n=3): G1 controle (sem contaminaçao); G2 contaminação antes do primer, com tratamento de lavagem e secagem; G3 contaminação antes do primer com tratamento de secagem; G4 contaminação após bond fotopolimerizado com tratamento de lavagem e secagem; G5 contaminação após bond fotopolimerizado com tratamento de secagem. Os dentes foram submetidos ao corte do terço oclusal da coroa para obtenção de superfície dentinária plana. Essa superfície foi regularizada com lixas SiC e a camada de esfregaço padronizada foi obtida com lixa SiC #600 por 1 min. Os espécimes foram contaminados, de acordo com os grupos experimentais, com sangue obtido de um único doador o próprio autor armazenado em tubos Vacuette® com heparina sódica e utilizado em até 7 dias. Então foram restaurados com uma camada de resina flow (Filtek Z-350 Flow 3M-ESPE) e duas camadas de resina microhibrida (Filtek Z-350 3MESPE). Após a construção dos espécimes, estes foram seccionados ao meio e passaram por preparo para análise em MEV. Os resultados obtidos foram descritos de duas formas: Análise Morfológica: onde foram observadas alterações na formação da camada híbrida (CH) em grupos com a presença do contaminante, e Análise Morfométrica, que foi analisada estatisticamente, e pode-se constatar uma relação entre a presença do contaminante e a diminuição do tamanho de tags em m, quando comparados ao grupo controle (p 0,05). Adicionalmente, foi observado que o tratamento de lavagem com água não foi suficiente para reestabelecer a formação de camada híbrida semelhante a observada no grupo controle. / Studies on contamination are difficult to compare due to the variety of experimental designs as the type of substrate, the time when contamination takes place during the adhesive procedure and how this contamination is treated in order to clean the operatory field. Thus, further studies are needed to investigate more thoroughly the conditions described in the literature and obtain a protocol to deal with contamination. This study aimed to observe, by scanning electron microscopy (SEM), the interface of adhesive restorations performed with a two-stepself-etching adhesive system (Clearfill SE Bond - Kuraray), contaminated with blood at two different times, receiving two different treatment to the contamination . Therefore, 15 selected human molars were divided into five experimental groups (n = 3): G1 - control (no contamination), G2 - contamination before primer, and rinsing and drying treatment, G3 - contamination before priming treatment, thendrying; G4 - contamination after light curing bond, rinsing and drying treatment; G5 - after light curing bond and drying. The teeth were then seccioned in order to obtain a flat dentin surface. This surface was regularized with SiC sandpaper and a standardized smear layer was obtained with SiC sandpaper # 600 for 1 min. The specimens were subsequently contaminated, according to the experimental groups, with blood obtained from a single donor - the author stored inVacuette ® tubes with sodicheparin and used within 7 days. They were restored with a layer of flowable composite (Filtek Z-350 Flow - 3M-ESPE) and two layers of microhybridresin (Filtek Z-350 - 3M-ESPE). After construction, the specimenswere divided in two, exposing the center of restorationand passed through preparation for SEM analysis. The results were described in two ways: Morphological Analysis where changes were observed in hybrid layer (HL) formation of groups in the presence of the contaminant, and Morphometric Analysis, which was analyzed statistically andaassociation between presence of the contaminant and a decreasing size of tags was found when compared to the control group (p 0.05). Additionally, it was observed that treatment of washing with water was not sufficient to restore the formation of hybrid layer similar to that observed in the control group.

A presente pesquisa se propôs a avaliar a influência de cinco tratamentos dentinários na resistência de união à dentina de quatro cimentos de ionômero de vidro modificados por resina (CIVRMs). O ensaio experimental foi realizado in vitro, fazendo uso de 200 incisivos bovinos. Destes, foram obtidos 200 fragmentos de dentina, que foram distribuídos aleatoriamente em 20 grupos (n=10), segundo os fatores de variação que compreendem cinco tratamentos dentinários (Grupo controle, ou seja, sem tratamento; Ácido Poliacrílico a 20%, Clearfil SE Bond; Single Bond Universal e Primer do Vitremer) e quatro cimentos ionoméricos (GC Fuji II LC® CAPSULE; GC Fuji LINING® LC (Paste Pak); Vitrebond® e Vitremer). Após a confecção dos corpos de prova e 24h de armazenamento em estufa à 37oC, foi realizado o teste de microcisalhamento na máquina de ensaios universal (Instron 5942 - Canton, MA, EUA) com velocidade de 1mm/min, seguido da análise do padrão de fratura em microscópio digital. A análise estatística dos 400 resultados obtidos foi feita por meio do teste paramétrico ANOVA para dois fatores de variação (cimento e tratamento) (p<0,05%) e pelo teste auxiliar de Tukey (p<0,05%). Os testes estatísticos demonstraram haver diferença estatística tanto entre os tratamentos, como entre os cimentos e na interação de ambos (p<0,0001). Os sistemas adesivos Clearfil SE (X?=18,26 ± 2,78) e SingleBond (X?=17,28 ± 2,49) promoveram os valores de resistência adesiva mais elevados em comparação aos demais tratamentos, mas sem apresentarem diferença estatística entre si, o que representou um aumento na resistência de união de 121% para o Clearfil SE e 109,2% para o Single Bond Universal em relação ao Grupo Controle. O uso do Ácido Poliacrílico (X?=9,94 ± 3,55) alcançou valores intermediários, correspondendo a um aumento de 20% na resistência adesiva em relação ao Grupo Controle. Esse tratamento se diferenciou estatisticamente dos maiores valores, porém não apresentou diferença frente ao Primer do Vitremer (X?=8,91 ± 2,97). O grupo controle (X?=8,26 ± 4,17) evidenciou os menores valores, se diferenciando estatisticamente dos sistemas adesivos e do Ácido Poliacrílico, mas com resultados que o equiparou ao tratamento com o Primer do Vitremer. Ao se analisar a interação entre cimento e tratamento, todos os cimentos de ionômero de vidro resinomodificados (CIVRMs) testados neste estudo apresentaram seus maiores resultados quando um dos sistemas adesivos foi utilizado como tratamento dentinário, independente de qual sistema adesivo. Com base nesses resultados, pôde-se concluir que os dois sistemas adesivos autocondicionantes foram capazes de melhorar significativamente a resistência adesiva dos CIVRMs. / This research aims to evaluate the influence of five dentin pretreatments on microshear bond strength of four resin-modified glass ionomer (RMGI). The experiment was performed in vitro, using 200 bovine incisors. From these, there were obtained 200 dentine fragments that were randomly distributed into 20 groups (n = 10) according to the variation factors comprising five dentin treatment (control group, i.e., no treatment; Polyacrylic Acid 20%; Clearfil SE Bond; Single Bond Universal and Vitremer Primer) and four glass ionomer cements (GC Fuji II LC® CAPSULE; GC Fuji LC LINING® (Paste Pak); Vitrebond® and Vitremer). After preparation of the samples and 24h storage at 37 °C, was performed microshear test in a universal testing machine (Instron 5942 - Canton, MA, USA) with speed of 1mm/min, followed by analysis of the pattern fractures in digital microscope. Statistical analysis of the 400 results was performed by ANOVA nonparametric test for two variation factors (cement and treatment) (p <0.05%) and the post-hoc Tukey (p <0.05%). The tests demonstrated there are statistical difference between treatments, cements and between the interaction of both (p <0.0001). The Clearfil SE (X?=18,26 ± 2,78) and SingleBond (X?=17,28 ± 2,49) promoted the highest bond strength values compared to the other treatments, but showing no statistical difference between them, which represented an increase in bond strength of 121% for Clearfil SE and 109.2% for Single Bond Universal compared to control group. The Polyacrylic Acid (X?=9,94 ± 3,55) has reached intermediate values, corresponding to a 20% increase in adhesive strength compared to control group. This treatment differed significantly from the higher values, but showed no difference compared to Primer Vitremer (X?=8,91 ± 2,97). The control group (X?=8,26 ± 4,17) showed the lowest values, statistically differing from the adhesives and polyacrylic acid, but with results that matched to the treatment with Vitremer Primer. When analyzing the interaction between cement and treatment, all cements tested in this study had higher results when one of the adhesive systems was used as dentin treatment, regardless of which adhesive system. Based on these results, it could be concluded that the two adhesive systems were able to significantly improve the adhesive strength of RMGIs.

A novel process for the fabrication of Long Range Surface Plasmon Polariton (LRSPP) waveguide based biosensors is presented herein. The structure of the biosensor is comprised of Au stripe waveguide devices embedded in thick CYTOP claddings with a SiO2 solvent diffusion barrier and etch-stop layer. The SiO2 layer is introduced to improve the end quality of Au waveguide structures, which previously deformed during the deposit of the upper cladding process and to limit the over-etching of CYTOP to create micro-fluidic channels. The E-beam evaporation method is adapted to deposit a thin SiO2 on the bottom cladding of CYTOP. A new micro-fluidic design pattern is introduced. Micro-fluidic channels were created on selective Au waveguides through O2 plasma etching. The presented data and figures are refractive index measurements of different materials, thickness measurements, microscope images, and AFM images. Optical power cutback measurements were performed on fully CYTOP-cladded symmetric LRSPP waveguides. The end-fire coupling method was used to excite LRSPP modes with cleaved polarization maintaining (PM) fibre. The measured mode power attenuation (MPA) was 6.7 dB/mm after using index-matched liquid at input and output fibre-waveguide interfaces. The results were compared with the theoretical calculations and simulations. Poor coupling efficiency and scattering due to the SiO2 are suspected for off-target measurements.

A novel process for the fabrication of Long Range Surface Plasmon Polariton (LRSPP) waveguide based biosensors is presented herein. The structure of the biosensor is comprised of Au stripe waveguide devices embedded in thick CYTOP claddings with a SiO2 solvent diffusion barrier and etch-stop layer. The SiO2 layer is introduced to improve the end quality of Au waveguide structures, which previously deformed during the deposit of the upper cladding process and to limit the over-etching of CYTOP to create micro-fluidic channels. The E-beam evaporation method is adapted to deposit a thin SiO2 on the bottom cladding of CYTOP. A new micro-fluidic design pattern is introduced. Micro-fluidic channels were created on selective Au waveguides through O2 plasma etching. The presented data and figures are refractive index measurements of different materials, thickness measurements, microscope images, and AFM images. Optical power cutback measurements were performed on fully CYTOP-cladded symmetric LRSPP waveguides. The end-fire coupling method was used to excite LRSPP modes with cleaved polarization maintaining (PM) fibre. The measured mode power attenuation (MPA) was 6.7 dB/mm after using index-matched liquid at input and output fibre-waveguide interfaces. The results were compared with the theoretical calculations and simulations. Poor coupling efficiency and scattering due to the SiO2 are suspected for off-target measurements.

As feature sizes in semiconductor devices become smaller and newer materials are incorporated, current methods for photoresist and post plasma etch residue removal face several challenges. A cleaning process should be environmentally benign, compatible with dielectric materials and copper, and provide residue removal from narrow and high aspect ratio features. In this work, sub-critical CO2 based mixtures have been developed to remove the etch residues; these mixtures satisfy the above requirements and can potentially replace the two step residue removal process currently used in the integrated circuit (IC) industry. Based on the chemical nature of the residue being removed, additives or co-solvents to CO2 have been identified that can remove the residues without damaging the dielectric layers. Using the phase behavior of these additives as a guide, the composition of the co-solvent was altered to achieve a single liquid phase at moderate pressures without compromising cleaning ability. The extent of residue removal has been analyzed primarily by x-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Various techniques such as attenuated total reflection - Fourier transform infrared (ATR-FTIR) spectroscopy, angle-resolved XPS (ARXPS), and interferometry were used to probe the interaction of cleaning fluids with residues. Model films of photoresists and plasma deposited residues were used to assist in understanding the mechanism of residue removal. From these studies, it was concluded that residue removal takes place primarily by attack of the interface between the residue and the substrate; a solvent rinse then lifts these residues from the wafer. It has been shown that transport of the additives to the interface is enhanced in the presence of CO2. From positronium annihilation lifetime spectroscopy (PALS) studies on a porous dielectric film, it has been shown that these high pressure fluids do not cause significant changes to the pore sizes or the bonding structure of the film. Hence, this method can be used to remove post etch residues from low-k dielectric films.

This research explores a novel in-situ technique for monitoring film thickness in the reactive etching process that incorporates a micromachined sensor. The sensor correlates film thickness with changes in resonant frequency that occurs in the micromachined platform during etching. The sensor consists of a platform that is suspended over drive and sense electrodes on the surface of the substrate. As material is etched from the platform, its resonant vibrational frequency shifts by an amount that is proportional to the amount of material etched, allowing etch rate to be inferred. This RIE monitoring methodology exploits the accuracy of resonant micromechanical structures, whereby shifts in the fundamental resonant frequency measure a physical parameter. A majority of these systems require free-standing mechanical movement and utilize a sacrificial layer process as the key technique to develop and release the structure on a substrate. A sacrificial layer technique that incorporates a low temperature sacrificial polymer was utilized to develop and release the suspended RIE sensor with excellent performance and is capable of fabricating other low cost, high performance and reliable suspended MEMS devices. The integration of sensors and electronic circuitry is a dominant trend in the semiconductor industry, and much work and research has been devoted to this effort. The RIE sensor relies on capacitive transduction to detect small capacitance changes and the resulting change in resonant frequency during the RIE process. The RIE sensor's overall performance is limited by the interface circuit, and integration with the proper circuit allows the RIE sensor to function as a highly sensitive measure of etch rate during the RIE process. A capacitive feedback charge amplifier interface circuit, when configured with the RIE senor at the input achieves very low noise sensing of capacitance changes and offers the potential for wide dynamic range and high sensitivity. As an application vehicle, process control was demonstrated in the PlasmaTherm SLR series RIE system located in the Georgia Tech Microelectronics Research Center.

<p>Semiconductor wafer bonding has been a subject of interestfor many years and a wide variety of wafer bonding techniqueshave been reported in literature. In adhesive wafer bondingorganic and inorganic adhesives are used as intermediatebonding material. The main advantages of adhesive wafer bondingare the relatively low bonding temperatures, the lack of needfor an electric voltage or current, the compatibility withstandard CMOS wafers and the ability to join practically anykind of wafer materials. Adhesive wafer bonding requires nospecial wafer surface treatmentssuch as planarisation.Structures and particles at the wafer surfaces can be toleratedand compensated for some extent by the adhesive material.Adhesive wafer bonding is a comparably simple, robust andlowcost bonding process. In this thesis, adhesive wafer bondingtechniques with different polymer adhesives have beendeveloped. The relevant bonding parameters needed to achievehigh quality and high yield wafer bonds have been investigated.A selective adhesive wafer bonding process has also beendeveloped that allows localised bonding on lithographicallydefined wafer areas.</p><p>Adhesive wafer bonding has been utilised in variousapplication areas. A novel CMOS compatible film, device andmembrane transfer bonding technique has been developed. Thistechnique allows the integration of standard CMOS circuits withthin film transducers that can consist of practically any typeof crystalline or noncrystalline high performance material(e.g. monocrystalline silicon, gallium arsenide,indium-phosphide, etc.). The transferred transducers or filmscan be thinner than 0.3 µm. The feature sizes of thetransferred transducers can be below 1.5 µm and theelectrical via contacts between the transducers and the newsubstrate wafer can be as small as 3x3 µm2. Teststructures for temperature coefficient of resistancemeasurements of semiconductor materials have been fabricatedusing device transfer bonding. Arrays of polycrystallinesilicon bolometers for use in uncooled infrared focal planearrays have been fabricated using membrane transfer bonding.The bolometers consist of free-hanging membrane structures thatare thermally isolated from the substrate wafer. Thepolycrystalline silicon bolometers are fabricated on asacrificial substrate wafer. Subsequently, they are transferredand integrated on a new substrate wafer using membrane transferbonding. With the same membrane transfer bonding technique,arrays of torsional monocrystalline silicon micromirrors havebeen fabricated. The mirrors have a size of 16x16 µm2 anda thickness of 0.34 µm. The advantages of micromirrorsmade of monocrystalline silicon are their flatness, uniformityand mechanical stability. Selective adhesive wafer bonding hasbeen used to fabricate very shallow cavities that can beutilised in packaging and component protection applications. Anew concept is proposed that allows hermetic sealing ofcavities fabricated using adhesive wafer bonding. Furthermore,microfluidic devices, channels and passive valves for use inmicro total analysis systems are presented.</p><p>Adhesive wafer bonding is a generic CMOS compatible bondingtechnique that can be used for fabrication and integration ofvarious microsystems such as infrared focal plane arrays,spatial light modulators, microoptical systems, laser systems,MEMS, RF-MEMS and stacking of active electronic films forthree-dimensional high-density integration of electroniccircuits. Adhesive wafer bonding can also be used forfabrication of microcavities in packaging applications, forwafer-level stacking of integrated circuit chips (e.g. memorychips) and for fabrication of microfluidic systems.</p>