The aim of this thesis was to investigate the physical and electrochemical properties of sub monolayer and monolayer of copper deposition on the polycrystalline iridium, ruthenium and its conductive oxide. The electrochemical methods cyclic voltammetry (CV) and chronocoulometry were used to study the under potential deposition. The electrochemical methods to oxidize the ruthenium metal are presented, and the electrochemical properties of the oxide ruthenium are studied. The full range of CV is presented in this thesis, and the distances between the stripping bulk peak and stripping UPD peak in various concentration of CuSO4 on iridium, ruthenium and its conductive oxide are shown, which yields thermodynamic data on relative difference of bonding strength between Cu-Ru/Ir atoms and Cu-Cu atoms. The monolayer of UPD on ruthenium is about 0.5mL, and on oxidized ruthenium is around 0.9mL to 1.0mL. The conductive oxide ruthenium presents the similar properties of ruthenium metal. The pH effect of stripping bulk peak and stripping UPD peak of copper deposition on ruthenium and oxide ruthenium was investigated. The stripping UPD peak and stripping bulk peak disappeared after the pH ≥ 3 on oxidized ruthenium electrode, and a new peak appeared, which means the condition of pH is very important. The results show that the Cl- , SO42- , Br- will affect the position of stripping bulk peak and stripping UPD peak: the stripping bulk peak will shift and decrease if the concentration of halide ions is increasing, and the monolayer of UPD will increase at the same time.

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The microelectronics industry requires continuous advances due to ever-evolving technology and the corresponding need for higher density substrates with smaller features. Specifically, new dielectric materials with enhanced electrical properties are needed. At the same time, adhesion must be maintained in order to preserve package reliability and mechanical performance. As a result, this research investigates the use of thin glass sheets as an alternative substrate material as it offers a number of advantages including coefficient of thermal expansion similar to silicon, good dielectric properties and optical transparency to assist in the alignment of buried features. As part of this project it was necessary to deposit metallic coatings onto the glass sheets to create electrical tracks, pads and microvias. In order to meet these requirements, the metallisation of both smooth as received glass surfaces and surfaces roughened by laser machining using electroless copper and nickel deposition were investigated. This study resulted in a number of important conclusions about the roles of chemical bonding and mechanical anchoring in both the adhesion and catalyst adsorption, that are key factors in the electroless metallisation process.....

Cheminio variavimo tirpalai bei cheminio variavimo procesai tiriami jau nuo XX a. vidurio iki šių dienų, ieškant vis efektyvesnių parametrų dangų funkcinėms bei dekoratyvinėms savybėms pagerinti. Pastaruoju metu vis didesnis dėmesys krypsta ne tik į nusodinamų dangų funkcionalumą, bet ir į ekologiškai nekenksmingus ar mažiau kenksmingus technologinius procesus, pzv., vykdoma ekologiškai nekenksmingų ligandų paieška. Kaip alternatyva šiuo metu siūlomos dvi cheminių junginių klasės t.y. alditoliai (polihodroksiliai alkoholiai) ir hidroksikarboksirūgštys. Pagrindinis darbo tikslas: ištirti cheminio variavimo sistemas ir jose vykstančius procesus, vario(II) jonų ligandais naudojant ekologiškai nekenksmingas citrinų ir vyno rūgštis. Cheminio variavimo sistemose panaudoti du nauji Cu(II) jonų ligandai t.y. citrinų rūgštis ir vyno rūgšties D-izomeras. Atliktų tyrimų duomenys rodo, kad minėti ligandai sėkmingai gali būti naudojami cheminio variavimo sistemose, kur reduktoriumi naudojamas formaldehidas. Nustatyta, kad 2-hidroksipropan-1,2,3-trikarboksirūgštis (citrinų rūgštis) ir 2,3-dihidroksibutano-1,4-dirūgštis (vyno rūgštis) šarminėje terpėje sudaro pakankamai patvarius kompleksus su vario(II) jonais ir yra tinkamas ligandas vario(II) kompleksinimui šarminiuose (pH > 12) cheminio variavimo tirpaluose. Ištirta vario(II)-citrato ir Cu(II)-D-, L- ir DL-tartratų kompleksų redukcija hidratuotu formaldehidu, apibūdintos gautosios vario dangos. Optimaliomis proceso vykdymo sąlygomis... [toliau žr. visą tekstą] / Electroless metal coating technique is one of the elegant ways of metal coating by controlling the temperature and pH of the plating bath in which there is no usage of electric current. The industrial electroless copper plating solution containing formaldehyde as reducing agent are known from the middle of the last century and are widespread in the practice up to now. However many chemical compounds used in such kind technological processes are hazardous for total environment, therefore the efforts are made to displace those substances with less hazardous or purely harmless compounds. Generally two classes of chemical compounds were proposed as EDTA alternative, namely alditols (polyhydroxylic alcohols) and hydroxypolycarboxylic acids. The aim of the work was to investigate peculiarities of formaldehyde containing alkaline electroless copper deposition systems using environment friendly hydroxycarboxylic acids as Cu(II) ligands. Two new Cu(II) ligands, namely citric acid and D-isomer of tartaric acid, were applied for the systems of electroless copper deposition. The results of the investigations show that the ligands mentioned can be successful applied in the processes of electroless copper deposition using formaldehyde as reducing agent. Citric acid (2-hydroxypropane-1,2,3-tricarboxylic acid) and different isomers of tartaric acid (2,3-dihydroxybutanedioic acid), namely L- and D-tartrate, and their racemic mixture DL-tartrate, forming sufficiently stable complexes with... [to full text]

Electroless metal coating technique is one of the elegant ways of metal coating by controlling the temperature and pH of the plating bath in which there is no usage of electric current. The industrial electroless copper plating solution containing formaldehyde as reducing agent are known from the middle of the last century and are widespread in the practice up to now. However many chemical compounds used in such kind technological processes are hazardous for total environment, therefore the efforts are made to displace those substances with less hazardous or purely harmless compounds. Generally two classes of chemical compounds were proposed as EDTA alternative, namely alditols (polyhydroxylic alcohols) and hydroxypolycarboxylic acids. The aim of the work was to investigate peculiarities of formaldehyde containing alkaline electroless copper deposition systems using environment friendly hydroxycarboxylic acids as Cu(II) ligands. Two new Cu(II) ligands, namely citric acid and D-isomer of tartaric acid, were applied for the systems of electroless copper deposition. The results of the investigations show that the ligands mentioned can be successful applied in the processes of electroless copper deposition using formaldehyde as reducing agent. Citric acid (2-hydroxypropane-1,2,3-tricarboxylic acid) and different isomers of tartaric acid (2,3-dihydroxybutanedioic acid), namely L- and D-tartrate, and their racemic mixture DL-tartrate, forming sufficiently stable complexes with... [to full text] / Cheminio variavimo tirpalai bei cheminio variavimo procesai tiriami jau nuo XX a. vidurio iki šių dienų, ieškant vis efektyvesnių parametrų dangų funkcinėms bei dekoratyvinėms savybėms pagerinti. Pastaruoju metu vis didesnis dėmesys krypsta ne tik į nusodinamų dangų funkcionalumą, bet ir į ekologiškai nekenksmingus ar mažiau kenksmingus technologinius procesus, pzv., vykdoma ekologiškai nekenksmingų ligandų paieška. Kaip alternatyva šiuo metu siūlomos dvi cheminių junginių klasės t.y. alditoliai (polihodroksiliai alkoholiai) ir hidroksikarboksirūgštys. Pagrindinis darbo tikslas: ištirti cheminio variavimo sistemas ir jose vykstančius procesus, vario(II) jonų ligandais naudojant ekologiškai nekenksmingas citrinų ir vyno rūgštis. Cheminio variavimo sistemose panaudoti du nauji Cu(II) jonų ligandai t.y. citrinų rūgštis ir vyno rūgšties D-izomeras. Atliktų tyrimų duomenys rodo, kad minėti ligandai sėkmingai gali būti naudojami cheminio variavimo sistemose, kur reduktoriumi naudojamas formaldehidas. Nustatyta, kad 2-hidroksipropan-1,2,3-trikarboksirūgštis (citrinų rūgštis) ir 2,3-dihidroksibutano-1,4-dirūgštis (vyno rūgštis) šarminėje terpėje sudaro pakankamai patvarius kompleksus su vario(II) jonais ir yra tinkamas ligandas vario(II) kompleksinimui šarminiuose (pH > 12) cheminio variavimo tirpaluose. Ištirta vario(II)-citrato ir Cu(II)-D-, L- ir DL-tartratų kompleksų redukcija hidratuotu formaldehidu, apibūdintos gautosios vario dangos. Optimaliomis proceso vykdymo sąlygomis... [toliau žr. visą tekstą]

The electro–mechanical connection between under bump metallization (UBM) and solder in flip–chip bonding is achieved by the formation of brittle intermetallic compounds (IMCs) during the soldering process. These IMCs continue to grow in the solid–state during storage at room temperature and service at an elevated temperature leading to degradation of the contacts. In this thesis, the diffusion–controlled growth mechanism of the phases and the formation of the Kirkendall voids at the interface of UBM (Cu, Ni, Au, Pd, Pt) and Sn (bulk/electroplated) are studied extensively. Based on the microstructural analysis in SEM and TEM, the presence of bifurcation of the Kirkendall marker plane, a very special phenomenon discovered recently, is found in the Cu–Sn system. The estimated diffusion coefficients at these marker planes indicate one of the reasons for the growth of the Kirkendall voids, which is one of the major reliability concerns in a microelectronic component. Systematic experiments using different purity of Cu are conducted to understand the effect of impurities on the growth of the Kirkendall voids. It is conclusively shown that increase in impurity enhances the growth of voids. The growth rates of the interdiffusion zone are found to be comparable in the Cu–Sn and the Ni–Sn systems. EPMA and TEM analyses indicate the growth of a metastable phase in the Ni–Sn system in the low temperature range. Following, the role of Ni addition in Cu on the growth of IMCs in the Cu–Sn system is studied based on the quantitative diffusion analysis. The analysis of thermodynamic driving forces, microstructure and crystal structure of Cu6Sn5 shed light on the atomic mechanism of diffusion. It does not change the crystal structure of phases; however, the microstructural evolution, the diffusion rates of components and the growth of the Kirkendall voids are strongly influenced in the presence of Ni. Considering microstructure of the product phases in various Cu/Sn and Cu(Ni)/Sn diffusion couples, it has been observed that (i) phases have smaller grains and nucleate repeatedly, when they grow from Cu or Cu(Ni) alloy, and (ii) the same phases have elongated grains, when they grow from another phase. A difference in growth rate of the phases is found in bulk and electroplated diffusion couples in the Au–Sn system. The is explained in AuSn4 based on the estimated tracer diffusion coefficients, homologous temperature of the experiments, grain size distribution and crystal structure of the phase. The growth rates of the phases in the Au–Sn system are compared with the Pd–Sn and the Pt–Sn systems. Similar to the Au–Sn system, the growth rate of the interdiffusion zone is found to be parabolic in the Pd–Sn system; however, it is linear in the Pt–Sn system. Following, the effect of addition of Au, Pd and Pt in Cu is studied on growth rate of the phases. An analysis on the formation of the Kirkendall voids indicates that the addition of Pd or Pt is deleterious to the structure compared to the addition of Au. This study indicates that formation of voids is equally influenced by the presence of inorganic as well as organic impurities.