by Chan To = 電鍍錫在銅質底材上晶鬚生長的硏究 / 陳濤. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2001. / Includes bibliographical references. / Text in English; abstracts in English and Chinese. / by Chan To = Dian du xi zai tong zhi di cai shang jing xu sheng chang de yan jiu / Chen Tao. / Abstract --- p.i / 論文摘要 --- p.ii / Acknowledgements --- p.iii / Table of Content --- p.v / Chapter Chapter 1 --- INTRODUCTION / Chapter 1.1 --- Lead-free movement and the problem of whisker --- p.1-1 / Chapter 1.2 --- Properties of tin and tin-copper intermetallics --- p.1-2 / Chapter ´Ø --- Tin --- p.1-2 / Chapter ´Ø --- Tin-copper intermetallics --- p.1-2 / Chapter 1.3 --- Literature Review of Whisker --- p.1-4 / Chapter 1.3.1 --- Feature of the whisker --- p.1-4 / Chapter 1.3.2 --- Conditions prone to whisker growth --- p.1-8 / Chapter 1.3.3 --- Growth mechanism of the whisker --- p.1-10 / Chapter 1.3.4 --- Methods to prevent or remove whisker --- p.1-11 / Chapter 1.4 --- Motivation & Aims of Studies --- p.1-12 / Chapter Chapter 2 --- EXPERIMENTAL & INSTRUMENTATION / Chapter 2.1 --- Sample Preparation --- p.2-1 / Chapter ´Ø --- Electroplating process --- p.2-1 / Chapter 2.2 --- Instrumentation --- p.2-6 / Chapter 2.2.1 --- Scanning Auger Microscope (SAM) analysis --- p.2-6 / Chapter ´Ø --- Experimental conditions --- p.2-9 / Chapter ´Ø --- Sample preparation for Auger analysis --- p.2-10 / Chapter ´Ø --- Depth profile analysis --- p.2-11 / Chapter ´Ø --- Mapping --- p.2-11 / Chapter ´Ø --- Line scan --- p.2-12 / Chapter 2.2.2 --- X-ray diffractometer (XRD) --- p.2-12 / Chapter 2.2.3 --- Scanning Electron Microscope (SEM) --- p.2-13 / Chapter Chapter 3 --- INFLUENCE OF CATHODIC/ANODIC ELECTROCHEMICAL CLEANING ON THE WHISKER GROWTH / Chapter 3.1 --- Introduction --- p.3-1 / Chapter 3.2 --- Theory --- p.3-2 / Chapter ´Ø --- Reactions occurring at the anode/cathode --- p.3-3 / Chapter 3.3 --- Sample description --- p.3-5 / Chapter 3.4 --- Results and discussion --- p.3-5 / Chapter ´Ø --- Surface morphology before electroplating --- p.3-5 / Chapter ´Ø --- Whisker observation --- p.3-7 / Chapter 3.5 --- Summary --- p.3-18 / Chapter Chapter 4 --- INFLUENCE OF COPPER CONCENTRATION IN THE PLATING BATH ON COPPER DIFFUSION AND WHISKER FORMATION / Chapter 4.1 --- Introduction --- p.4-1 / Chapter 4.2 --- Theory and Literature Review --- p.4-2 / Chapter ´Ø --- Diffusion kinetic --- p.4-2 / Chapter ´Ø --- Influence of solute atoms --- p.4-5 / Chapter 4.3 --- Sample description --- p.4-6 / Chapter 4.4 --- Results and discussion --- p.4-6 / Chapter ´Ø --- SEM observations --- p.4-6 / Chapter ´Ø --- Cross-sectional analysis --- p.4-8 / Chapter ´Ø --- Surface and depth profile analysis --- p.4-15 / Chapter ´Ø --- XRD analysis --- p.4-21 / Chapter 4.5 --- Summary --- p.4_24 / Chapter Chapter 5 --- ANNEALING EFFECT ON THE WHISKER GROWTH / Chapter 5.1 --- Introduction --- p.5-1 / Chapter 5.2 --- Theory and Literature Review --- p.5-2 / Chapter 5.3 --- Sample description --- p.5-3 / Chapter 5.4 --- Results and discussion --- p.5-4 / Chapter ´Ø --- SEM whisker observation --- p.5-4 / Chapter ´Ø --- Cross-sectional Auger analysis --- p.5-4 / Chapter ´Ø --- Surface and depth profile analysis --- p.5-16 / Chapter 5.5 --- Summary --- p.5-27 / Chapter Chapter 6 --- FORMATION MECHANISM OF THE STRIATION ON WHISKER / Chapter 6.1 --- Introduction --- p.6-1 / Chapter 6.2 --- Results and discussion --- p.6-2 / Chapter ´Ø --- Texture of the striation --- p.6-2 / Chapter ´Ø --- Time evolution in the surface morphology --- p.6-6 / Chapter ´Ø --- Stage of whisker growth --- p.6-6 / Chapter 6.3 --- Summary --- p.6-12 / Chapter Chapter 7 --- CONCLUSIONS & FUTURE STUDIES / Chapter 7.1 --- Conclusions --- p.7-1 / Chapter 7.2 --- Future studies --- p.7-3 / Reference

The Semiconductor Industry Association (SIA) has identified the integration of copper (Cu) with low-dielectric-constant (low-k) materials as a critical goal for future interconnect architectures. A fundamental understanding of the chemical interaction of Cu with various substrates, including diffusion barriers and adhesion promoters, is essential to achieve this goal. The objective of this research is to develop novel organic polymers as Cu/low-k interfacial layers and to investigate popular barrier candidates, such as clean and modified tantalum (Ta) substrates. Carbon-silicon (C-Si) polymeric films have been formed by electron beam bombardment or ultraviolet (UV) radiation of molecularly adsorbed vinyl silane precursors on metal substrates under ultra-high vacuum (UHV) conditions. Temperature programmed desorption (TPD) studies show that polymerization is via the vinyl groups, while Auger electron spectroscopy (AES) results show that the polymerized films have compositions similar to the precursors. Films derived from vinyltrimethyl silane (VTMS) are adherent and stable on Ta substrates until 1100 K. Diffusion of deposited Cu overlayers is not observed below 800 K, with dewetting occurred only above 400 K. Hexafluorobenzene moieties can also be incorporated into the growing film with good thermal stability. Studies on the Ta substrates demonstrate that even sub-monolayer coverages of oxygen or carbide on polycrystalline Ta significantly degrade the strength of Cu/Ta chemical interactions, and affect the kinetics of Cu diffusion into bulk Ta. On clean Ta, monolayer coverages of Cu will de-wet only above 600 K. A partial monolayer of adsorbed oxygen (3L O2 at 300 K) results in a lowering of the de-wetting temperature to 500 K, while saturation oxygen coverage (10 L O2, 300 K) results in de-wetting at 300 K. Carbide formation also lowers the de-wetting temperature to 300 K. Diffusion of Cu into the Ta substrate at 1100 K occurs only after a 5-minute induction period. This induction period increases to 10 min for partially oxidized Ta, 15 min for carbidic Ta and 20 min for fully oxidized Ta.

Future copper interconnect systems will require replacement of the materials that currently comprise both the liner layer(s) and the capping layer. Ruthenium has previously been considered as a material that could function as a single material liner, however its poor ability to prevent copper diffusion makes it incompatible with liner requirements. A recently described chemical vapor deposition route to amorphous ruthenium-phosphorus alloy films could correct this problem by eliminating the grain boundaries found in pure ruthenium films. Bias-temperature stressing of capacitor structures using 5 nm ruthenium-phosphorus film as a barrier to copper diffusion and analysis of the times-to-failure at accelerated temperature and field conditions implies that ruthenium-phosphorus performs acceptably as a diffusion barrier for temperatures above 165 °C. The future problems associated with the copper capping layer are primarily due to the poor adhesion between copper and the current Si-based capping layers. Cobalt, which adheres well to copper, has been widely proposed to replace the Si-based materials, but its ability to prevent copper diffusion must be improved if it is to be successfully implemented in the interconnect. Using a dual-source chemistry of dicobaltoctacarbonyl and trimethylphosphine at temperatures from 250-350 °C, amorphous cobalt-phosphorus can be deposited by chemical vapor deposition. The films contain elemental cobalt and phosphorus, plus some carbon impurity, which is incorporated in the film as both graphitic and carbidic (bonded to cobalt) carbon. When deposited on copper, the adhesion between the two materials remains strong despite the presence of phosphorus and carbon at the interface, but the selectivity for growth on copper compared to silicon dioxide is poor and must be improved prior to consideration for application in interconnect systems. A single molecule precursor containing both cobalt and phosphorus atoms, tetrakis(trimethylphosphine)cobalt(0), yields cobalt-phosphorus films without any co-reactant. However, the molecule does not contain sufficient amounts of amorphizing agents to fully eliminate grain boundaries, and the resulting film is nanocrystalline. / text

abstract: Programmable Metallization Cell (PMC) devices are, in essence, redox-based solid-state resistive switching devices that rely on ion transport through a solid electrolyte (SE) layer from anode to cathode. Analysis and modeling of the effect of different fabrication and processing parameter/conditions on PMC devices are crucial for future electronics. Furthermore, this work is even more significant for devices utilizing back-end- of-line (BEOL) compatible materials such as Cu, W, their oxides and SiOx as these devices offer cost effectiveness thanks to their inherent foundry-ready nature. In this dissertation, effect of annealing conditions and cathode material on the performance of Cu-SiOx vertical devices is investigated which shows that W-based devices have much lower forming voltage and initial resistance values. Also, higher annealing temperatures first lead to an increase in forming voltage from 400 °C to 500 °C, then a drastic decrease at 550 °C due to Cu island formation at the Cu/SiOx interface. Next, the characterization and modeling of the bilayer Cu2O/Cu-WO3 obtained by annealing the deposited Cu/WO3 stacks in air at BEOL-compatible temperatures is presented that display unique characteristics for lateral PMC devices. First, thin film oxidation kinetics of Cu is studied which show a parabolic relationship with annealing time and an activation energy of 0.70 eV. Grown Cu2O shows a cauliflower-like morphology where feature size on the surface increase with annealing time and temperature. Then, diffusion kinetics of Cu in WO3 is examined where the activation energy of diffusion of Cu into WO3 is calculated to be 0.74 eV. Cu was found to form clusters in the WO3 host which was revealed by imaging. Moreover, using the oxidation and diffusion analyses, a Matlab model is established for modeling the bilayer for process and annealing-condition optimization. The model is built to produce the resulting Cu2O thickness and Cu concentration in Cu-WO3. Additionally, material characterization, preliminary electrical results along with modeling of lateral PMC devices utilizing the bilayer is also demonstrated. By tuning the process parameters such as deposited Cu thickness and annealing conditions, a low-resistive Cu2O layer was achieved which dramatically enhanced the electrodeposition growth rate for lateral PMC devices. / Dissertation/Thesis / Doctoral Dissertation Electrical Engineering 2020

One main reason for the use of Fe-Cu-C system in PM industry is the presence of liquid phase (copper) at the start of sintering (1120oC). The diffusion of liquid copper into iron causes swelling in the structure. This in turn can cause high dimensional change and, if not controlled properly, may cause distortion. So it is of paramount importance to control the copper diffusion. Carbon, added as graphite, reduces the swelling of copper by changing the dihedral angle. The affect of graphite on copper diffusion depends on the graphite type, particle size of graphite and heating rate. The aim of this work was to find the influence of graphite type and particle size of graphite on copper diffusion. Water Atomized iron (ASC100.29) produced in Höganäs AB was taken as the base powder.  Two types of graphite were used each with two different particle sizes. Two different graphite quantities (0.2% & 0.8%) for each type was taken. Natural fine graphite (UF4), Natural coarse graphite (PG44), Synthetic fine graphite (F10) and  Synthetic coarse graphite (KS44) were the graphites used in this work. Powders were compacted at 600 Mpa and the sintering was done at 1120oC for 30 minutes in 90/10 N2/H2. Dilatometry and metallographic investigation of the samples sintered in the production furnace were used to understand the graphite influence.   The investigation showed that at low graphite levels (0.2%), the affect of graphite type or graphite size was not significant on copper diffusion. At high graphite levels (0.8%),  synthetic graphites were more effective in reducing the swelling of copper. Influence of  particle size of synthetic graphites on Cu diffusion was not significant compared to the influence of particle size of natural graphite. There was also a considerable affect of heating rate on graphite dissolution and copper swelling.