Ruthenium, proposed as a new candidate of diffusion barrier, has three different kinds of oxides, which are native oxide, electrochemical reversible oxide and electrochemical irreversible oxide. Native oxide was formed by naturally exposed to air. Electrochemical reversible oxide was formed at lower anodic potential region, and irreversible oxides were formed at higher anodic potential region. In this study, we were focusing on the effect of copper electrodeposition on each type of oxides. From decreased charge of anodic stripping peaks and underpotential deposition (UPD) waves in cyclic voltammetry (CV), efficiency of Cu deposition dropped off indicating that interfacial binding strength between Cu and Ru oxides was weakened when the Ru surface was covered with irreversible oxide and native oxide. Also, Cu UPD was hindered by both O2 and H2 plasma modified Ru surfaces because the binding strength between Cu and Ru was weakened by O2 and H2 plasma treatment. Cu/Ru and Cu/Ta bimetallic corrosion was studied for understanding the corrosion behavior between diffusion barrier (Ta and Ru) and Cu interconnects under the post chemical mechanical planarization (CMP) process in semiconductor fabrication. Gallic acid is used in post CMP slurry solution and is known well as antioxidant which is supposed to oxidize itself to prevent other species from oxidizing. However, in this study under the observation of Cu microdot corrosion test, copper was corroded only in gallic acid at specific pH region of alkaline condition which is close to the pH region for post CMP solution formula. With different pH alkaline condition, gallic acid formed different oxidized products which are characterized by cyclic voltammetry and UV-Vis spectroscopy. Therefore, the specific oxidized product from particular pH region condition caused the Cu corrosion. Also, the corrosion rate of Cu microdots was influenced by substrate effect (Cu/Ru and Cu/Ta) and ambient control, which was included in this study.

<p>U ovom radu efikasnost odabranih derivata tiazola u inhibiciji korozije bakra u kiseloj<br />sulfatnoj sredini određena je u funkciji koncentracije inhibitora metodom merenja<br />gubitka mase, elektrohemijskom impedansnom spektroskopijom i potenciostatskom<br />polarizacijom. Polarizacionim merenjima takođe je određena zavisnost inhibitorske<br />efikasnosti od&nbsp; temperature i kinetički parametri procesa korozije bakra&nbsp; kao i&nbsp; model<br />adsorpcione izoterme prema kojem se odigrava proces adsorpcije&nbsp; inhibitora i&nbsp;odgovarajući termodinamički parametri. Merenjima kvarc kristalnom mikrovagom&nbsp;<em>in&nbsp;</em><br /><em>situ&nbsp; </em>je praćen proces elektrohemijskog rastvaranja bakra i adsorpcije ispitivanih<br />inhibitora. SEM/EDX analizom&nbsp; proučavana&nbsp; je promena morfologije bakarne povr&scaron;ine<br />usled dejstva korozione sredine i rastvora inhibitora.&nbsp; Rezultati eksperimentalnih<br />ispitivanja korelirani su&nbsp; sa teorijskim proračunima na nivou teorije funkcionala<br />gustine.</p> / <p>In this work, the efficiency of selected thiazole derivatives in&nbsp; the inhibition of corrosion of copper in the acidic sulfate solution is determined in&nbsp; the function ofthe inhibitors&nbsp; concentration by weight loss method,&nbsp; electrochemical impedance spectroscopy and potentiostatic polarization. The dependence of the inhibition efficiency of temperature and kinetic parameters of the process of corrosion ofcopper&nbsp; as well as&nbsp; adsorption isotherm model&nbsp; according to which takes place the process of adsorption of inhibitors and the corresponding thermodynamic parameters were also&nbsp; determined by polarization measurements.&nbsp; A process of electrochemical copper&nbsp; dissolution and&nbsp; adsorption of tested inhibitors is followedin situ&nbsp; by&nbsp; quartz crystal microbalance&nbsp; measurements Changes in the morphology of the copper surface due to the effects of corrosive environment and the solutions of the&nbsp; inhibitors were studied by SEM/EDX analysis.The experimental results were correlated with theoretical calculations at the density functional theory level.</p>

As multistep, multilayer processing in semiconductor industry becomes more complex, the role of cleaning solutions and etching chemistries are becoming important in enhancing yield and in reducing defects. This thesis demonstrates successful formulations that exhibit copper and tungsten compatibility, and are capable of Inter Layer Dielectric (ILD) cleaning and selective Ti etching. The corrosion behavior of electrochemically deposited copper thin films in deareated and non-dearated cleaning solution containing hydrofluoric acid (HF) has been investigated. Potentiodynamic polarization experiments were carried out to determine active, active-passive, passive, and transpassive regions. Corrosion rates were calculated from tafel slopes. ICP-MS and potentiodynamic methods yielded comparable Cu dissolution rates. Interestingly, the presence of hydrogen peroxide in the cleaning solution led to more than an order of magnitude suppression of copper dissolution rate. We ascribe this phenomenon to the formation of interfacial CuO which dissolves at slower rate in dilute HF. A kinetic scheme involving cathodic reduction of oxygen and anodic oxidation of Cu0 and Cu+1 is proposed. It was determined that the reaction order kinetics is first order with respect to both HF and oxygen concentrations. The learnings from copper corrosion studies were leveraged to develop a wet etch/clean formulation for selective titanium etching. The introduction of titanium hard-mask (HM) for dual damascene patterning of copper interconnects created a unique application in selective wet etch chemistry. A formulation that addresses the selectivity requirements was not available and was developed during the course of this dissertation. This chemical formulation selectively strips Ti HM film and removes post plasma etch polymer/residue while suppressing the etch rate of tungsten, copper, silicon oxide, silicon carbide, silicon nitride, and carbon doped silicon oxide. Ti etching selectivity exceeding three orders of magnitude was realized. Surprisingly, it exploits the use of HF, a chemical well known for its SiO2 etching ability, along with a silicon precursor to protect SiO2. The ability to selectively etch the Ti HM without impacting key transistor/interconnect components has enabled advanced process technology nodes of today and beyond. This environmentally friendly formulation is now employed in production of advanced high-performance microprocessors and produced in a 3000 gallon reactor.

Lead and copper in drinking water are known to pose aesthetic and health concerns for humans and pets. The United States Environmental Protection Agency (US EPA) Lead and Copper Rule (LCR) set 90th percentile action levels for lead (15 ppb) and copper (1.3 mg/L), above which utilities must implement systemwide corrosion control. However, gaps in the US EPA LCR leave at least 10% of residents using municipal water and all private well users vulnerable to elevated lead and copper in their drinking water. To help address these gaps in the LCR, this dissertation 1) Evaluates accuracy of at-home lead in water test kits to help residents identify lead problems, 2) Refines orthophosphate corrosion control guidance to help reduce cuprosolvency, 3) Identifies challenges to mitigating cuprosolvency by raising pH, and 4) Develops guidance that can help residents assess and address cuprosolvency problems. Lead in drinking water can pose a variety of health concerns, particularly for young children. The revised LCR will still leave many residents unprotected from elevated lead in their drinking water and potentially wondering what to do about it. Many consumers concerned about lead may choose to purchase at-home lead in water test kits, but there is no certification authority to ensure their accuracy. Most off-the-shelf tests purchased in this work (12 of 16) were not able to detect dissolved or particulate lead at levels of concern in drinking water (i.e. near the lead action level of 15 ppb) due to high detection limits (5,000-20,000 ppb). Binary type tests, which indicate the presence or absence of lead based on a trigger threshold of 15 ppb, were often effective at detecting dissolved lead, but they failed to detect the presence of leaded particles that often cause high lead exposures in drinking water problems. Some of these problems detecting particles could be reduced using simple at-home acid dissolution with weak household acids such a vinegar or lemon juice. Our analysis points out the strengths and weaknesses of various types of at-home lead in water tests, which could be particularly important considering potential distrust in official results in the aftermath of the Flint Water Crisis. Elevated cuprosolvency, or copper release into drinking water, can be an aesthetic concern due to fixture staining, blue water, and green hair and can pose health concerns for residents and pets. In addition to the general gaps in the LCR described above, compliance sampling in the LCR focuses on older homes at highest risk of elevated lead, rather than the newer homes at highest risk of elevated copper. Problems with elevated copper can sometimes go undetected as a result. Guidance was developed to help proactive utilities address cuprosolvency issues through the addition of orthophosphate corrosion inhibitors or pH adjustment as a function of a water's alkalinity. Linear regressions developed from pipe cuprosolvency tests (R2>0.98) determined a "minimum" orthophosphate dose or a "minimum" pH for a given alkalinity that was expected to almost always reduce copper below the 1.3 mg/L EPA action level in a reasonable length of time. The subjective nature of the terms "almost always" and "reasonable length of time" were quantitatively discussed based on laboratory and field data. Orthophosphate addition was generally very effective at cuprosolvency control. Orthophosphate treatment in copper tube cuprosolvency tests produced cuprosolvency below the action level within the first week of treatment. As expected, orthophosphate treated waters sometimes resulted in higher long-term cuprosolvency than the same waters without orthophosphate corrosion control treatment. This is consistent with the formation of phosphate scales which have an intermediate solubility between the cupric hydroxide in new pipes and the malachite or tenorite scales expected in pipe aging without orthophosphate. A linear regression (R2>0.98) was used to determine the orthophosphate dose needed for a given alkalinity to yield copper below the 1.3 mg/L action level in the pipe segments with the highest, 2nd highest, 3rd highest copper concentrations (100th, 95th, or 90th percentile, n=20 replicates, five each from four manufacturers) after 4 or 22 weeks of pipe aging. This regression was generally in good agreement with a bin approach put forth in the 2015 Consensus Statement from the National Drinking Water Advisory Council, but in some cases the regression predicted that higher orthophosphate doses would be needed. In contrast, due to the greater complexity of the reactions involved, a similar simplistic approach for pH adjustment is not widely applicable. A linear regression predicted that higher "minimum" pH values would be needed to control cuprosolvency compared to those suggested by the 2015 National Drinking Water Advisory Consensus Statement. Results indicate that factors such as the potential for calcite precipitation, pipe age, and significant variability in cuprosolvency from pipes of different manufacturers may warrant further research. Field LCR monitoring data indicated that 90th percentile copper concentrations continued to decline over a period of years or decades when orthophosphate is not used, and our laboratory results demonstrate a few cases where copper levels even increased with time. Consideration of confounding effects from other water quality parameters such as natural organic matter, silica, and sulfate would be necessary before the "minimum" pH criteria could be broadly applied. Guidance was then developed to help address cuprosolvency issues on a single building or single home basis for residents with private wells or those with high copper in municipal systems meeting the LCR. A hierarchy of costs and considerations for various interventions are discussed including replumbing with alternative materials, using bottled water or point use pitcher, tap, or reverse osmosis filters to reduce copper consumption, and using whole house interventions like more conventional orthophosphate addition and pH adjustment, or unproven strategies like granular activated carbon filtration, reverse osmosis treatment, and ion exchange treatment. Laboratory and citizen science testing demonstrated that some inexpensive at-home tests for pH and copper, were accurate enough to serve as inputs for this guidance and could empower consumers to diagnose their problems and consider possible solutions. Citizen science field testing and companion laboratory studies of potential interventions indicate that short-term (<36 weeks) use of pH adjustment, granular activated carbon, anion exchange and reverse osmosis treated water were not effective at forming a protective scale for the resident's water tested. In this case-study, cuprosolvency problems were ultimately related to water chemistry and linked to variability in influent water pH. Overall, this work highlighted weaknesses in the current US EPA Lead and Copper Rule. It attempted to close some of these gaps by assessing the accuracy of at-home citizen science tests for lead and copper detection and developing guidance to support voluntary interventions by utilities or consumers. Ideally, local authorities (utilities, health departments, cooperative extension programs) could adapt this guidance to account for local water quality considerations and support consumers in resolving cuprosolvency issues. This guidance may also serve as a citizen science approach that some consumers could use to make decisions on their own. Future work could extend and improve on these initial efforts. / Doctor of Philosophy / Lead or copper in drinking water can come from corrosion of plumbing materials. Elevated levels of these metals can cause aesthetic concerns like blue water and fixture staining, as well as health concerns for humans and pets. The United States Environmental Protection Agency (US EPA) Lead and Copper Rule (LCR) is designed to address system wide lead and copper corrosion problems in municipal water supplies. According to the LCR, utilities must notify consumers and implement corrosion control if more than 10% of homes sampled have lead above 15 ppb or copper above 1.3 mg/L. However, gaps in the US EPA LCR leave at least 10% of residents using municipal water and all private well users vulnerable to elevated lead and copper in their drinking water. To help address these gaps in the LCR, this dissertation 1) Evaluates how accurate residential at-home tests are at detecting lead in water, 2) Refines orthophosphate corrosion control guidance to help address elevated cuprosolvency (i.e. copper release to water), 3) Identifies challenges addressing cuprosolvency issues by raising the pH, and 4) Develops guidance to help residents detect and address cuprosolvency problems. Lead in drinking water can come from corrosion of lead bearing plumbing such as lead service lines and lead solder. Lead can pose a variety of health concerns, particularly for young children. In spite of recent revisions, the LCR will still leave many residents unprotected from elevated lead in their drinking water and potentially wondering what to do about it. Many consumers concerned about lead may choose to purchase at-home lead in water test kits, but there is no certification authority to ensure that they are accurate. Most off- the-shelf tests purchased in this work (12 of 16) were not able to detect dissolved lead or lead from particulate at concentrations expected to occur in drinking water due to high detection limits (5,000-20,000 ppb). Binary type tests, which indicate the presence or absence of lead based on a trigger threshold of 15 ppb, were often effective at detecting dissolved lead, but they failed to detect the presence of leaded particles that often cause high lead exposures in drinking water problems. Some of these problems detecting particles could be reduced using a simple procedure to attempt to dissolve the particles using weak household acids like vine- gar or lemon juice. Our analysis points out the strengths and weaknesses of various types of at-home lead in water tests, which could be particularly important considering potential distrust in official results in the aftermath of the Flint Water Crisis. Elevated cuprosolvency, or copper release into drinking water, primarily causes aesthetic problems like fixture staining and blue water, and it can also pose acute and serious health concerns for residents and some pets. Many of the same issues with the LCR that leave residents at risk of lead can also lead to unaddressed issues with elevated copper. In addition to those issues, the LCR focuses on collecting water samples in older homes at highest risk of lead, instead of newer homes at highest risk of copper. This means that many cuprosolvency problems could go undetected. Guidance was developed to help proactive utilities address cuprosolvency problems throughout the whole water system by adding orthophosphate corrosion inhibitors or adjusting the pH of their water. Linear relationships were developed from cuprosolvency testing in copper pipes (strong correlations, R2>0.98) to determine the "minimum" orthophosphate dose or pH value needed based on the water alkalinity that was expected to almost always reduce copper below the 1.3 mg/L EPA action level in a reason- able length of time. We also discuss the subjective nature of the terms "almost always" and "reasonable length of time" based on laboratory and field data. Adding orthophosphate was generally very effective at controlling cuprosolvency. In tests in copper pipe segments, copper concentrations in the water were below the action level within one week of starting to add orthophosphate. As expected, sometimes waters with orthophosphate treatment resulted in higher long-term copper concentrations than waters without orthophosphate. This is in agreement with reports of formation of phosphate mineral scales which have an intermediate solubility between those in new pipes and the scales expected in pipe aging without orthophosphate. A linear regression (strong correlation, R2>0.98) was used to determine the orthophosphate dose needed for a given alkalinity to yield copper below the 1.3 mg/L action level in the worst, second worst, and third worst pipes of the 20 pipe segments tested (100th, 95th, or 90th percentile) after 4 or 22 weeks of pipe aging. This linear relationship was generally in good agreement with a bin approach put forth in the 2015 Consensus Statement from the National Drinking Water Advisory Council, but in some cases the regression predicted that higher orthophosphate doses would be needed. In contrast, we showed that adjusting the pH to control cuprosolvency was too simplistic to be widely applicable because the chemical reactions involved are more complex. The linear relationship we developed predicted that higher "minimum" pH values would be needed to control cuprosolvency compared to those suggested by the 2015 National Drinking Water Advisory Consensus Statement. Other factors such as the potential calcite precipitation, which can clog pipes, pipe age, and significant variability in copper coming off pipes from different manufacturers may require consideration when considering treatment options. LCR monitoring data from utilities indicated that copper concentrations continued to decline over a period of years or decades when orthophosphate was not used, and our laboratory results demonstrate a few cases where copper levels even increased with time. We also showed that other water quality components like natural organic matter, silica, and sulfate can affect cuprosolvency and could make it difficult to broadly apply the "minimum" pH approach for controlling cuprosolvency in places with different water qualities. Guidance was then developed to help address cuprosolvency issues on a single building or single home basis for residents with private wells or those with high copper in municipal systems meeting the LCR. A hierarchy of costs and considerations is described for various interventions including replumbing with alternative materials, using bottled water or point use pitcher, tap, or reverse osmosis filters to reduce copper consumption, and using whole house interventions like more conventional orthophosphate addition and pH adjustment, or unproven strategies like granular activated carbon filtration, reverse osmosis treatment, and ion exchange treatment. Laboratory and citizen science testing demonstrated that some in- expensive at-home tests for pH and copper, were accurate enough to serve as inputs for this guidance and could empower consumers to diagnose their problems and consider possible solutions. Testing of potential water treatments in the laboratory and citizen science testing in a resident's home showed that short-term (<36 weeks) use of pH adjustment, granular activated carbon, anion exchange, and reverse osmosis treated water did not form a permanent, low-solubility protective scale for this resident's water. In this case-study, cuprosolvency problems were ultimately related to water chemistry and linked to variability in incoming pH of the water. This thesis highlighted weaknesses in the current US EPA Lead and Copper Rule. It at- tempted to address some of these issues by determining the accuracy of at-home citizen science tests to help residents detect lead and copper and developing guidance to support voluntary interventions by utilities or consumers. Ideally, local authorities (utilities, health departments, cooperative extension programs) could adapt this guidance to account for local water quality considerations and support consumers in resolving cuprosolvency issues. This guidance may also serve as a citizen science approach that some consumers could use to make decisions on their own. Future work could extend and improve on these initial efforts.

No description available.

The US Safe Drinking Water Act (SDWA), established in 1974, has improved water quality nationwide through the introduction of maximum contaminant levels, source water protection, and treatment guidelines and requirements. Despite the obvious success many important water quality issues are not covered by regulation. These include the following four topics in this dissertation: 1) Support infrastructure for private well users, 2) Identification and analysis of contaminants in private wells, 3) Leaks or corrosion within building plumbing, and 4) The role of citizen scientists in addressing water quality concerns. Private wells, which provide water for approximately 13% of the population (42.5 million people), are not subject to any federal regulation and well users are responsible for ensuring their own water safety. When water quality issues do arise, state or local organizations can provide critically important support. For instance, in North Carolina (NC) local health departments (LHDs) are required to have private well programs that enforce statewide well construction standards, offer water testing services, and provide well water outreach and assistance. Little is known about the effectiveness of such programs, however, so this work conducted a survey of all NC LHDs to determine their capacity for well water outreach and identify differences among programs around the state. All LHDs reported overseeing the construction of new wells as required by law. However, services provided to existing well users were offered infrequently and/or inconsistently offered. Lack of uniformity was observed in the number of LHD staff and their assigned responsibilities; the costs and availability of well water testing; and the comfort of LHD staff communicating with well owners. While the total number of staff was lower in LHDs in rural counties, the number of outreach activities and services offered was typically not related to the number of well users served. Variations in structure and capacity of well programs at LHDs has created unequal access to services and information for well users in NC. Such gaps in NC, which has among the most stringent state guidelines for well water support, suggests the need to examine conditions in other states nationwide. While direct support to private well users is more common at the state and local levels, the scientific information and resources needed by these officials can be supplemented at the federal level or through academia, especially with respect to emerging contaminants, which many officials may not yet have experience with. For instance, following Hurricane Florence in 2018, dam failures and flooding of coal ash disposal and reuse sites in NC prompted concerns about potential contamination of well water with hexavalent chromium. There is also widespread naturally occurring Cr(VI) in the groundwater however, and methods accessible to state and local officials to identify sources are needed. Literature was reviewed related to source tracking techniques and they were applied to Cr(VI) data we collected from 1,265 private wells across 22 NC counties. Almost two thirds of private wells tested (62.0%) exceeded the Cr(VI) public health goal of 0.07 ppb, with concentrations ranging from <0.02-13.9 ppb (median=0.12 ppb). In the literature review, we identified 33 Cr(VI) groundwater tracking techniques from 51 publications and only 5 techniques were used in more than 12 papers. All papers used different combinations of techniques. We applied these techniques to our well sampling data, and inconclusive results were reported for 7 techniques, while three techniques suggested potential geogenic sources whereas three techniques indicated anthropogenic Cr(VI) sources. Specifically looking at coal ash, two techniques did not support coal ash as a primary source and three were inconclusive. Overall, these techniques did not agree as to the origins of Cr(VI) in well water. This may be due to the fact that these techniques primarily focused on regional scale identification, rather than household-level occurrence. This study demonstrates the difficulty and complexity in identifying and distinguishing the source(s) responsible for Cr(VI) in well water. In addition to private wells, another gap in the SDWA framework involves corrosion of plumbing within a home or private building. The Lead and Copper Rule (LCR) was the first SDWA legislation to include sampling at the tap in private buildings, although these results are only used to inform control of the corrosivity of the water at the treatment plant. Thus, there is no maximum level of lead or copper enforced at the consumers tap, and protection against excessive private plumbing corrosion is not required. A survey conducted about a decade ago suggested that recent efforts to increase temperatures of hot water systems to better control Legionella bacteria might also be increasing pinhole leaks in copper plumbing. Recently, an overseas large building experienced at least 300 pinhole leaks in a hot water recirculation system that frequently exceeded > 65°C in 2018. The occurrence of leaks along the top of the pipes where thick deposited of metal oxides were not visibly protective, was not consistent with conventional patterns of failure, but seemed to be a manifestation of an unusual type of hot water pitting due to the presence of cathodic iron or manganese oxide suggested in prior literature. A macro-cell apparatus was developed and tested to mechanistically test this novel hot water pitting corrosion mechanism experimentally. Cathodic manganese oxides deposits were shown to drive pitting corrosion on a part of the pipe surface without deposits. Pitting occurred over a wide range of pH and was worst at a high ratio of sulfate to bicarbonate. While iron oxide coatings tested in this work did not behave cathodically, as suggested in prior literature, further research could determine if some iron oxides might behave similarly to the manganese oxide tested in this work. Past failures to follow provisions of the SDWA has undermined trust in water safety nationally. Collaborations between citizens and scientists can sometimes expose problems with water safety. Over the last decade we have helped consumers evaluated their concerns using citizen science collaborative approaches. We documented and summarized several case studies conducted by the U.S. Water Study team at Virginia Tech that had varying degrees of success in exposing problems with water supplies via citizen science collaborations. The case studies start with a discussion of work in Flint, MI (lead and Legionella bacteria) in 2015 and St. Joseph, LA in 2016 (lead and iron). Later cases included: Enterprise, LA (lead and iron), Denmark, SC (lead, iron, and Halosan), Chicago, IL (lead), Moore, OK (arsenic), Santa Barbara, CA (copper), anonymous town in SC (Acanthamoeba), and Harrisonburg, VA (Legionella). Approaches, challenges and outcomes of each case study are reviewed along with lessons learned. Overall, this dissertation explored water quality issues which, for various reasons, fall outside of the existing SDWA regulatory framework. The importance of well water support was emphasized by documenting inequalities between local health departments well services and by critically reviewing literature to find a lack of scientific guidance for source determination for an important emerging contaminant. Development of a novel apparatus for monitoring of chemistry related hot water pitting allows for a better understanding of this mechanism and provides a baseline of guidance for avoiding or mitigating such problems in the future. Finally, the use of citizen science to address past water quality concerns and that considers reasonable expectations for future work was evaluated. / Doctor of Philosophy / In the United States, drinking water is usually collected and treated by a local drinking water treatment plant before being sent out to all customers within a city or community. Since the 1970's, the US Environmental Protection Agency (EPA) has regulated treatment plants to make sure they do not send out water that could be potentially dangerous to the health of those drinking, cooking, or bathing with it. These EPA regulations have helped deliver cleaner and cleaner water across the country, but they do not protect every aspect of drinking water for every person in the US. This dissertation covers four topics that EPA regulations do not cover including: 1) Support systems for people getting their water from private wells, 2) Understanding dangers to safe water in unregulated private wells, 3) Leaks in plumbing within a building, and 4) The role of citizens working closely with scientists to determine if their water is safe. More than 1 in 10 people in the US get their drinking water from private wells, and EPA regulations do not protect the safety of that water. Instead, consumers are on their own to make sure it is safe to drink. When water that could be dangerous is discovered, state or local governments are important sources where residents can get help in treating it. For instance, in North Carolina (NC), local county health departments are required to have programs focused on private wells. The goals of these programs are to make sure new wells are built according to legal codes, offer to test well water for residents, and answer questions people have about their well water. No one has ever determined how well how well health departments meet these goals. This work sent a survey to each health department in NC to figure out how much each was doing and identify any differences between counties. All health departments were checking new wells to make sure they were installed according to state law. But all health departments did not provide support or answer questions of people who had older wells. Some of the differences were due to the number of staff working on these problems, costs charged for well water testing, and the confidence with which staff answered well water questions. Well users in different NC counties get a different level of service as a result. The fact that these differences exist in NC, a state believed among the best in supporting private well owners, suggests a need for a similar analysis in other states. Local health departments and state agencies are more likely to work directly with people concerned about their well water. College or federal government researchers can still help support these groups. Extra support is important when contaminants that state or local officials haven't experienced before become concerning. In one example, after Hurricane Florence in NC in 2018, sites where coal power plants had been throwing away their coal ash became flooded, and coal ash was introduced into floodwaters. Coal ash has been known to contain Cr(VI), which can is believed to increase chances of cancer if consumed in drinking water. Cr(VI) also occurs naturally, when it is leached from rocks in groundwater. Figuring out where Cr(VI) found in a private well is from is difficult. To determine methods of figuring out the sources of Cr(VI) we reviewed scientific literature and documented the methods that had been used before to determine Cr(VI) sources. Then, we conducted a sampling campaign across the state, and sampled 1,265 private wells from 22 different NC counties. Cr(VI) was found in many of the wells we tested, and nearly 2/3 had Cr(VI) above the level established by the NC state government as a potential health concern. From previous literature, we reviewed 51 papers and found 33 methods that had been used to determine the source of Cr(VI) in groundwater. Only five of these methods were used by more than 12 papers and while many papers used more than one method, no papers used the same grouping of methods. When we used the methods from the literature to see how the results compared between methods, they did not all agree. Three said that Cr(VI) was coming from natural sources, three indicated it came from industry, and seven made no prediction. Overall, this study shows how difficult it can be to find out the source of Cr(VI) that occurs in private wells. Leaks in copper plumbing inside of a home or building are also not covered at all by EPA laws. The Lead and Copper Rule (LCR), passed in 1991, does include testing the water coming out of peoples' faucets for copper. But those testing results are only used to make changes at the water treatment plant to make the water less corrosive. Over the last 10-20 years, scientists have become worried that pipes may be at risk of forming more leaks, when higher hot water temperatures are used to prevent the growth of dangerous bacteria that can grow in plumbing. In one large building outside the US, at least 300 leaks were found in hot water pipes, costing large amounts of money to fix. In the past, most leaks like this were at the bottom of pipes, under settled particles with iron and manganese oxides in them. In this building though, leaks were at the top of pipes, where there was no deposit, which was very surprising. One reason for this could have been a type of reaction from past studies where iron or manganese coatings cause a reaction which forms leaks in nearby copper pipe. No experiments have ever proven this reaction though. Our study made a lab setup to learn more about this reaction and proved that it is possible and was due to manganese oxide. We found the most corrosion occurred in water with high pH and high levels of sulfate. Iron oxide particles did not cause the reaction in our study, but it is possible that other types of iron oxide could still have a role in making the reaction happen. Past examples of cities or towns not following EPA rules has caused distrust in public drinking water. Citizens and scientists working closely together have sometimes been able to find out about such problems and get them fixed. Over the last 10 years, we have helped people learn more about their water concerns by working with them to take and analyze water tests. We documented a number of those cases which had different levels of success. The first case we talk about is Flint, MI in 2015, then St. Joseph, LA in 2016. Later cases include cities in Louisiana, South Carolina, Illinois, Oklahoma, California, and Virginia, with a number of different water risks. The first two cases caused drastic and quick changes to water safety and drinking water emergencies were declared. But after that the response was less urgent. If scientists want to pursue work with citizens who have concerns, they will need to be ready for keep working on it for a long time, and face disagreement from agencies and government groups who provide the water. Overall, this work tried to help people, who were not being protected by government rules, or who felt that they were being harmed by governments or companies who were breaking the rules. Many of these problems make people worried about their water, or create worries that are not necessary, or cost consumers a lot of money. More work is needed to address this type of problem.

Copper (Cu) electrodeposition on ruthenium (Ru) oxides was studied due to important implications in semiconductor industry. Ruthenium, proposed as the copper diffusion barrier/liner material, has higher oxygen affinity to form different oxides. Three different oxides (the native oxide, reversible oxide, and irreversible oxide) were studied. Native oxide can be formed on exposing Ru in atmosphere. The reversible and irreversible oxides can be formed by applying electrochemical potential. Investigation of Cu under potential deposition on these oxides indicates the similarity between native and reversible oxides by its nature of inhibiting Cu deposition. Irreversible oxide formed on Ru surface is rather conductive and interfacial binding between Cu and Ru is greatly enhanced. After deposition, bimetallic corrosion of Cu/Ru in different polyphenols was studied. Polyphenols are widely used as antioxidants in post chemical mechanical planarization (CMP). For this purpose, different trihydroxyl substituted benzenes were used as antioxidants. Ru, with its noble nature enhances bimetallic corrosion of Cu. Gallic acid (3,4,5 - trihydroxybenzoic acid) was chosen as model compound. A mechanism has been proposed and validity of the mechanism was checked with other antioxidants. Results show that understanding the chemical structure of antioxidants is necessary during its course of reaction with Cu.

The present diploma thesis concerns the research of plasmachemical reduction of copper corrosion layers. The process was based on using low pressure hydrogen RF plasma in which copper samples are treated for several hours. Four series of copper corrosion layers were prepared in four different corrosion atmospheres. The first two were prepared using saturated vapors of HCl and ammonium acetate that affected copper samples for one week. The second two sets were prepared by samples dipping in HNO3 and H2SO4. EDX analysis confirms visual composition of corrosion layers – chlorides, nitrides and sulphate, respectively. The ammonium acetate produced no corrosion layers and thus this set of samples was omitted. The optical emission spectroscopy was used to find out reactions in a hydrogen RF discharge. At the first, a character of plasma without samples was taken by measuring in continuous and pulsed regime. The integral spectrum intensity (300-700 nm) and intensities of hydrogen atomic lines were observed in the dependences on hydrogen flow, power and duty cycle. After that copper samples were treaded under various conditions in continual and pulse regime, typically at pressure of 170 Pa, 200 W power and hydrogen flow rate of 10.2 ml/min. The integral OH radical spectral intensity in the range of 305 – 330 nm was used as a monitor of plasma treatment process. The experimental results showed that intensities of OH radical depended strongly on the corrosion layer kind as well as on the RF discharge mode. Reduction of corrosion layers treated in the pulsed regime was not so satisfactory then in the continuous regime probably due to lower temperature of sample during the treatment. The total supplied energy into the system was also lower in this case. The sample sputtering was observed during the reduction in continuous regime. It means the corrosion was successfully removed but the process was not stopped at that moment, so it is necessary to propose another additional monitoring process besides observing OH radicals. Our experimental results are the first step in the spread research of plasmachemical treatment of copper made archaeological artifacts.

Orientador: David Mendez Soares / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-06T09:05:00Z (GMT). No. of bitstreams: 1 Pinto_EdilsonMoura_M.pdf: 2421703 bytes, checksum: 4f88cfbf1bf972bc5ed1991a06982550 (MD5) Previous issue date: 2004 / Resumo: Neste trabalho, a QCM (Quartz Crystal Microbalan e) Microbalança de Cristal de Quartzo, como ténica alternativa para o estudo da corrosão /inibição do metal cobre. Estudamos a proteção anti-corrosão de superfícies de cobre mediante a adsorção de inibidores voláteis de corrosão (VCI-CHAB,Ciclohexilamina-Benzoato). Utilizamos uma QCM, composta de um cristal de quartzo de 6MHz, recoberto por um filme de ouro depositado por sputtering. Utilizamos Técnicas eletroquímicas para caracterizar a corrosão. Para isto, estudamos a corrosão do metal cobre em diferentes ambientes, básicos e ácidos, na presença e ausência dos inibidores. Aplicamos a QCM acoplada à um potenciostato (EQCM), como método de determinação de variação de massa e e carga de correntes da corrosão/inibição. A presença dos filmes VC I sobre a superfície de cobre, também foi demonstrada pela técnica Reflection-Absorption Infra-Red Spectros opy (RAIRS), através da Micros copia de infravermelho razante, esta técnica é indicada para situações em que os filmes formados são Ultra-finos. Baseado nos resultados das medidas feitas, propomos e des revemos um modelo para a dsorção dos filmes VCI sobre a superfície metálica, incluindo a formação da corrosão por pitting / Abstract: In this work we used the QCM (Quartz Crystal Microbalance) as an alternative technique for the studying of the corrosion/inhibition of cooper. We studied the protection of cooper surfaces due to the adsorption of a volatile corrosion inhibitor, (VCI-Cyclehexilamine-Benzoate). We used electrochemical techniques to characterize the corrosion in different environments. We applied the QCM together with the potentiostat as a method of determination of charge and mass variations. In this work the QCM has been used as a complementary technique for investigating the corrosion of copper with and without adsorbed inhibitors. The protection of copper surfaces due to the adsorption of a volatile corrosion inhibitor (VCI) ¿ Cyclohexylamine Benzoate ¿ has been studied by electro chemical techniques to characterise the corrosion in aqueous environments over a wide range of pH values. The presence of VCI films on the copper surface was also shown by Reflection-Absorption Infra-Red Spectroscopy (RAIRS), a technique indicated for situations when very thin films are formed. The EQCM, which used 6 MHz gold-sputtered quartz crystals coated with electrodeposited copper films, was applied to the simultaneous determination of the charge and frequency variations associated with the corrosion process, with and without adsorbed inhibitor. Based on the measurements, a model has been developed to describe the dynamics of adsorption of the VCI on the metalli surface, including the formation of pits on the surface / Mestrado / Superfícies e Interfaces ; Peliculas e Filamentos / Mestre em Física

To form Cu interconnects, dual-damascene techniques like chemical mechanical planarization (CMP) and post-CMP became inevitable for removing the "overburden" Cu and for planarizing the wafer surface. During the CMP processing, Cu interconnects and barrier metal layers experience different electrochemical interactions depending on the slurry composition, pH, and ohmic contact with adjacent metal layers that would set corrosion process. Ruthenium as a replacement of existing diffusion barrier layer will require extensive investigation to eliminate or control the corrosion process during CMP and post CMP. Bimetallic corrosion process was investigated in the ammonium citrate (a complexing agent of Cu in CMP solutions) using micro test patterns and potentiodynamic measurements. The enhanced bimetallic corrosion of copper observed is due to noble behavior of the ruthenium metal. Cu formed Cu(II)-amine and Cu(II)-citrate complexes in alkaline and acidic solutions and a corrosion mechanism has been proposed. The currently used metallization process (PVD, CVD and ALD) require ultra-high vacuum and are expensive. A novel method of Si surface metallization process is discussed that can be achieved at room temperature and does not require ultra-high vacuum. Ruthenation of Si surface through strong Si-Ru covalent bond formation is demonstrated using different ruthenium carbonyl compounds. RBS analysis accounted for monolayer to sub-monolayer coverage of Si surface. Interaction of other metal carbonyl (like Fe, Re, and Rh) is also discussed. The silicon (111) surface modifications with vinyl terminated organic compounds were investigated to form self-assembled monolayers (SAMs) and there after these surfaces were further functionalized. Acrylonitrile and vinylbenzophenone were employed for these studies. Ketone group of vinylbenzophenone anchored to Si surface demonstrated reactivity with reducing and oxidizing agents.