Using a Hazard and Operability Study (HAZOP) to Evaluate a Copper Waste Treatment System Shree Dharasker and Joan

Ning, Applied Materials 3135 Kifer Road, M/S 2763,Santa Clara, California 95054

Abstract Applied Materials (AMAT), the worlds largest manufacturer of wafer processing equipment, announced the opening of a new Equipment and Process Integration Center (EPIC) in 1998. The center houses several new products, including all the technologies needed for making the copper interconnect (Barrier/Seed Copper deposition, dielectric deposition, chemical mechanical polishing, and electroplating of Copper). EPIC operations therefore generate a significant amount of copper waste that must be addressed via treatment. Due to a low, local discharge limit for Copper (0.4 mg/l), a specific copper treatment system was needed to remove copper from the waste stream. Working together, Applied Materials Facilities, Environmental, and Lab Operations designed and built a Copper Waste Treatment System (CWTS) to effectively treat and minimize this waste stream. The CWTS contains several unit operations that were new to Applied Materials and local regulatory agencies. To evaluate and accept the new treatment system, the design team conducted a Hazard and Operability Study (HAZOP). The HAZOP provided an overall system review that enabled AMAT to thoroughly understand, operate, and permit this system. This paper will describe the final CTWS solution, the HAZOP process used, and they key benefits of conducting this study. With the increasing importance of Copper in semiconductor device structures, this paper will emphasize practical solutions for addressing aqueous copper waste streams. Introduction: As device performance increases, line widths on semiconductors continue to shrink. This has created problems for aluminum conductors that are currently used on devices. At the 0.18 micron level, aluminum conductors experience increased signal delays, reliability and heat generation, all of which can damage the device. It is widely expected that copper will be the metal of choice for 0.18 micron devices and beyond. Copper has several advantages over aluminum including a higher melting point (1083 0 C), low resistivity (1.77 umho/cm), and high electromagnetic resistance. Along with the process advantages, copper also has significant disadvantages such as a low etch rate, high diffusivity into Silicon, and greater environmental impact. As a result of copper processing, there are

new wastes generated which often need special treatment that is not commonly found at Semiconductor Fabrications Facilities. Copper Processing and Waste Treatment at Applied Materials In 1998, Applied Materials announced the opening of a new Equipment and Process Integration Center (EPIC). The center had several tools and modules, including all the technologies required to develop the copper interconnect. EPIC would be used to demonstrate the capability of Applied Materials equipment to build a copper-based semiconductor. Copper processes at EPIC are based on the Copper Dual-Damascene Process which included the following processes: barrier layer deposition using PVD/IMP Copper Seed layer deposition using Copper CVD Copper Electroplating to fill the interconnect Copper CMP used to flatten the oxide layer

Operation of these processes resulted in several new waste streams that were to be handled by the facility. These included, particulate air emissions from the Copper CVD and PVD processes, dilute rinsewaters with low copper concentration, concentrated copper sulfate solutions from the electroplating processes, copper slurry wastes from CMP processes, and miscellaneous contaminated solid wastes from maintenance activities. Based on the regulatory requirements and design considerations, separate treatment technologies were selected for each of the waste streams. To remove particulate copper air emissions, hot and cold traps are used in pre and post pump lines. The traps remove particulate air emissions from liquid precursors that are used to deposit copper liners on the wafer substrate. While eliminating air emissions, the traps also protect the pump from particulate damage. For dilute copper wastewater, generated by wafer rinsing, an ionexchange system was designed to remove copper from the waste stream. To treat concentrated copper waste such as that generated by electroplating processes, a traditional precipitation/filtration/evaporation system was designed to reduce waste. CMP slurry is pumped to an ultrafiltration unit to remove solids and then fed to the Ion exchange system for copper removal. Figure 1 is a flow chart of the Copper treatment system. Effluent from the ion exchange system is pumped to the Acid Waste Neutralization (AWN) System for treatment and discharge to the City POTW. Solid waste generated from filtration and evaporation activities are characterized and disposed of at approved disposal sites. Table 1 summarizes the waste streams generated and the treatment technologies used. Due to the low waste discharge limit for Copper (0.4 mg/l), it was important that the Copper Treatment System operate efficiently, and contain several checks and balances to ensure that there was no release to the sanitary sewer that

could result in notices of violations and penalties. In addition, due to the complex nature of the copper treatment system, it was important to ensure that operations, facilities and environmental personnel fully understood system operations. The design team therefore decided that a detailed review was necessary to fully understand system operations and checks and balances required to maintain compliance with the requirements. Hazard and Operability Studies: Hazard and Operability Studies (Hazops) are recommended by the American Institute of Chemical Engineers (1) to evaluate the risk associated with automated and semi-automated processes. There are a number of recommended techniques for evaluating hazards such as, What- if analysis, Process Checklists, Preliminary Hazard Analysis, and the Hazops guide word method. A Hazops study identifies hazards and operability problems. It involves investigating how a plant or treatment system might deviate from design intent. Solutions to these deviations are discussed and noted if appropriate. A Hazops is based on the principle that several experts with different backgrounds can interact and identify more problems when working together than when working separately and combining results, as in a typical design review. In most new facilities, the project engineers and architects generate design drawings that are then reviewed in parallel or in sequence by environmental, safety, industrial hygiene, maintenance and operations personnel. In a Hazops study, the design drawings are reviewed by key personnel together, greatly enhancing the effectiveness of the design review. The Hazops is conducted in a series of meetings where a multidisciplinary team methodically brainstorms the plant design, following the structure provided by the guide words and team leaders experience. The primary advantage of this brainstorming is that it stimulates creativity and generates ideas. Participation is the key to a successful Hazops, (quantity breeds quality), and team members must refrain from criticizing each other in the meetings. The Hazops team focuses on specific points in the design (called study nodes), one at a time. At each study node deviations in the process parameters are examined using guide words. The guide words are used to ensure that the design is explored in every conceivable way. The task of the team is to think about each node and what possible deviations can occur, so that their potential causes and consequences can be identified. The best time to conduct a Hazops is typically at the 60 percent design review stage, when the design is fairly firm and the cost is not substantial to make changes from the Hazops. Key terms that are used during a Hazops are: a) Study Nodes: The locations on the drawings at which process parameters are investigated for deviations (e.g. Equalization Tank) b) Intention: The expected operation of the system in the absence of deviations (e.g. No copper in effluent)

c) Deviations: These are departures from intentions that are obtained by applying the guidewords (e.g., tank overflow) d) Causes: The reasons why deviations might occur. There could be one or many causes to deviations (e.g. hardware failure, human error, power failure) e) Consequences: These are results of deviations should they occur (e.g. release of copper to sanitary sewer, equipment damage). Since there will be several consequences, it is important to consider only those that have serious consequences relative to the study objective f) Guide Words: These are words which are used to qualify or quantity the intention in order to guide and stimulate the brain storming process and so discover deviations (e.g., no, less, more, part of, reverse, other than) g) Corrective Actions: These are actions assigned to prevent serious consequences (e.g., increase maintenance, add redundancy) h) Process Parameters: Variables that could cause deviations (e.g., pressure, temperature, flow) Copper Treatment System Hazard and Operability Study: The Hazops concepts discussed above were put into practice using the following methodology 1. Defining the purpose, objectives, and scope of the study: The purpose of the Hazops study was to identify release scenarios that could result in a discharge of copper wastewater to the sanitary sewer. The objectives therefore were to understand the system operation, ensure compliance with requirements and develop mitigation measures to eliminate or reduce risks identified during the Hazops. Scope of this Hazops was limited to the Copper Treatment System 2. Selecting the Hazop team: A multidisciplinary team consisting of AMAT and contractor personnel was formed to brainstorm the Copper Treatment System. These included representatives from the manufacturer, construction contractor, maintenance, ESH, building operations, and facilities. The team leader briefed the participants on the Hazops methodology before starting the Hazops. 3. Preparing for the study: Before starting the Hazops, the team leader reviewed the design drawings, facility layout, flow charts, and operation and maintenance manuals to understand the operations. The entire treatment process was divided into 4 sub system; dilute copper waste water treatment, Ion exchange regeneration system, CMP slurry treatment, and concentrated copper sulfate waste treatment. Process flow in each subsystem was broken into nodes, or points

at which deviations could be studied. Nodes in the dilute copper waste treatment system included, feed tank, carbon polishing, ion exchange resins, and treated water storage tank. Nodes for the Ion exchange regeneration system included chemical rinse tanks, regeneration process, and storage tank. Nodes studied for CMP slurry treatment included equalization tank, slurry concentration tank, ultrafiltration process, filter press, and storage tank. Lastly, nodes for the concentrated Copper waste treatment were the feed tank and transfer pumps, evaporator holding tank, filter press, evaporators, and drum evaporator. Information available was rearranged based on the nodes and sub-systems 4. Conducting the team meetings: A series of meetings were conducted to brainstorm the Copper Treatment Systems. One meeting was devoted to each sub system to limit the time spent at one sitting. At the Hazops meeting, each node was thoroughly evaluated using guide words such as more, less, and none to process parameters pressure, temperature, reaction, time, and flow. Combining the guide words with process parameters led to possible deviations that might occur. Consequences of the deviations and suggested corrective actions were discussed by the Hazops team. The guide-word procedure was continued for each node and suggested actions noted for any deviations. 5. Recording the results: The results of the Hazops meetings were recorded on spreadsheets for each node and sub system. Entries were made into the spreadsheets as the Hazops study progressed. All corrective actions suggested were recorded in the spreadsheets 6. Selecting and Assigning Action Items There are several ways to select and assign action items. The conservative approach is to assign all action items to an owner for correction. Due to time restraints however, it is better to rank each consequence in terms of probability and severity. Each consequence of a deviation is considered by the Hazops team and given a probability of unlikely, possible, or likely. Similarly, severity of occurrence is rated as, insignificant, moderate, and significant. The results are plotted on a probability/severity graph 2 (see figure 2). Consequences that are both probably and severe are considered credible, and action items to mitigate these are assigned to appropriate personnel. At Applied Materials, the conservative approach was used and all action items generated during the Hazops were assigned to plant personnel for completion. Conclusions:

The Hazops technique was found to be effective for this design review, particularly since the system was new and relatively complex. It greatly increased the understanding, safety and environmental compliance of the Copper waste treatment systems, particularly for maintenance personnel who are responsible for keeping the system up an running. In addition, specific modifications to design were made based on the Hazops study results. A detailed Hazops however, can take significant time and resources. It is difficult to schedule, and follow up on action items becomes difficult as the team disbands. At least a minimum version of a Hazop study however, is recommended for all new and complex environmental protection and abatement systems. As a result of Copper Treatment System Hazop, certain proposed actions included, increased alarm notifications with tighter alarm parameters, increased preventive maintenance procedures (PMs) on transfer pumps, installation of sight glass for visual monitoring of all tanks, heat jackets on caustic tanks to prevent freezing, reevaluation of design parameters, emergency power to critical systems to prevent failure in power outage, and installation of fluoride sensors. This form of detailed evaluation is not possible without a thorough hazard and operability study. The team agreed to revisit the study and installation within a year of operation. Maintenance personnel agreed to keep the necessary records with this review in mind. The follow up review will determine if the recommended changes did indeed improve the operation of the system and if any additional changes to procedure or modification of the system is warranted based on this period of operation. As a key system with clear environmental aspects and impacts, the study and operational findings are expected to exceed Environmental Management System (ISO14001) requirements when certification is obtained for this area of our business. Attachments: Table 1: Figure 1: Figure 2: Copper Waste Streams and Treatment Technologies Used Flow Chart of Copper Treatment Process Probability/Severity Graph

References 1) The Center for Chemical Process safety of the American Institute of Chemical Engineers, 1985 Guidelines for Hazard Evaluation Procedures,.

2) United States Environmental Protection Agency, 1987, Technical Guidance for Hazard Analysis, Emergency Planning, and Extremely Hazardous Substances

Authors: Shree Dharasker, P.E., REA Shree is Member of Technical Staff at Applied Materials, Santa Clara, California. He is currently responsible for Product Environmental Support at Applied Materials. Previously, he was responsible for Applied Materials-Santa Clara environmental and emergency response management. He has a BS in Chemical Engineering from the Indian Institute of Technology in Bombay, India, and an MS in Environmental Engineering from New Jersey Institute of Technology, Newark, New Jersey. Shree is a Registered Professional Engineer (Chemical) and a Registered Professional Assessor in California. He is an active member of SSA, SEMI, and other professional associations.

Joan Ning Joan is an environmental engineer in Applied Materials Lab Operations group, responsible for environmental compliance in the laboratories. Joan has a BS in Environmental Science from San Jose State University, San Jose California. Joan is an active member of SSA and other professional associations.