3039 Atr

S68 Final Report: Template Methodology and Lessons Learned for Sampling and Analyzing Tool Effluents
SEMATECH
Technology Transfer 95123039A-TR
SEMATECH and the SEMATECH logo are registered service marks of SEMATECH, Inc. Applied Materials and Precision 5000 are registered trademarks of Applied Materials, Inc. CONCEPT ONE is a registered trademark of Novellus Systems, Inc. Freon, Tedlar, and Teflon are registered trademarks of E.I. du Pont de Nemours and Company. Swagelok is a registered trademark of Swagelok Co.
1995 SEMATECH, Inc.
S68 Final Report: Template Methodology and Lessons Learned for Sampling and Analyzing Tool Effluents
Technology Transfer # 95123039A-TR SEMATECH
December 31, 1995

Abstract: This template methodology provides guidance for the construction, verification, and operation of sampling and analysis systems to characterize and quantitate semiconductor plasma manufacturing tool effluents after the ballast gas is added, but before house abatement systems. The results represent qualitative values for tool emissions upstream of abatement devices; they do not represent emissions from the facility. The methodologies have been applied to several plasma etch and chemical vapor deposition (CVD) processes and are based on the application of online configurations of mass spectrometry (MS) and Fourier transform infrared (FTIR) spectrometry to monitor representative samples of gaseous tool effluents. Lessons learned pertain to sampling manifold design and construction; instrument calibration and quality control (QC); and data collection, storage, and analysis. This document is meant to serve as a knowledge base to be built as investigations in this area continue.
Keywords:
Calibration, Chemical Vapor Deposition, Emissions, Fourier Transform Infrared Spectroscopy, Plasma Etching, Material Balance, Gauge Capability, Byproduct Characterization, Spectrometry, Employee Safety
Authors:
Melissa D. Tucker, G. Dean Marbury, John S. Stanley, J. Eugene ODonnell, Lance M. Henning
Approvals:
Albert Cheng, Project Manager Phyllis Pei, Program Manager Ray Kerby, Director Laurie Modrey, Technical Information Transfer Team Leader
iii Table of Contents 1 2 EXECUTIVE SUMMARY........................................................................................................1 1.1 Summary of Results Relative to Project Objectives..........................................................1 MANIFOLD DESIGN AND USE.............................................................................................2 2.1 Tool Sampling ...................................................................................................................6 2.2 Lessons Learned About the Manifold Design and Use .....................................................8 ANALYTICAL SAMPLING AND CALIBRATION .............................................................11 3.1 Mass Spectrometry ..........................................................................................................12 3.1.1 Mass Spectrometry Sampling at Chamber............................................................12 3.1.2 Mass Spectrometry Sampling, Post-pump............................................................12 3.1.3 Mass Spectrometry Description and Calibration..................................................12 3.1.4 Lessons Learned About Mass Spectrometry Sampling and Data Analysis..........13 3.2 FTIR.................................................................................................................................14 3.2.1 FTIR Sampling, Post-pump ..................................................................................14 3.2.2 FTIR Description ..................................................................................................14 3.2.3 FTIR System Setup and Calibration for Tool Survey...........................................14 3.2.4 Lessons Learned About FTIR Sampling, Calibration, and Data Analysis............16 APPLICABILITY OF THE METHODOLOGY .....................................................................18 ADDITIONAL ANALYSES OF PROCESS BYPRODUCTS ...............................................20 5.1 Sampling and Analysis of Condensed Phase Particulates ...............................................21 5.2 Odors Analysis During Preventive Maintenance.............................................................22 AN EXAMPLE OF A DETAILED TOOL ANALYSIS BY FTIR.........................................24 6.1 Measurement System.......................................................................................................26 6.2 Gauge Study.....................................................................................................................26 6.3 Time Response of the Sampling System Study...............................................................39 6.4 Off-Site Calibrations .......................................................................................................40 6.5 On-Site Testing................................................................................................................42 6.5.1 Instrumentation Setup and Quantification ............................................................42 6.5.2 Point-of-Use Calibration.......................................................................................42 6.5.3 FTIR Data Acquisition, Processing, and Management.........................................43 6.6 Passive Data Collection Based Sampling and Analysis ..................................................43 AN EXAMPLE OF A DETAILED TOOL ANALYSIS BY MS............................................43 7.1 Instrument Selection........................................................................................................44 7.2 MS Systems Used For This Study...................................................................................44 7.3 Instrument Preparation and Characterization ..................................................................45 7.4 Instrument Installation.....................................................................................................45 7.5 Initial and Continued Quality Control.............................................................................46 7.6 Sampling..........................................................................................................................46 BIBLIOGRAPHY....................................................................................................................47 FTIR SUGGESTED READING..............................................................................................47
4 5
8 9
10 GLOSSARY ............................................................................................................................48
Technology Transfer # 95123039A-TR
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iv List of Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Direct Sampling Manifold Schematic...........................................................................4 Sampling Manifold Schematic with Instrumentation (FTIR and MS) .........................5 Plot of C2F6 and COF2 Absorbance as a Function of Time in an Oxide Etch Process ..........................................................................................................................7 General Sampling Plan of the Tool...............................................................................8 Connection System for MS to Tool Sampling............................................................10 Impinger Sampling System.........................................................................................21 Scheme for Analysis of Condensed Phases and Pump Oils .......................................23 Selecting an Approach to Byproduct Characterization...............................................25 Key to Chart Box Shapes............................................................................................27
Figure 10 General Decision Tree for the example of a Detailed Tool analysis by FTIR............28 Figure 11 Flowchart for the Gauge Study Procedures in the Example of a Detailed Tool Analysis by FTIR........................................................................................................29 Figure 12 Flowchart for the Time Response Study Procedures in the Example of a Detailed Tool Analysis by FTIR.................................................................................32 Figure 13 Flowchart for the Off-site Calibration Procedures in the Example of a Detailed Tool Analysis by FTIR.................................................................................33 Figure 14 Flowchart for the On-Site Testing Procedures in the Example of a Detailed Tool Analysis by FTIR ...............................................................................................34 Figure 15 Flowchart for the Point-of-use Calibration in the Example of a Detailed Tool Analysis by FTIR........................................................................................................38
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v List of Tables Table 1 Table 2 Table 3 Table 4 Construction Details of the Sampling Manifolds .........................................................6 Criteria for MS, GC/MS .............................................................................................14 QC Criteria for FTIR ..................................................................................................15 Chemicals Used by MRI.............................................................................................41
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1 1 EXECUTIVE SUMMARY
This template methodology is intended to provide guidance to nonscientists and scientists characterizing semiconductor manufacturing tool byproducts. Because of safety concerns in SEMATECHs cleanroom, the template uses FTIR technology; less effort was spent on developing MS technology. The method presented is not a final method. The results may not apply to other similar systems because of differences in processing variables and the system and facility interface. The results represent qualitative values for tool emissions upstream of abatement devices; they do not represent emissions from the facility. 1.1 Summary of Results Relative to Project Objectives
SEMATECH has undertaken the characterization of semiconductor manufacturing tool process byproducts to give its member companies analytical methodologies and information needed to improve stewardship of process chemicals and a better understanding of the byproducts of various manufacturing technologies. The results and methodologies from this effort are intended to aid in the selection of personal protective equipment (PPE), waste disposal options, and treatment technologies. This study focused on two types of processes: plasma etch and chemical vapor deposition (CVD). The following results were obtained for the four study objectives: Objective 1. Develop methodologies to collect byproduct data and characterize air emission and waste byproducts for the following priority plasma etching and tungsten CVD processes: poly etch, oxide etch, metal etch, tungsten etchback, and tungsten CVD. A preliminary methodology for sampling and analysis of process byproducts was developed and tested. The methodology uses sampling equipment constructed of tubing, gas cells, and valves that allow process gases to be sampled from the tool exhaust streams after the mechanical pump and abatement devices. The process gases flow into the analytical sampling system, which consists of an FTIR with appropriate cells and a mass spectrometer (MS). The sampling methodology for off-gases obtained during preventive maintenance (PM) operations was developed and tested by open-path FTIR and gas chromatography/mass spectrometry (GC/MS) analysis of SUMMA canister samples. No significant emissions from the tools during PM were found by open-path FTIR. SUMMA canisters of representative tool exhausts were collected, and GC/MS was used to analyze the samples. A reliable method for GC/MS analysis of the corrosive gases contained in the SUMMA canisters was not possible with existing commercially available columns. However, some useful, corroborative, qualitative data were obtained by GC/MS. The stability of SUMMA samples during transportation and storage is also unknown. The preliminary tool investigation included only limited QA/QC procedures. Objective 2. Develop an understanding of the reaction byproducts to aid in the selection of PPE, waste disposal options, and treatment technologies. For seven tool processes, both process gases and gas phase byproducts have been identified so that PPE may be considered by experts in these areas.
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2 Objective 3. Provide a generic methodology to characterize other process byproducts. A preliminary template methodology for the analysis of a semiconductor manufacturing tool gas exhaust was developed. The health and safety utility of the sampling and analysis methodology can be assessed. As a result of the findings of this initial project phase, calibration library spectra for FTIR are available. Objective 4. Combine results with other databases or models to predict process byproducts. Because of the complexity of the plasma modeling, this objective was not considered as part of this project, but is instead a long-term goal for SEMATECH and its member companies. 2 MANIFOLD DESIGN AND USE
A sampling manifold can be designed and constructed from commercially available materials that allows easy installation and disassembly while remaining safe for use under anticipated sampling conditions (see Figure 1, Figure 2, and Table 1 for an example). Swagelok components can be used for all connections as well as standard valves and flow controllers for gases. The safety of the design should be verified by safety personnel. The sampling manifold should be leak free, and the design should allow pump effluent to be returned safely to the tool piping for subsequent abatement. The construction material for the manifold should be selected according to the anticipated chemistries. For a stream of corrosive materials, limited experiments were conducted to compare stainless steel (SS) and Teflon materials. Preliminary results in the laboratory of the validation experiments indicated > 95% recovery for hydrogen chloride (HCl) and hydrogen bromide (HBr) but < 60% recovery for chlorine (Cl2) using metal manifolds.2 The performance characteristics of the manifold should be verified using process gas flowed with a known flow rate through the tool without plasma or wafers. The purity of the gases, operationally defined as the presence or absence of nonprocess gas species observed at the tool sampling points, can be determined in situ or on site with FTIR or MS. The theoretical concentration of the process gas can be calculated using the known flow of the reactant gas (es) into the tool and an measured flow of the ballast gas. The theoretical concentration can be compared to the measured concentration at the instrumentation. If mass balance figures are to be calculated, a calibration check should be performed by flowing unvented (plasma off) gases through the etcher. The theoretical and measured concentrations can then be compared. A specific example of these studies is outlined in Section 8.5.2. A similar calibration check should also be achieved by using MS technology. Because of the time limitation, a protocol was not developed. A manifold that connects the tool sampling points to the analytical instrumentation may be necessary to minimize the number of instruments used within the confined space of the facility and to ensure that the time response of the measurements is well within the time scale of the process being studied. For the tools tested at SEMATECH, the process steps ranged from 10 sec to several minutes long. Additional instruments can be installed where ample space is available or where distance between the tool and abatement device precludes a single manifold system. For example, abatement devices sometimes are located in a room separate from the tool. However,
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3 additional operators and coordination are required for additional instruments, adding to the expense and time requirements.
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Figure 1
Direct Sampling Manifold Schematic
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Figure 2
Sampling Manifold Schematic with Instrumentation (FTIR and MS)
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6 Table 1
Dwg. No. 1,2,7,8 3 4 5, 6 9 10 All All Pump 1,2 Pump 3,4 Item On/off ball valves Press/flow-control valve On/off plug valve Flow-control valve Diaphragm flowcontrol valve Bellows flow-control valve Connectors Tubing Vacuum pumps Vacuum
Construction Details of the Sampling Manifolds

Mfg Whitey (series 40) Nupro (series-U) Nupro Nupro (series-S) Nupro (series DL) Nupro (series BM) Swagelok Supelco Edwards Edwards
1 1
Description /4 in SS Swagelok w. TFE seals /4 in monel bellows valve, Swagelok connectors /2 in SS
1 1
/8 in SS Swagelok needle valve, TFE glands and seals

1
/4 in SS Swagelok /4 in Monel Swagelok
all SS, sized as needed; typical 1/8- and 1/4-in materials 304 SS passivated tubing (precleaned) 1/8 in OD 2.1 mm ID typical 2-stage diaphragm (dry) pumps for flow control E2M 2-stage wet-pumps, Krytox fluids for MS systems
Manifold materials constructed of SS and Swagelok or VCR fittings have the greatest safety margins, but tend to react with the process gases Cl2, HBr, and BCl3 and with the byproducts HCl, HF, and Br2. Alternative materials such as Teflon may reduce, but not eliminate, reactivity since water is usually entrained in these more porous materials and can be available to react. A heated manifold may help to reduce the entrained water. The extent of this reactivity is not fully characterized/quantified for the manifold. However, based on limited experiments in the facility on one tool, data suggest that the MS interface, rather than the manifold leading to the MS, contributes the most to artifacts arising from chemical reactivity with manifold materials. 2.1 Tool Sampling
A preliminary investigation (survey) of the tool effluent is desirable to provide information on any species that are potentially present and to determine the concentration ranges so the calibration gases can be purchased for future quantification efforts. This tool survey may provide important information about the manifolds performance and the selection of appropriate manifold materials. The preliminary information is used to guide the detailed single-day or replicate multiple-day sampling and analysis efforts.
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Figure 3
Plot of C2F6 and COF2 Absorbance as a Function of Time in an Oxide Etch Process
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8 A schematic of a generic wafer fabrication tool, along with the possible locations for sampling, is shown in Figure 4. These locations represent where ports can be installed to obtain real-time samples at the chamber and before pumping (B), after the foreline pump and before abatement (post-pump, pre-abatement C), and after abatement (post-abatement E). Points A and D, respectively, represent locations where chamber and post-pump condensed materials can be obtained (only during disassembly of the tool during PM operations). The ballast gas flow rate through tool pump packages should be monitored with a mass flow meter (MFM) so that mass balance can be accurately calculated.
Figure 4 2.2
General Sampling Plan of the Tool
Lessons Learned About the Manifold Design and Use
During the construction and use of the sampling manifold, the following lessons were learned. The construction materials used are detailed in Table 1; Figure 1 and Figure 2 show a sample manifold schematic. 1. Validation of the sampling apparatus for analysis of reactive species, such as HCl and BCl3, was not achieved in the field. Evidence indicates the necessity of a different sampling and analysis approach for such gases as Cl2, F2, and HF. To analyze HF, a heated manifold is used to minimize the further reaction of the HF with the wall of the pipe because of the residual moisture. Sampling reactions occur with the conventional SS tubing and sample manifolds used for both FTIR and MS analyses. 2. The behavior of reactive halogens, such as Cl2, F2, and Br2, and inorganic acids, such as HCl, HF, and HBr, with regard to reactions/sorptions with surface materials is variable and difficult to predict, control, or eliminate. This creates a fundamental problem with the tool-to-instrument interface of the MS (Figure 5). These homonuclear diatomic species are not amenable to FTIR analysis. Consequently, extensive research and development of an analytical methodology suitable for the quantitative analysis of reactive species is required.
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9 3. A study of the optimum material for manifold construction should be conducted. Candidates for investigation include off-the-shelf SS, electropolished SS, Teflon-coated SS, PVDF-coated SS, and gold-plated SS. 4. While most of the constituents in the tool effluents were consistent with process chemistries, for certain processes, there were logical inconsistencies between what was observed and what was realistically expected to have been present. 5. The pressure within the sampling system should be monitored and controlled to assure that pressure drops, if observed, are characterized and recorded. Pressure consistency should be assessed as a function of flow rate in the sampling system. Before studies begin, pressure transducers should be placed upstream and downstream of the cells to assess the continuity of the pressure within the system. The flow rate of the gas in the manifold during sampling at the tool and calibrations should be kept constant to assure that the calibration spectra best represent the data collected at the tool. 6. The manifold should be compact and portable. When possible, a copy of the floor plan with measurements of the area in the facility where work will be done should be obtained. The footprint of the sampling system should be minimized to reduce opportunities for surface reactions between the manifold and the gas stream. 7. It is recommended that personnel performing the studies visit the facility where the work will be done to eliminate any unforeseen complications, such as availability of room for sampling equipment and personnel, whether the actual sampling location will be in cleanroom or not, location/availability of electrical outlets, location of sampling port and manifold, and availability of other facilities. 8. If an analysis is performed at a cleanroom, insulating materials should be chosen carefully to ensure that they are appropriate for work done in the cleanroom facility (i.e., materials do not release particulate to the cleanroom environment). 9. If the cells and manifold are to be heated, care should be taken to heat components to temperatures at which they will function properly, or components must be selected that will withstand the selected temperature. 10. If a heated gas stream is not thermally homogenous (e.g., cool in the center of the manifold but hot on the wall), the temperature of the gas in the cell may vary with inlet gas temperature. 11. If a manifold is heated, methods for obtaining the temperature of contained gas streams should be investigated, and the thermal decomposition and reactions of gases within the sample stream should be considered. 12. Studies on the appropriate temperature for the sampling system should be conducted. All heated cells should be thermally isolated from any components used to isolate the purged optical path and/or any baseplate of the sampling system.
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10
Figure 5
SEMATECH
Connection System for MS to Tool Sampling

11 The near-ambient pressures downstream of the pump allow for extractive sampling and analysis by both MS and FTIR. A single sampling port with a manifold for the distribution of the extracted gases to each of the analytical instruments is recommended, but it may not be the best course for all sampling situations. Once analyzed, the extracted gases should be returned to the tool piping at a point well downstream of the extraction point. A discussion of manifold design considerations can be found in Section 2. Sampling requires the installation of a sampling port in the tool piping as well as return port for sampled gases returned after analysis. Access ports can be installed in advance by maintenance personnel, preferably while the tool is down for repair or scheduled maintenance. The sampling port should be located far enough downstream of the pump to allow the tool chamber effluent to mix completely with the ballast gas introduced at the pump. The access ports can be fitted with appropriate ball-type valves to allow the sampling manifold to be connected without disrupting the tool operation. The analytical instrumentation and related manifold assembly should be connected to the tool piping well in advance of any sampling activity to allow time for the system to be purged and/or conditioned. Once installed, the system should be heated to the desired operating temperature and checked for leaks. Sampling activities should be initiated only after the system is determined to be free of leaks and contaminants above a predetermined level. The purge gas should be monitored periodically for contaminants. Sampling at post-abatement locations is fundamentally the same as for post-pump locations except as noted below. If the abatement device is located near (within 5 m) the post-pump sample take-off valve, then the switching arrangement shown in Figure 1 and described in the manifold operation section can be used. If space and distance do not permit the two-location system to be used, then the operation of the manifold is identical to that used for the post-pump tests. Exceptions to this approach are detailed as follows. Burn-box type abatement systems may produce copious particulate materials that may clog the small valves used in the sampling manifold due to the moisture level from the point of use scrubber. The materials used to construct the tool and associated components, such as mechanical pumps and piping, may react with process gases and byproducts , as evidenced by discoloration of interior tool surfaces and particulate materials observed during PM activities. This sink for byproducts may introduce both low and high bias in mass balance determinations using the template methodology unless solids are thoroughly investigated. A detailed description of sampling and analysis of condensed phase particulates is outlined in Section 5.1 of this document. 3 ANALYTICAL SAMPLING AND CALIBRATION
Many types of chemical analysis instruments can be used to identify and quantify the real-time gas stream. This methodology was developed using both FTIR and MS Technologies. Both techniques offer valuable information about the process byproducts, but FTIR was more thoroughly investigated in the studies used to formulate this template methodology. The instruments (MS and FTIR) are used concurrently in an initial investigation to determine the response range of all compounds present in the tool exhaust and to provide cross-verification
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12 of7newly identified species. Both instruments use personal computers (PCs) for data collection, analysis, and display. FTIR and MS must be used together as a minimum analytical approach; however, neither FTIR nor MS techniques are adequate for analyzing diatomic halogens species in the presence of their respective acids. 3.1 3.1.1 Mass Spectrometry Mass Spectrometry Sampling at Chamber
The process chamber, point B in Figure 4, is analyzed using MS only. Extractive FTIR requires a gas load beyond what the tool can supply for analyses, and optical paths through the tool chamber require extensive modifications to the chamber housing and are therefore impractical. The MS can be connected to the chamber using fittings and a valve; it can be operated simultaneously but independently from the other analytical instrumentation. Figure 5 shows an example of a possible connection. The fittings are installed on the chamber by locating an existing access port. Each tool must be fitted with the sampling manifold on an individual basis in consultation with the tool engineer as recommended. A stand-alone MS operated in the electron-impact mode may be attached directly to the process chamber (point A, Figure 4) through a simple manifold connection (Figure 5), allowing direct sampling of compounds in the process chamber. A system capable of scanning a broad mass range (0 to 600 amu) is preferred. Additional information about selection of a MS system and system used by MRI can be found in Section 7. 3.1.2 Mass Spectrometry Sampling, Post-pump
MS may be operated in the electron-impact mode without chromatographic separation and may be attached to the sampling manifold to provide the mass-to-charge ratio of fragments and therefore, a chemical identification of compounds occurring at post-pump (point C of Figure 4) can be obtained. (See Section 7 for additional information.) 3.1.3 Mass Spectrometry Description and Calibration
Calibration checks are performed for zero concentration (only pump ballast gas flowing) when acceptable source pressure is achieved. It may take several hours of pumping to reach that level. A perfluorotributylamine (PFTBA) calibration system built into the MS as a standard feature is preferred. This calibration system will reliably verify mass assignment, mass resolution, and overall sensitivity. Maintaining the compound-specific quantitative calibrations, performed in the laboratory, after the MS systems are moved is difficult. However, qualitative identification of byproducts relies only on correct mass assignment, and the ease of PFTBA mass calibration in facilities proves beneficial. The MS data must be acquired continuously from the initial tool chamber pumpdown step (this occurs when wafers enter the loadlock or chamber) until the last wafer of a load exits the chamber and any clean and passivation steps are completed. Data should be plotted as intensity of total ion current versus time and, where specific masses of interest are to be plotted, time versus specific mass intensity should also be plotted. Spectra at peak maxima should be plotted,
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13 along with plots to show nonsaturated signals, where possible. QC criteria, as outlined in Table 2, should be carefully adhered to and recorded. Because of the highly sensitive nature of the MS system, an on-site and in situ calibration of the target byproducts is highly recommended to obtain a quantitative result. 3.1.4 Lessons Learned About Mass Spectrometry Sampling and Data Analysis
MS provides information for most of the compounds observed at the chamber and at post-pump locations during tool operation. Some molecules interfere with each other because they break down into the same fragments. 1. The process chamber can be passively sampled with MS. 2. Direct MS sampling from the exhaust stream requires some additional interface development to overcome accumulation and/or corrosion problems. 3. MS sampling is essential for the quantitation and/or identifications of the diatomic halogens because they are not infrared active. 4. On-site and in situ calibration of the MS system is necessary to generate a quantitative result. Improved calibration techniques (e.g., preparing and handling a known concentration of corrosive and reactive gas for work in the testing facility) need to be further study. 5. SUMMA canister analysis, as currently performed, is subject to artifacts from reactions between the corrosive samples and the chromatographic column. Further column selection and development work are required. In addition, the short- or long-term integrity of reactive species in SUMMA canisters also need further study. 6. Because the intensity of MS fragmentation can vary with concentration, multiple concentration replicate calibration curves are essential for accurate quantitation. 7. Lower concentration mixes were at lower limits of the MFCs accuracy. Extreme care needs to be taken while preparing these standards. 8. At lower flow limits, the MFC needed time to stabilize at the selected flow setting. 9. Once the studies begin, modifications to the sampling system should be minimized to ensure that all tests, calibrations, and tool sampling are done under the same conditions. 10. Because of the high concentrations of compounds found in most data, qualitative identification was fairly straightforward for many compounds; however, many unknowns continued to account for an unknown amount of the mass balance. Communication with other SEMATECH or SEMI/SEMATECH companies with MS libraries would expedite the identification of unknowns. 11. Sufficient means of transferring large data files from within the cleanroom to an office environment should be planned (e.g., from a tape drive to a diskette). 12. Data files should be assessed for data quality immediately after data collection.
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14 Table 2
Analysis Tuning, FC-43 QC Parameter Resolution
Criteria for MS, GC/MS

Frequency Before/after run Criterion m/z 69/70 unit @baseline m/z 502/503 50% valley
Peak shape Sensitivity
Before/after run Before/after run
m/z 69, 264 symmetry < 1.5:1 each m/z 502 > 5:1 S/N 502:69 > 0.2 %
Mass axis Blank Zero N2
Before/after run Each day
m/z 502 < 0.2 amu of theoretical All signals < 0.1 ppm for each cpd.
3.2 3.2.1
FTIR FTIR Sampling, Post-pump
An FTIR spectrometer can be connected to the sampling manifold (described in Section 2) to provide compound-specific identification and quantification of the process stream in the postpump location (point C, Figure 4), where the addition of nitrogen at the pump has brought the stream up to near atmospheric pressure. Measurements made before abatement of the process stream indicate byproducts from plasma processes in tool. The measurement of ballast gas (nitrogen) added at the pump is critical to correlate the concentration observed at the FTIR (in ppm) to the gas added to the tool chamber, as it is necessary for mass balance calculations. 3.2.2 FTIR Description
Spectral resolution is suggested for preliminary investigations to give maximum information about peak shape useful for the identification of compounds in the stream. Because of the broad range of concentrations observed in the process streams, both high concentration process gases and lower concentration byproducts that may occur together in a single sample stream must be analyzed. 3.2.3 FTIR System Setup and Calibration for Tool Survey
FTIR allows calibrations conducted in the laboratory (on or off site) to be used to quantitate any spectra collected using the same instrument. Therefore, FTIR is particularly powerful for byproduct characterization. In addition, the FTIR spectrometer allows many compounds to be unambiguously identified through high resolution (0.5 cm-1 resolution is possible), frequencyprecise spectra. The FTIR system is set up with the manifold and sampling cells in place. The cells should be lined (including mirrors) with a corrosive resistant coating such as teflon. An example of one sampling system is described in the example of a detailed tool analysis in Section 7. The relationship between absorbance and concentration is governed by Beers Law, which states: Absorbance = (absorption coefficient) (path length) (concentration) or
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15 A = (a) (b) (c) The value for absorbance (A) is observed from the absorbance spectrum at a specific frequency, characteristic of a particular vibration of a molecule. The absorbance value reported is unitless and is the maximum peak absorbance at a frequency characteristic of a molecular vibration, minus the baseline absorbance. The absorption coefficient (a) is a constant for a particular vibrational frequency of a compound; it is used to relate absorbance(A) to pathlength and concentration. The units for the absorption coefficient are one over parts per million (ppm) times meters (m). This product, together, is abbreviated by ppm-1 m-1. The concentration (c) of the molecules over the path that contains them is given in ppm. This unit means parts (or molecules) of the compound of interest per million (106) parts (or molecules) of everything present. In the laboratory, the cell is filled with parts of a compound per parts of nitrogen (plus parts of compound) to supply an inert atmosphere. Nitrogen is used instead of air because it is desirable to minimize the effects of strong absorbers such as water and CO2 found in air. The concentrations used for calibrations can be determined from the concentrations observed in the initial investigation. Because it is desirable to bracket the observed concentrations in all studies, concentrations should be chosen that are higher and lower than those anticipated in tool studies. The gas to be calibrated is delivered to the calibration cell at a known concentration using some dilution system. An example of one dilution system is given in Section 6. The cell should be evacuated and filled to atmospheric pressure with pure, dry nitrogen. Two background spectra are obtained. These spectra are used to create an absorbance file. The root mean square (rms) noise, once determined, can be used to assess detector performance as indicated in Table 3. Table 3
Analysis All QC Parameter N2 blank absorbance file CTS Sample absorbance All quantitations 5-point curve
QC Criteria for FTIR

Frequency Before/after run Before run Each compd. 5 replicates Criterion Rms, noise, < .009 absorbance units > 60:1 S/N freq. 0.5 cm-1 of theoretical Not saturated, but above baseline noise R2 = > 0.99; coefficient of variation < 10% at each point, < 25% for regressed line.
A calibration transfer standard (CTS) is used to assess the day-to-day reproducibility and longterm stability of the instrument. A compound is chosen for the CTS that is stable and inexpensive and that has peaks in the 800 to 1,200 cm-1 region of the spectrum that absorbs well over the path length(s) used in studies. For the example in Section 6 , ethylene was used as the CTS; the absorbance of the peak at 995 cm-1 is recorded before each run to assess the day-to-day reproducibility and long-term stability of the instrument. A calibration curve is determined using multiple, replicate spectra of a compound to determine the absorption coefficient. A spectral feature or band is chosen and IR absorption of the band in
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16 each spectrum is measured. A regression plot of absorbance as a function of concentration (in ppm) times path length (in meters) yields an absorption coefficient, which is the slope of the plot, in units of concentration-1 distance-1 (ppmm)-1. The statistical correlation coefficient (R2 value) of the plot must be a minimum of 0.99 for the absorption coefficient to be used for calibration. This compound-specific, wavenumber-specific absorption coefficient can be used on site to determine the concentration of the compound using the peak because of a specific compound. The observed absorbance, absorption coefficient, and path-length can be used with Beers Law to calculate the concentration of the compound collected at the tool. Another way to determine the concentration in the field is to use one of the calibration spectra known to lie on the linear calibration plot. It is important that the plot lie exactly on the curve or else errors are introduced. The calibration spectrum can be subtracted from the field spectrum until there is no more absorbance because of the peak in the spectrum. Currently available software allows the user to subtract interactively; a subtraction coefficient is available. Since the subtracted spectrum is of a known concentration and the relationship between absorbance and concentration is linear, this subtraction coefficient can be multiplied by the concentration of the calibration file to get the concentration in the field spectrum. The appendix contains plots of spectra used for qualitative identification of compounds that may be seen in the post-pump effluent stream from plasma etch and CVD tools. For each compound, peaks are shown for various concentrations of the compound. In many cases, the peak is not onscale for the entire concentration range available. A peak is on-scale if the absorbance is less than 1 absorbance unit and greater than two times the peak-to-peak noise in the appropriate region. 3.2.4 Lessons Learned About FTIR Sampling, Calibration, and Data Analysis
The following are lessons learned about FTIR sampling, calibration, and data analysis.: 1. Because FTIR spectral characteristics can vary with concentration, multiple concentration, replicate calibration curves are essential for accurate quantification. 2. FTIR multipoint calibrations (five concentrations, five replicates) are essential quantitative information. 3. Precision for several Beers law calibration plots decreased as the concentration of the gas increased because of the higher flows of calibration gas required, which were limited by the range of the MFC. 4. The permeability of Tedlar bags does not allow them to be used for corrosive gas mixture preparations. However, noncorrosive gases were mixed and delivered to the system successfully in Tedlar bags. 5. A minimum of 2 hours is required to purge the FTIR system by dry nitrogen to eliminate any trace moisture before an acid gas is introduced into the system. 6. In addition, heat may be applied to the manifold system to minimize the level of residual moisture. 7. Lower concentration mixes were at lower limits of the MFCs accuracy. 8. At lower flow limits, the MFC needed time to stabilize at the selected flow setting. 9. WF6 reacted in the Teflon delivery line in the 12 hours following testing to create an unknown pink reactant, which was not seen in any other part of the system.
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17 10. The optical path between the interferometer and the detector should be purged with nitrogen. 11. A serial configuration of gas flow through the gas cells allows for conformity of flow conditions and cell exposure history for all testing and maintains purge through the idle cell while the active cell is monitored (unlike the insulated parallel gas flow configuration). 12. If a small and a large cell are used in a serial arrangement, the small cell should be placed upstream of the large cell. 13. Ultrapure, dry nitrogen is required for backgrounds, dilutions, and purging of the optical path. 14. Sampling system modifications should be minimized, once the studies begin, to ensure that all tests, calibrations, and tool sampling are done under the same conditions. 15. FTIR data handling was slow compared to MS data systems. Large amounts of disk space were required for each real-time acquisition. In addition, it was necessary to process two FTIR runs for each tool process: one short path and one long path, unless a variable pathlength cell or a short followed by a long serial configuration was used for sampling. 16. Methods of automated data interpretation, such as partial least squares (PLS) or classical least squares (CLS) analysis, are useful to speed up data analysis time. However, the data must be well characterized before any automation can be done with confidence. A data analysis methodology that automates the redundant portions of the work, but does not isolate the user from the data, is suggested for future studies. 17. Because of the high concentrations of compounds found in most data, qualitative identification was fairly straightforward for many compounds; however, many unknowns continue to account for an unknown amount of the mass balance. Collaboration with other SEMATECH or SEMI/SEMATECH companies with IR libraries would expedite the identification of unknowns. A collection of calibration files would still be required for quantification, but qualitative identification would indicate the gases that should be procured. 18. Recent studies at MRI lead to the preliminary assessment that lower resolution may be sufficient for future studies for the mixture of the byproducts seen so far. Low resolution data collection is less time-consuming, both in the field and in the laboratory, and, in turn, the data are less expensive to collect and store. Faster data collection would allow for co-additions every 2 seconds or better resolution in step with the process sequence. Zero filling the interferogram and careful selection of the apodization function are recommended in future studies. 19. An FTIR spectrometer system that allows for data collection at a rate sufficient to analyze concentration changes in real time should be used. Acquisition rates of a scan per 2 seconds at 0.5 cm-1 spectral resolution were used for the survey work. The spectral resolution can be decreased to gain higher time resolution. However, some process events occur in less than 10 seconds, thus a fast scan rate is essential for accurate quantitative information in time. 20. The PC used for data collection should have a large hard drive (at least 2 gigabytes) to allow for data collection, storage, and manipulation. It should also have 8 to 16 megabytes of memory and a Pentium or faster processor. 21. Because s large number of files are required to characterize the gas stream in time, large data files will be collected. However, the file size should be minimized. For example, files should be collected in matrices to eliminate writing the header information multiple times. Only the time and spectral resolution required should be used during data collection. Zero filling should be done just before Fourier transform of the data.
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18 22. Sufficient means of transferring large data files from within the cleanroom to an office environment should be planned (e.g., from a tape drive to a diskette). 23. Data files should be assessed for data quality immediately following data collection. 24. Because of the large number of files, sufficient time should be allowed for Fourier transforms and the calculation of absorbance or transmittance files from single-beam spectra. 25. Data should be collected as interferograms to allow for quick data collection and for further investigations. The data should include resolution degradation, change in apodization function, and/or change in zero filling. 26. All interferograms should be backed up on tape. 27. A study of different coating mixtures for FTIR cell such as gold, platinum is necessary to determine the inertness of the cell with regards to the corrosive and reactive byproducts. 4 APPLICABILITY OF THE METHODOLOGY
This methodology applies to the determination of compound-specific concentrations in singleand/or multiple-component gas phase samples using FTIR and MS. Portions of this methodology have been field-tested on plasma etch and tungsten CVD systems results (see Section 6) and are applicable to those systems within the limitations described below. It was determined during preliminary tests that highly reactive species, such as homonuclear diatomic halogens (F2, Cl2, Br2), BCl3, and inorganic acids (HF, HCl, HBr) may produce both qualitative and quantitative artifacts as a result of reactions occurring on sampling manifold surfaces, instrument inlets, and/or in tool piping systems. Selection of sampling manifold materials (i.e., SS, Teflon-coated SS, PVDF-coated SS, gold-plated SS, or electropolished SS) and options of heating the sampling manifold and transfer lines should be considered when monitoring these species. Halogens (i.e., Br2, Cl2, F2) are transparent to FTIR and are reactive in most of the MS ionization sources especially when they are in low PPM concentration range and therefore may not be reliably detected or quantified by the methods described in this document. In addition, the overall accuracy of quantification using any methodology is affected by the individual accuracies of the flow measurements for process gases, pump ballast gases, reproducibility and ruggedness of the instrumentation, and limitations of calibration systems. General methodology limitations and lessons learned are as follows: 1. The nature of the reactant chemicals and potential byproducts associated with these manufacturing processes requires handling of toxic, explosive, and pyrophoric materials to obtain the necessary calibrations within the laboratory setting and during process monitoring activities. Safety is of primary concern. All activities and procedures should be reviewed with the tool owner, process engineer and the Environment, Safety, and Health (ESH) representatives before implementation. 2. Often, the necessary chemicals for calibration are not readily available from commercial sources at appropriate concentration levels. Therefore, planning before monitoring activities is necessary because of the often lengthy procurement time for chemical standards. Alternatively, the investigator(s) may choose to use a dilution device to prepare standards at the necessary concentration levels for pure gas in ultrapure nitrogen.
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19 3. Byproducts were observed for all seven processes tested at SEMATECH and were generated by both nonplasma and plasma-related gas-phase reactions and by plasma/substrate reactions (Table 1). 4. For silicon etch processes (poly and oxide), byproducts were correlated with specific process chemistries and the addition of process gases. Rapid interconversion of process gases was observed in the process chamber for poly etch. Instantaneous reactions occur for process gases in poly etch, which may suggest that reactive species other than process gases are actual etch mediators. Byproducts for photoresist (PR) strip process were principally carbon containing, both as oxidation and reduction products. 5. Equilibration/surface reactions in the tool create significant uncertainties in diatomic acids and reactive species quantitations. These reactions may be independent of the sampling and analysis equipment and may potentially be one of the dominant sources of uncertainty in quantification. 6. Rotameters for ballast gas control are poorly characterized/calibrated at the pump. This may introduce significant uncertainty in mass balance calculations, independent of the sampling and analysis equipment. Studies should be conducted to correlate the concentration of a gas observed at the post-pump location to the concentration gas at the chamber. Therefore, a mass flowmeter (MFM) should be installed at the ballast gas to calculate any mass balances. 7. A flow rate through the sampling system should be selected that is rapid enough to allow a low residence time in the largest cell used. A minimum residence time assures that the sampling apparatus does not observe a substantial lag in time from the changes occurring in the tool. Tests to determine residence time in the cells are outlined in Section 6.3. 8. Scheduling of the tools should be done well in advance of the studies, and process engineers should be briefed on the studies performed. They may provide valuable information about their tools and process chemistry. 9. Ambiguous fragmentation and mass interferents (e.g., CF4 and C2F6 isobaric ions at m/z 69) may limit concurrent detection of these compounds in the tool stream by MS. Fortunately, these types of ambiguities can be avoided when using FTIR measurements with the MS measurements in parallel. Because FTIR provides a compound-specific fingerprint for each species, compounds such as CF4 and C2F6 exhibit unique spectral characteristics using FTIR spectroscopy. 10. Ion source surface and filament reactions with process compounds may lead to the formation of artifact ions that complicate interpretation of mass spectra. In addition, gas-phase reactions may occur in the ionization source of the MS. 11. Because of the instability of MS calibrations in time, there is a need for some internal standards or calibration of MS in the facility just before sampling at the tool. This requires coordination with the ESH staff of the facility operations to approve the use of necessary calibration gases within the cleanroom facility. Use of high concentration calibration gas mixtures in facility operations may be prohibited and impractical. 12. Homonuclear diatomic species are not infrared active; therefore, the FTIR spectrometer cannot detect them. A second analysis technique, such as MS, is necessary to monitor the presence of these species.
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20 13. The linear dynamic range for calibration on a peak is limited. The wide range of compound concentrations (reactant gases and byproducts ) requires the calibration for use of a minimum of two FTIR path lengths to achieve quantitative measurements ranging from the percent level down to parts per million concentrations. FTIR offers lower sensitivity (higher limit of detection) relative to MS techniques for many compounds. 5 ADDITIONAL ANALYSES OF PROCESS BYPRODUCTS
Additional samples may be collected that consist of materials gathered during routine maintenance of the manufacturing tool. Condensed phase samples include solid material scrapped from process lines and chambers, solids collected in cold traps and abatement devices, wipes of interior surfaces of the tools, and fluids from pumps. Collection of scrapings, wipes, and pump oils cannot be easily correlated with the gas phase sampling described earlier in the template methodologies. Therefore, it is difficult to develop an estimate of mass balance for these materials. Additional data on the use of the tool during the last reported or known PM activity should be gathered. Pertinent information includes last scheduled or unscheduled maintenance date, total number of process cycles, and types of chemistries conducted. It is feasible to collect condensible materials using cold trap impinger systems (Figure 6). The investigator should be aware that these collection procedures may result in the concentration of toxic, pyrophoric, or explosive materials.
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21
Figure 6 5.1
Impinger Sampling System
Sampling and Analysis of Condensed Phase Particulates
The focus of real-time sampling and analysis efforts is on gas streams during actual wafer processing. However, condensed phases, such as large particulates, chamber wall coatings, pump fluids, or polymeric materials formed during processing also may contain byproducts of interest. These condensed phases can be sampled only during tool downtime, such as PM operations. A battery of separation and analysis techniques can be used to analyze these materials (Figure 7).
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22 Solid and condensible materials entrained in gas streams should be collected using a cold trap device (Figure 6) connected to the gas stream at the manifold connection point C or E of Figure 4. A known volume of tool gas should be drawn through the cold trap for a known time period, typically a 10-wafer run. The collected materials should be removed and weighed on an analytical balance to a precision of 1%. The total mass of solids should be used in calculations of the amount of solid sorbed onto the tool as solids. The solids may be characterized by many analytical techniques including direct probe MS, ion chromatography, and FTIR. Particulate deposition in sample lines, valves, or cell interiors may be observed. Process gases may cause reactions and/or adsorptions to cell walls and manifold components. Filtering devices may be used to limit the particulates entering the sampling system. SS traps may react with process gases; Teflon particulate filters are susceptible to leaks. Qualitative information from solid or liquid condensed phase samples has limited use in mass balance calculations. The uncertainty of the spatial distribution of condensed materials in the tool and any tool history contribute to the overall uncertainty of the mass balance. 5.2 Odors Analysis During Preventive Maintenance
Open-path testing during PM activities was largely inconclusive. No compounds were detected by FTIR during any of the PM tests. It is likely that one or more of the following factors contributed to this: no compounds were actually present because of tool cleanliness or previous PM activity; compounds were present but failed to cross the IR beam because of cleanroom air currents; and/or compounds crossing the IR beam were not detected because of the extremely short path length. Work by Shih-Yi and coworkers2 detected solvent vapors in the 50 to 200 ppbv range. Extremely short (5 to 7 ft) path lengths were used for the open-path PM tests, which is much shorter than the length required to fully collimate the beam. Hot spots were noticed along the path, requiring some tedious adjustments to achieve optimum alignment and signal strength because of the close range. For further work in this area, the instrumentation should be optimized for open-path FTIR data collection. In addition to condensed phases, odors that occur during PM operations can be sampled using point sampling, integrated with techniques such as SUMMA canisters, and analyzed using high sensitivity MS. These offline sampling and analysis techniques described below are characterized as solids analysis, liquids analysis, and odor characterization. Open-path FTIR and GC/MS analyses of SUMMA canisters were performed when tool chambers were opened for PM. The stability of SUMMA canisters was not characterized to determine whether constituents were actually present in the exhaust stream or whether they were generated in reactions during transport and storage of the samples. No compounds were detected above background, except in the TEOS chamber for oxide CVD (Applied Materials 5000), where ethanol was detected during preliminary studies. The presence of ethanol is consistent with the TEOS chemistry, in that TEOS may react with available water to form the alcohol.
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23
Figure 7
Scheme for Analysis of Condensed Phases and Pump Oils
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24 Solid materials obtained from chambers and tool ducts should be collected in Teflon containers. The surface area of the sampled regions should be recorded so that the amount per area and total mass balance per tool can be determined. Fractions from these tests should be analyzed using ICP/MS, ICP-AES, AAS, or other multielement techniques, yielding a total profile for each fraction. 6 AN EXAMPLE OF A DETAILED TOOL ANALYSIS BY FTIR
A detailed tool analysis by FTIR should include several pre-sampling steps such as a gauge study and a time response study. The gauge study ensures stability of the measurement system, while the time response study identifies the temporal response of the sampling system to changes in gas flows. After these studies, the calibrations and on-site sampling can proceed. For the work presented in these sections, detailed flowcharts convey the sequence of events and decisions. Figure 9 is a key to the meaning symbolized by the shapes used in the logical flowcharts. Figure 10. is the general decision tree for the sampling and analysis plan described but does not include the preliminary decisions outlined in Figure 8. The process in Figure 1 should be done before the processes in Figure 10 through Figure 15, which are for procedures outlined in this section.
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25
Figure 8
Selecting an Approach to Byproduct Characterization
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26 6.1 Measurement System
The FTIR measurement system used for studies by MRI is a Midac Corporation Model 2500 FTIR instrument equipped with a potassium bromide (KBr) beam splitter. The FTIR sampling system uses a 15 cm fixed path-length cell and a variable path-length cell at a 4 m path. The optical path may pass through either cell with a simple mirror adjustment (see Figure 10). The gas flows through both cells in series, the 15 cm cell followed by the 4 m cell (Figure 6). The variable path length cell is adjusted to 4 m path before all testing and verified periodically in the field using a known concentration ethylene calibration transfer standard (CTS). Both the FTIR cells and the internal mirror-mounting hardware used for these experiments are Teflon-coated. The internal mirrors are made of protected silver. The cells are operated at 130C to maximize moisture removal and prevent the adsorption of compounds onto sample system surfaces. All sample extraction lines, connections, and valves are made of Teflon or Monel. The length of the extraction lines is minimized to keep surface area to a minimum. Cell pressure was measured with an Edwards Barocell Model 600AB attached immediately downstream of the cell. As necessary, the cell is isolated by closing a Monel leak-free valve between the cell and the pump. It is important to remember that this is only one of the arrangements that can be used for FTIR sampling. Other options include using two FTIRs and two cells, many cells, and a multi-pass cell that can be adjusted to yield many path lengths. These path-length adjustments on a single multipass cell are difficult in the cleanroom because of the cleanroom gloves, but are not as difficult in the laboratory. If more than one FTIR is used on multiple cells, the files must be manipulated so that responses among the instruments agree. 6.2 Gauge Study
Figure 11 is a flowchart of the gauge study procedures. This procedure should be performed at the beginning of every sampling session and for at least one of the gases targeted for analysis when in the facility. A process gas, such as C2F6, is recommended. Before conducting on-site sampling, a study of tool repeatability (gauge study) should be performed using the sampling system described above. The study is designed to measure the stability of the entire measurement system; it should measure the following characteristics: 1. Stabilization time and short-term stability of the complete sampling system, as a function of reference gas absorbance/concentration and flow rate. 2. Stability of the IR system to the change in optical path encountered if switching between cells is required. 3. Day-to-day repeatability of the sampling system and measurement method. This is needed only if a Passive Data Collection (PDC)-based detailed study (see Section 6.6) is planned.
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27
Figure 9
Key to Chart Box Shapes
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28
Figure 10
General Decision Tree for the example of a Detailed Tool analysis by FTIR
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29
Figure 11
Flowchart for the Gauge Study Procedures in the Example of a Detailed Tool Analysis by FTIR
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30
Figure 11 (Continued)
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31
Figure 11
(Continued)
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32
Figure 12
Flowchart for the Time Response Study Procedures in the Example of a Detailed Tool Analysis by FTIR
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33
Figure 13
Flowchart for the Off-site Calibration Procedures in the Example of a Detailed Tool Analysis by FTIR
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34
Figure 14
Flowchart for the On-Site Testing Procedures in the Example of a Detailed Tool Analysis by FTIR
On-site Testing Procedures Include (a) Instrumentation Setup and Quantification;
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35
Figure 14 (Continued) (b) Point-of-Use Calibration and Time Response Study; and
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36
Figure 14b (Continued)
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37
Figure 14 (Continued) (c) Sampling at the Tool During Process Runs
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38
Figure 15
Flowchart for the Point-of-use Calibration in the Example of a Detailed Tool Analysis by FTIR
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39 The reference gas should consist of dry nitrogen solutions generated using the gas dilution system containing representative compounds for the specific tool being tested. The gas dilution system used for this example is a Kin-Tek 491M with a permeation oven and a second module containing an MFC. The following procedure should be performed daily. 1. If an MCT detector is used, it is cooled with liquid nitrogen and stabilization is monitored based on the interferogram peak-to-peak energy. The time required for stabilization is recorded. Leak check the system and verify that the residual moisture is within the limits established in the QC criteria below (Table 2). 2. Flow 20 ppm ethylene through the first cell and record the temperature, pressure, and measured absorbance. 3. Collect two backgrounds, convert to absorbance, and check the RMSs < 0.009 between 850 and 950 cm-1. 4. Flow reference gas mixture through the first cell, and record the temperature, pressure, and measured absorbance. The gas flow rate is constant yielding a cell pressure near that anticipated during tool sampling. a. Ten measurements of the absorbance at 10-second intervals are recorded. b. Both the inlet and outlet valves to the cell are closed, and the absorbance is recorded 20 times at 5-second intervals. Again, record the cell temperature and pressure. c. The inlet and outlet valves to the cell are opened to allow the gas flow to restabilize, and 10 more sets of absorbance at 10-second intervals are recorded. Again, record the cell temperature and pressure. d. Both valves are closed again and the absorbance is recorded 20 more times at 5-second intervals. Again, record the cell temperature and pressure. 5. The steps above are repeated for the second cell and for any other reference gases to be tested. 6. All gases are shut off and a 4-hour 100% stability test is performed on the IR system. The system must be purged of gas and a 100% measurement is performed each half hour for 4 hours. This test is performed by allowing the IR beam to pass through one cell each night at the end of the studies. The cell used for this study is alternated between nights. The spectrometer will be set up to collect in multi-collect mode with 30 minutes between scans. Each subfile contains 16 coadditions. The detector should be filled with liquid nitrogen. 7. The data collected are reviewed and if they meet QC criteria (Table 2), the system is suitable for tool tests. 6.3 Time Response of the Sampling System Study
Figure 12 is a flowchart of the time response study procedures. The time response of the sampling system study should focus on the temporal response of the sampling and measurement system to changes in the inlet gas flow and composition. This test should be performed with gases representative of those expected at the tool. The gases, C2F6, CO2, SiF4, and HF, are representative of those expected in this example. The sampled gas should be diluted to the chosen concentration with ultrapure nitrogen and the manifold should be heated to an external
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40 temperature of 130C (if diatomic acids are anticipated) and the cell pressure maintained at the pressure expected during sampling. The time response should be measured as follows: 1. For each of the gases mentioned above, three concentrations are selected ranging between one-tenth and 10 times the concentration expected in the on-site sampling. This range may be modified if the MFCs do not allow for gas concentrations in this absorbance range. 2. The Kin-Tek dilution system is adjusted to yield the selected gas concentration. At time = 0 seconds, nitrogen is sampled; at time = 10 seconds, begin sampling the selected gas concentration. 3. Absorbance measurements are recorded at 1-second intervals until the signal has reached stability (or 180 seconds have passed). Once reaching stability, the gas is turned off and the absorbance measurements recorded until signal has returned to the background level. 4. This procedure is repeated for the other concentrations, all gases, and both cells. 5. The response time of the manifold is calculated. The time response data should be reviewed by laboratory personnel to determine whether the observed time lags will interfere with the successful completion of the sampling program. If the lags are greater than theory predicts, then it may be necessary to redesign the sampling system before proceeding. 6.4 Off-Site Calibrations
Figure 13 is a flowchart of the off-site calibration procedures. A detailed outline of suggested calibrations is found in Section 3.2.3. FTIR is calibrated for quantitation of real-time gases off site using a minimum 5-point standard curve. The calibration curve information has been used to establish a library for subsequent quantitations of FTIR data acquired in real-time. Representative spectra are shown in the appendix. Replicate analysis at each point, linear regression, and confidence interval for line and individual points are performed to establish the statistical validity of the quantitations. Pure gas in nitrogen should be added directly to the FTIR cell using a Kin-Tek 491M. The gas suppliers, purity, CAS number, molecular formulas, and compounds are detailed in Table 4. The Kin-Tek system should be modified by replacing standard MFCs with acid-resistant MFCs to handle HF. Once the gas concentration in the sampling system has stabilized, a calibration consisting of 256 co-added scans should be collected. Concentrations should be modified as needed to bracket the estimated sample concentration, to quantitate only on nonsaturated (absorbance < 1 absorbance unit) peaks in the linear range of the calibration curve, and to be in a concentration range allowing determination of the detection limit for the compound by extrapolation to 3:1 signal/noise. The 5-point curve consisting of the five concentrations bracketing the sample concentration is repeated five times in random order.
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41 Table 4
Compound Boron Trichloride Carbon Dioxide Carbon Dioxide Carbon Monoxide Carbon Monoxide Carbon Tetrachloride Carbon Tetrafluoride(Freon 14) Carbonyl Fluoride Chlorine Ethylene Hexafluoroethane Hydrogen Bromide Hydrogen Chloride Hydrogen Fluoride Hydrogen Fluoride Hydrogen Fluoride Silicon Tetrachloride Silicon Tetrafluoride Sulfur Hexafluoride Trifluormethane(Freon 23) Tungsten Hexafluoride
Chemicals Used by MRI

CAS No. 10294-34-5 124-38-9 124-38-9 630-08-0 630-08-0 56-23-5 75-73-0 353-50-4 7782-50-5 74-85-1 76-16-4 10035-10-6 7647-01-0 7664-39-3 7664-39-3 7664-39-3 10026-04-7 7783-61-1 2551-62-4 75-46-7 7783-82-6 Purity 99.9% 1% 99.995% 1% 99.995% 99.9% 99.9% 85% 99.5% 20ppm 98% 99% Anhydrous Anhydrous 1% Perm tube Perm tube 99.99% 99.8% 98% 99.9% Supplier Aldrich Scott Matheson Scott Matheson Aldrich Aldrich Atomergic Aldrich Scott Aldrich Aldrich Matheson Matheson Matheson KinTek KinTek Pfaltz & Bauer Scott Aldrich Aldrich
Molecular Formula BCl3 CO2 CO2 CO CO CCl4 CF4 COF2 Cl2 C2H4 C2F6 HBr HCl HF HF HF SiCl4 SiF4 SF6 CHF3 WF6
Chemicals Purchased by MRINever Used Nitrous Oxide Nitrogen Trifluoride Ammonia Phosgene N2O NF3 NH3 COCl2 10024-97-2 7783-54-2 7664-41-7 75-44-5 99% Technical 99.99% Aldrich Air Products Aldrich Matheson
SEMATECH
42 6.5 On-Site Testing
Figure 14 is a flowchart of the various procedures for on-site testing. Sampling should proceed in several stages, as defined below: 6.5.1 Instrumentation Setup and Quantification
After the sampling system is installed at the tool, the first step should be to ensure that the equipment is operational and performs as it did during the gauge study. After leak checks are performed according to the facility safety procedures, the daily procedure outlined previously in the gauge study should be performed twice (possibly within a single day), and the data obtained should be reviewed to determine if the sampling system is unchanged. After the verification of sampling system, the variability of the entire system being tested (tool, sampling manifold, and analytical instrument) must be determined. To accomplish this, one process gas should be manually admitted into the tool chamber at three different concentrations. The highest concentration should be at the recipe maximum flow for the gas to be tested, with the other two concentrations being at 50% of the maximum and at 10% of the maximum. For each concentration, at least 30 scans should be taken, which should be used to establish variance of the tool, instrument, and sampling system. 6.5.2 Point-of-Use Calibration
Figure 15 is a flowchart of the point-of-use calibration procedures. After the sampling system is determined to be operating properly, a check of sampling bias should be performed. The first step involves flowing unreacted gases as outlined above through the system. The measured concentrations, as determined by calculations using the calibration information determined earlier, are compared to the expected values (as determined by process recipe, tool MFC, and ballast gas MFM). Review the resulting data to determine if additional calibration is necessary. If additional calibration is required, postsampling calibration according to the methodology used in off-site calibrations should provide valid quantitation. The time response of the measurement system to changes in the flow rate (of unreacted gases) should be measured and compared to the time resolution needed to adequately capture process changes. The time response is determined by flowing a process gas such as C2F6 through the tool with the sampling valve closed while the manifold is pumping. The valve is opened and the time required to achieve a steady state is recorded. If the time responses of unreacted gases are similar to those observed in the accumulation and gauge studies, the plasma-on time response should be measured. The IR signals for all gases for which calibration was performed should be monitored as a function of time during a process resembling the normal etch or deposition. The plasma is struck in the usual fashion, then C2F6 is introduced under the recipe conditions of gas flow, pressure, and RF power. This state is maintained until all IR signals reach steady state or until 120 seconds have elapsed (whichever is shorter), at which time the process recipe step is ended and the next step is initiated. The step-by-step test continues until all FTIR signals have stabilized, at which time the plasma should be extinguished. These tests should be reviewed to ensure the response of the sampling system is 10% of the process step time.
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43 6.5.3 FTIR Data Acquisition, Processing, and Management
The general format for the sampling and analysis events should involve alternating periods of data collection and analysis. Laptop(s) and a PC, with adequate disk space, should be provided to store and manipulate data in a real-time fashion. FTIR interferograms should be collected at the tool and transferred to a data storage media such as a SyQuest removable hard disk. The data should be Fourier transformed and converted to absorbance files. The interferograms, spectra, and absorbance files should be backed up. Conventional plots should be printed showing a spectrum at a specific time, a plot of concentration as a function of time, and a plot of spectra as a function of time. Once set-up and point-of-use calibrations have been completed on-site, tests should begin after the following: 1. Confirm with the process engineer that the tool is in functional condition and available for sampling. 2. Obtain and characterize an adequate supply of wafers. Record lot numbers, size, photoresist type and lot, substrate, etc. 3. Ensure that the data collection and interpretation systems are equipped with tape drives or other means for convenient archival and transport of data. 6.6 Passive Data Collection Based Sampling and Analysis
For purposes of validity, precision, and reproducibility, it is necessary to conform to SEMATECH PDC guidelines and objectives specified in Technology Transfer #91090684AENG, Passive Data Collection and Analysis. PDC samples a process while running in normal production mode. The data collection is passive because no active engineering adjustments are made to the process beyond those required for normal operation. Specific goals of the PDC guide the details of the sampling plan. Multiple runs for each test help to identify variability and to determine statistical confidence for the process. For a single-wafer system, at least 10 wafers should be run for a given test. This should afford the needed population of wafers to determine the wafer-to-wafer statistical variation. After data collection, the data are analyzed for stability and capability through graphical and statistical methods. Process stability occurs when the mean is constant and variability is predictable over time. A capable process occurs when all measurements fall within the specified limits. Data should be summarized and conclusions drawn from the PDC. 7 AN EXAMPLE OF A DETAILED TOOL ANALYSIS BY MS
Many commercial MS systems are available featuring a wide variety of capabilities. The best choice of instruments primarily depends upon the specific requirements of a particular investigation (Figure 8). The specific analysis procedures employed and minimum performance criteria also will depend on the purpose of the investigation as well as the type of instrument being used. If an MS system is used to perform quantitative analyses, procedures similar to FTIR spectrometry (described in Sections 6.1 through 6.6) need to be developed for MS. Time and other limitations precluded the development of such procedures for this template methodology. The following detailed information about MS systems can be used to develop an MS protocol before beginning on-site MS sampling program. The MS systems used for this work are described in detail, and a general sampling and analysis approach is presented. The analysis
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44 procedure should be modified to fit the requirements of the particular investigation and the capabilities of the analytical system. 7.1 Instrument Selection
The MS and data acquisition system selected for this type of work should have a mass range capability of at least 1 to 500 amu. A secondary electron multiplier detector is recommended over a Faraday cup detector because it provides greater sensitivity and faster scan rates. The system should be capable of scanning the entire mass range in 1 second or less to provide the temporal resolution required to accurately track tool process steps. The vacuum chamber should be equipped with a pressure monitoring device. A Bayard-Alpert type ion gauge is recommended because it provides adequate sensitivity for accurate control of the analyzer pressure. If the MS is to be connected directly to the tool process chamber, an alarm function of the pressure monitoring device can be used to trigger a solenoid-activated isolation valve located between the MS and the tool chamber, thereby protecting the tool in case the vacuum pump fails. Turbomolecular vacuum pumps are recommended because they are compact and convenient and provide a clean vacuum without the need for cold traps, etc. The mechanical forepump should be filled with a corrosive-resistant fluid, such as Krytox, to withstand corrosive gases to which it is exposed. The inlet to the ion source must be fitted with a high pressure sampling system to restrict the flow of gas into the ion source. A system that employs a controllable flow restriction (e.g., metering valve) is recommended over a fixed restriction. A controllable flow restriction is less susceptible to plugging when sample gas streams contain particulates, which allows for control of the analyzer pressure. 7.2 MS Systems Used For This Study
Two quadrupole MS systems were used for the direct sampling activities in this work: one was connected directly to the tool process chamber and the other was connected to the sampling manifold in the post-pump and post-abatement locations. Both instruments used were Fisons MD-800 models controlled by LAB-BASE data acquisition software. The systems were equipped with a closed-type electron impact ion source and a secondary electron multiplier detector. The vacuum chambers were pumped by 60 L/minute turbomolecular pumps backed by mechanical pumps filled with Krytox fluid. A Bayard-Alpert type ion gauge was fitted to the vacuum chamber of each instrument for monitoring the analyzer chamber pressure. Both were equipped with self-contained perfluorotributulamine (PFTBA) reference gas systems to be used for mass calibration. MS systems are capable of scanning from 1 to 800 amu in less that a second in the full scan operating mode with unit amu resolution over the entire scan range. For this work, scan ranges of 10 to 750 amu were typically used. To provide for good temporal resolution of the obtained data, scanning rates of 1 scan/second were used when directly monitoring the tool process chamber. Temporal resolution requirements are less stringent at the post-pump and post-abatement locations because of the large influx of ballast gas at the pump and the relatively long lag times involved. At these locations, scanning rates of 5 sec/scan were typically used.
SEMATECH
45 The gas flow into the MS that was interfaced directly to the tool process chamber was restricted through the use of an all SS metal bellows-sealed metering valve. The ion source entrance line also was modified to allow for the higher conductances required for sampling from lower pressures (e.g., 10 m Hg typical of some of the tools encountered in this study). The valve used for these studies (Nupro 4-BMW) had a flow coefficient (Cv) of 0.019. This technique proved to work well at the pressures encountered in this work (200 m Hg). It is expected that a larger metering valve would be required for sampling from pressures as low as 10 m Hg. For sampling gases from near atmospheric pressure, as in the case of post-pump exhaust line sampling, a much finer metering valve was required. The valve used for this study (Nupro-SS4) had a maximum flow coefficient of 0.004. The flow control provided by this valve was somewhat coarse but was adequate when adjusted carefully. 7.3 Instrument Preparation and Characterization
The ion source of MS requires low operating pressures (typically < 1 10-4 torr). This means the ion source inlet must be fitted with a flow-restricting interface to allow for direct sampling from higher pressures. Since MS performance is often sensitive to ion source pressure variations, a controllable flow restriction (e.g., metering valve) is recommended so that the optimum pressure can be maintained. The complete system should be assembled and tested in the laboratory before deployment for field sampling. System performance should be evaluated under the conditions similar to those expected to be encountered during actual sampling activities, and the parameters (e.g., analyzer pressure, tuning parameters, etc.) required for optimum performance should be established. The system also should be challenged with any corrosive or highly reactive gases that might be encountered during sampling to evaluate the overall performance of the system when exposed to these compounds. A multiplier gain curve should be established for each instrument. This is accomplished by systematically varying the voltage applied to the secondary electron multiplier and recording the resulting change in sensitivity. This information can subsequently be used to set the instrument sensitivity to a level that is suited to the needs of the analysis at hand. A benchmark spectral response profile should be established for each instrument based on the relative intensities of several PFTBA peaks when the instrument-tuning parameters are optimized. This response profile will be used as a target for daily tuning of the MS. 7.4 Instrument Installation
The MS should be installed at the appropriate sampling locations well in advance of any scheduled sampling activity to allow ample time for pumpdown and background stabilization. Once the instruments are installed, pumpdown is initiated and the ion source and interface heaters are brought to operating temperature. The ion source filament can be turned on when the pressure inside the analyzer chamber has dropped to < 1 10-4 torr, as indicated by the ion gauge reading. Tuning, mass calibration, etc., can be initiated once the analyzer pressure (with the inlet blanked off) has reached a level significantly lower (e.g., 0.1 X) than the desired operating pressure. The time required for complete pumpdown will vary, depending on how long the system was open
SEMATECH
46 and the environment that it was exposed to. A minimum of 1 to 2 hr can generally be expected. Longer periods are recommended (overnight, if possible) to allow for background stabilization. 7.5 Initial and Continued Quality Control
Once the instrument has pumped down, the entire MS system should be checked for leaks. This can be accomplished by several techniques, such as monitoring leakup rates, observing air peaks in the background spectra; and flooding the MS with an inert gas, such as helium or argon, and observing the instrument response for the appropriate ion. At the beginning of each sampling day the instrument should be tuned and the mass range should be calibrated for accurate mass assignment. This is normally done with a self-contained reference gas inlet system. The scan parameters (scan range and cycle time) are set to the values that are to be used for sampling. The reference gas is turned on, and the tuning parameters are adjusted until the spectral profile matches a predetermined benchmark profile to within a predetermined criteria with < unit mass-to-charge ratio resolution over the entire scan range. The mass assignment of the individual reference gas peaks are compared with their known true values. The mass assignments should agree with the true value to within 0.1 amu over the entire scan range. If the spectral profile and mass assignment do not meet acceptance criteria, the instrument should be returned and recalibrated. If it still fails to meet acceptance criteria, the ion source probably needs cleaning. In this case, the instrument should be shut down and the ion source removed and cleaned according to the manufacturer's instructions. A log should be kept of each day's tuning parameters, spectral profile, mass assignment accuracy, and the analyzer pressure with the ion source inlet blanked off. 7.6 Sampling
Once acceptable instrument performance has been demonstrated, sampling can begin. The instrument sensitivity should be adjusted to a level that is suitable to the demands of the investigation by adjusting the voltage on the electron multiplier. A predetermined electron multiplier curve can be helpful in selecting a suitable setting. The isolation valve between the ion source inlet and the tool process chamber or sampling manifold is opened, and the ion source inlet metering valve is adjusted to provide the desired analyzer pressure. Data acquisition can now be initiated in accordance with the particular data system in use.
SEMATECH
47 8 BIBLIOGRAPHY
1. Byproduct Characterization: Qualitative Results from Six SEMATECH Tools, Technology Transfer #95022711B-ENG (1995). 2. Shih-Yi Chang, Tai-Ly Tso and Jiunn-Gung Lo, Determination in Situ of Chemical Solvent Vapors in a Semiconductor Workplace with an Open Path FTIR Spectrometer, Journal of the Chinese Chemical Society (1994), Vol. 41, pp. 685-692. 9 FTIR SUGGESTED READING
1. P. R. Griffiths and J. A. deHaseth, Fourier Transform Infrared Spectrometry, New York: Wiley-IntersciencePublishers (1986), pp. 1-11, 213-15. 2. I. N. Levine, Molecular Spectroscopy, New York: Wiley-Interscience (1975). 3. I. N. Levine, Physical Chemistry, Third Edition, New York: McGraw-Hill (1988) pp. 699-761. 4. D. A. Skoog, Principles of Instrumental Analysis, Third Edition, New York: Saunders College Publishing (1985), pp. 160-181, 315-357 5. E. B. Wilson, Jr., J. C. Decius, and P. C. Cross, Molecular Vibrations: The Theory of Infrared and Raman Vibrational Spectra, New York: Dover Publications (1955).
SEMATECH
48 10 AAS abatement AES ballast gas Beers Law chamber CLS CTS GLOSSARY Atomic absorption spectroscopy The process stream is burned in an abatement system Atomic emission spectroscopy Nitrogen is added to the processes gases after the chamber to bring the pressure of the stream to approximately atmospheric pressure Beers Law is the basis of FTIR calibrations. Absorbance = (path concentration absorption coefficient); see details in Section 3.2.3 Plasma etch or CVD process occurs in the tool chamber Classical least squares Calibration transfer standardThe absorbance of the same concentration of a chosen gas is measured and used to assess longand short-term stability of the FTIR instrument Chemical vapor deposition Environment, Safety, and Health Fourier transform infrared spectrometry Gas chromatography/mass spectrometry Heteronuclear diatomic is a molecule consisting of two unlike atoms Homonuclear diatomic is a molecule consisting of two like atoms Inductively coupled plasma Mercury cadmium tellurideMCT is a semiconductor used as a detector of IR energy when cooled to liquid nitrogen temperatures Mass flow controllerAn MFC is used to control the flow of gas through the sampling system Mass flowmeterMFM measures, but does not control, the flow of the gas stream Mass spectrometry The optical beam passes through the cell multiple times to increase the available pathlength per cell length Passive data collection PerfluorotributylamineThis compound is used for a calibration system built into most MS systems as a standard feature Partial least squaresPLS is a multivariate statistical technique Preventive maintenance
CVD ESH FTIR GC/MS heteronuclear diatomic homonuclear diatomic ICP MCT MFC MFM MS multi-pass cell PDC PFTBA PLS PM
SEMATECH
49 point-of-use calibration Point-of-use calibration is a calibration of the absorbance of a peak for a compound as a function of the concentration of the compound added to the chamber Personal protective equipment Parts per millionMolecules of the compound of interest per million molecules of everything present Photoresist Quality control Root mean square Stainless steel SUMMA canisters are used to collect gaseous samples, a point sampling technique using the canisters Tetraorthosilicate VCR is a trade name
PPE ppm PR QC rms SS SUMMA canisters TEOS VCR fittings
SEMATECH
SEMATECH Technology Transfer 2706 Montopolis Drive Austin, TX 78741 http://www.sematech.org

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S68 Final Report: Template Methodology and Lessons Learned for Sampling and Analyzing Tool Effluents

1995 SEMATECH, Inc.

December 31, 1995

Technology Transfer # 95123039A-TR

Technology Transfer # 95123039A-TR

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Technology Transfer # 95123039A-TR

Direct Sampling Manifold Schematic

Technology Transfer # 95123039A-TR

Sampling Manifold Schematic with Instrumentation (FTIR and MS)

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Construction Details of the Sampling Manifolds

Description /4 in SS Swagelok w. TFE seals /4 in monel bellows valve, Swagelok connectors /2 in SS

/8 in SS Swagelok needle valve, TFE glands and seals

/4 in SS Swagelok /4 in Monel Swagelok

Technology Transfer # 95123039A-TR

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General Sampling Plan of the Tool

Lessons Learned About the Manifold Design and Use

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Connection System for MS to Tool Sampling

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Criteria for MS, GC/MS

Peak shape Sensitivity

Before/after run Before/after run

Mass axis Blank Zero N2

Before/after run Each day

FTIR FTIR Sampling, Post-pump

QC Criteria for FTIR

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Impinger Sampling System

Sampling and Analysis of Condensed Phase Particulates

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Scheme for Analysis of Condensed Phases and Pump Oils

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Selecting an Approach to Byproduct Characterization

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26 6.1 Measurement System

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Key to Chart Box Shapes

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On-site Testing Procedures Include (a) Instrumentation Setup and Quantification;

Technology Transfer # 95123039A-TR

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Figure 14b (Continued)

Technology Transfer # 95123039A-TR

Figure 14 (Continued) (c) Sampling at the Tool During Process Runs

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