Background Statement for Ratification Ballot of SEMI Draft Document #5765 Revision to SEMI C TEST METHOD FOR ppm AND ppb HUMIDITY STANDARDS

Transcription

1 Background Statement for Ratification Ballot of SEMI Draft Document #5765 Revision to SEMI C TEST METHOD FOR ppm AND ppb HUMIDITY STANDARDS Note: This background statement is not part of the balloted item. It is provided solely to assist the recipient in reaching an informed decision based on the rationale of the activity that preceded the creation of this document. Note: Recipients of this document are invited to submit, with their comments, notification of any relevant patented technology or copyrighted items of which they are aware and to provide supporting documentation. In this context, patented technology is defined as technology for which a patent has issued or has been applied for. In the latter case, only publicly available information on the contents of the patent application is to be provided. Notice: This document was approved with additional technical change during adjudication of Letter Ballot # 5495 by the European Chapter of the Liquid Chemicals Global Technical Committee during its meeting on 10/6/2015. This Ratification Ballot is issued in order to satisfy the conditions for Letter Ballot approval by the Liquid Chemicals Global Technical Committee in accordance with of the Regulations. If the Ratification Ballot voting response meets the minimum acceptance conditions per Regulations 10, then it will be automatically published. One copy of the revised Draft Document is included to show the intended final published version. Only these proposed additional technical changes are shown in the other copy of the Draft Document with revision markups showing these intended changes, as an aid to the voter. Additions are indicated by underline and deletions are indicated by strikethrough. Contents for vote are limited to only considering these proposed additional technical changes. All content for a new Standard and Safety Guideline or all proposed technical and editorial changes for revisions of Standards and Safety Guidelines that were included in the original Letter Ballot and passed TC Chapter review, including the ones passed with editorial changes, are incorporated, without revision markups, in both copies. All other editorial changes, if any, made and approved during the TC Chapter review are incorporated also, without revision markups, in both copies. Background The following is the complete list of the new proposed technical change(s) with their justifications: Technical Changes: 1. Below Equation 3: From: where P is the emission rate of water from the certified permeation or diffusion tube (nanograms per minute), F is the flow rate of dilution gas in ml/min, k converts P to nanoliters per minute. To: where P is the emission rate of water from the certified permeation or diffusion tube (nanograms per minute), F is the flow rate of dilution gas in ml/min, k converts P to nanoliters per minute. The factor k is the molar volume of gas at a reference temperature divided by the molecular weight of the permeating compound. For water (molecular weight 18), when the reference temperature is 0 C, k=1.24. At reference temperature 25 C k=1.36. Justification: state values for K From: Adjust the calibration to Ca for R1 response.

2 To: Adjust the reading (or calibration correction curve) to indicate concentration Ca for R1 response. Justification: Clarity 3. Delete equation 6 in 7.5.1: The definition of dilution factor is revised to: (6) 4. In 7.5.1, delete paragraph following equation 6: The background, B, is determined by removing the permeation or diffusion tube from the system and capping off its point of connection, or by preventing the source from delivering moisture by some other means. The same equation for c applies as does the statement regarding analytical uncertainty. Review and Adjudication Information Task Force Review Committee Adjudication Group: Task Force for Permeation Tubes Joint EU Gas & Liquid Chemicals TC for Trace Moisture Calibration Chapter Date: October 26, 2016 October 26, 2016 Time & 10am 12 pm, CET 2pm-5pm, CET Timezone: Location: SEMICON Europa SEMICON Europa City, Country: Grenoble, France Grenoble, France Leader(s): Jean-Marie Collard (Solvay) jean-marie.collard@solvay.com Jean-Marie Collard (Solvay) jean-marie.collard@solvay.com Standards Staff: James Amano, jamano@semi.org James Amano, jamano@semi.org *This meeting s details are subject to change, and additional review sessions may be scheduled if necessary. Contact the task force leaders or Standards staff for confirmation. Telephone and web information will be distributed to interested parties as the meeting date approaches. If you will not be able to attend these meetings in person, but would like to participate by telephone/web, please contact Standards staff. Notice: Additions are indicated by underline and deletions are indicated by strikethrough.

3 SEMI Draft Document #5765 Revision to SEMI C TEST METHOD FOR ppm AND ppb HUMIDITY STANDARDS *Copy with Technical Change Markup* 1 Purpose 1.1 This test will determine whether or not the quantity of moisture delivered by a gaseous moisture standard is in agreement with that predicted for the standard on the basis of physical principles. It is expected that this method will be used to validate moisture standards before they are first placed in use, when deviation from expected performance is likely or suspected, and at other times as seems necessary. 1.2 The test method assumes the existence of a reliable moisture analyzer. Although extensive precautions are described to ensure the validity of the analyzer, it is always possible that the test could yield a faulty result through some unforeseen defect in the analytical equipment. 1.3 Given that moisture generation is subject to many pitfalls, it will be required that the predicted moisture concentration delivered by the standard and the measurement of that level by the analyzer agree. The level of agreement can vary depending on the degree of precision claimed for the moisture standard, but in any case the measured and predicted results should be within 10% over the entire range of the moisture standard. If not, then the validation should be repeated after verifying the physical measurement upon which the prediction is based and any other parameters deemed suspect. 2 Scope 2.1 This method is intended to be applicable to any type of gaseous standard delivering a quantity of moisture in the ppm range or lower, provided the delivered moisture concentration is predictable on the basis of fundamental principles of physics. Thus, any standards which rely solely on characterization by analysis are specifically excluded. 2.2 As part of this test, a procedure is described for qualifying certain moisture analyzers considered suitable for use in qualifying moisture standards. Moisture analyzers intended for other applications may need to satisfy different criteria. 2.3 As the most accurate and reliable moisture analyzers currently available operate primarily in the ppm range, this test focuses on validation of moisture standards in this range. The need for ppb moisture standards is addressed by specifying procedures for reducing the output of ppm moisture standards to the ppb range. NOTICE: SEMI Standards and Safety Guidelines do not purport to address all safety issues associated with their use. It is the responsibility of the users of the Documents to establish appropriate safety and health practices, and determine the applicability of regulatory or other limitations prior to use. 3 Limitations 3.1 If no higher level of accuracy is specified by the user, then a moisture standard shown to be valid by this method will generate moisture levels which deviate from the expected values by no more than 20%. The method leaves open to the user the option of using sound statistical methods to specify that a given moisture standard will generate levels showing a closer agreement with expected values. 3.2 Validation based on this test method is good for a limited time. The acceptable interval between validations depends on the nature of the standard and is not addressed by this method. Thus any citation of validation results should be accompanied by the date(s) on which validation was performed. 4 Referenced Standards and Documents 4.1 This method is based upon principles outlined in F. Mermoud, M.D. Brandt, and J.J.F. McAndrew, Low Level Moisture Generation. Analytical Chemistry, (1991): pp Page 1

4 5 Device Under Test (Test Specimen) 5.1 Definition of a Moisture Standard A moisture standard is defined to be any device capable of delivering a flow of humidified gas at controlled pressure, with no input being provided by the user except nitrogen of UHP grade (moisture <1 ppm) or air of equivalent purity. Any device, such as a permeation tube, which can provide a predictable amount of moisture but does not include a means to deliver gas to and from it, will not be considered a moisture standard by itself. A device which requires gas of higher purity than UHP grade will include a purifier capable of purifying UHP nitrogen to this level. 5.2 Examples of Moisture Standards Some examples of moisture standards and the principles upon which they are based are as follows: Permeation and Diffusion Tube Standards These must include purification means and some means of regulating the outlet pressure. The moisture delivery rate can be calculated based on the weight loss of the tube. Cylinder Standards The standard will include a regulator specified for use with the cylinder. The moisture concentration delivered can be calculated based on that added to the cylinder in preparation. A minimum use pressure must be specified. Methods based on saturation of gas with water vapor at a fixed temperature and pressure. The moisture concentration in the gas may then be calculated from a knowledge of the saturation vapor pressure of water over a plane of the pure phase of ice at the saturation temperature and of the interaction virial coefficients of the gasvapor mixture. The two-pressure and two-temperature methods are refinements of this approach requiring additional chambers whose temperature and pressure must be known. 5.3 Dilution of Standards For all moisture generation methods, lower concentrations can be generated by dynamic dilution (i.e., by combining a known flow of the standard gas with a known flow of dilution gas). A diluted standard is acceptable provided: The standard is validated at high concentration (with the lowest concentration validated being no more than 10,000 times the use concentration), The dilution gas has a moisture level below the stated precision of the analysis (to be verified using the same flow path as during the subsequent analysis, and at the lowest flow rate to be used), The absolute accuracies of the dilution system components are verified by comparison with a reliable flow standard, The linearity of the dilution system can be demonstrated over the entire range of operation. The last criterion is particularly important whenever some portion of the combined flow is discarded, as mixing problems can easily arise at large dilution factors. 6 Procedure 6.1 Validation will be performed using a hygrometer whose output can be directly related to the moisture concentration on the basis of physical laws or using an analyzer which has recently been calibrated by comparison with such an analyzer. 6.2 Hygrometer Qualification Primary Hygrometers Hygrometers can be certified by the National Institute for Standards and Technology (NIST) in the U.S., and similar certification is available in other countries, although the lowest concentration at which certification is available will vary. Repeated certification at yearly or longer intervals can be used to establish reliability. A hygrometer which has been certified by a national standards laboratory to 1 ppm (or lower) moisture in air or nitrogen, and for which reliability has been established over a period greater than or equal to that which has elapsed since certification occurred, is acceptable for validation of a moisture standard and will be referred to as a primary hygrometer Because hygrometers which are suitable for use as primary hygrometers may be less convenient or less readily available than other hygrometers, the use of other hygrometers for validation is also acceptable, provided adequate precautions are taken to ensure that they are operating correctly. These precautions (to be described below) require Page 2

5 using a moisture source to compare a secondary hygrometer with the primary hygrometer. The moisture source need not have been validated in this case Validation of Secondary Hygrometers Secondary hygrometers may be validated by comparing their output with a primary hygrometer when connected in parallel to the same moisture source. The degree of agreement required can vary depending upon the precision to be claimed, but in any case the difference in reading between the two hygrometers should be no more than 10% at any point. Comparison should be made at four moisture concentrations or at two per decade of proposed operation, whichever is less. Half of the comparisons should be made while increasing concentration and half while decreasing, including at least one comparison at the highest point of the concentration range. The first and last comparisons should be at the lowest point of the concentration range. For example, in order to validate a hygrometer for operation between 1 and 100 ppm, it would be acceptable to generate moisture levels at 1, 30, 100, 50, 1 ppm (in that order) and compare the primary with the secondary hygrometer. Comparison of the measured level between the two 1 ppm tests provides a ready indication of hysteresis in the system. If the secondary hygrometer requires calibration using its own standard, calibration should be effected before validation. However, it is acceptable to adjust the calibration in order to improve agreement with the primary hygrometer Frequency of Hygrometer Validation The frequency of validation required for a secondary hygrometer will vary dependent upon the performance established for hygrometers of the same general type. If three successive monthly validations show continuing agreement (within 10%) with the primary hygrometer without calibration adjustment, the validation interval may be extended to three months. Similar extensions of validation interval to six months and one year may be made if no drift is apparent and no calibration adjustments are necessary to bring the secondary within 10% of the primary at all points. 6.3 Validation Procedure for Moisture Standards Validation Within the Range of an Available Primary Hygrometer If a primary hygrometer is available, and its detection limit is no higher than the lowest concentration at which it is desired to use the moisture standard, this is the simplest case. Use the standard to generate four concentration levels or two per decade (whichever is less) in which the standard will be used, half of the concentrations generated while increasing concentration, half while decreasing, including at least one comparison at the highest point of the concentration range. The first and last comparisons should be at the lowest point of the concentration range. If the generated levels, calculated according to the basic properties of the generator (e.g., weight loss of a permeation tube) agree with the measured levels to within 10%, the standard may be considered validated with an accuracy of 10%. Higher validation accuracy requires better agreement. It has been assumed that the precision of the primary hygrometer, as determined by a national standards laboratory, is much better than 10% and may be neglected for validation at the 10% level. Validation at higher accuracy requires explicit consideration of the certification precision If a standard generates only one level, connect it to the hygrometer and allow to come to equilibrium. Assuming the equilibrium level agrees with the calculated level of the generator, disconnect the hygrometer and bring it to equilibrium with either dry nitrogen or ambient air. Then reconnect the moisture standard and reestablish equilibrium between the standard and the hygrometer. Disconnect again and measure a third time. If the three measurements agree within 10% among themselves and with the generated level, the standard is validated It is implicit in the above that the background moisture level of the system be less than 50 ppb so that it can be neglected for all measurements above 1 ppm with an error no larger than 5%. The background moisture can usually be neglected when validating moisture standards in this concentration range Validation Using Secondary Hygrometers If no primary hygrometer is available, then validation can be performed using a secondary hygrometer. If the lowest concentration to be generated using the standard is no higher than the detection limit of the primary hygrometer used for validation of the secondary hygrometer, then the procedure is as above, except that the secondary must first have been validated over the entire concentration range which the standard will be used to generate. (A secondary hygrometer and a moisture standard can be validated simultaneously if the primary and secondary hygrometers are connected in parallel to the moisture standard.) When assessing the accuracy of validation using a secondary hygrometer, it is necessary to take into account the precision of the comparison of the primary hygrometer with the secondary hygrometer as well as the precision of the comparison of the generator with the secondary hygrometer. Page 3

6 7 Practice for Generating ppb Moisture Standards 7.1 The detection limit of the primary hygrometer will generally be on the order of 1 ppm, whereas it will frequently be necessary to use the moisture standard at concentrations below this level, by a factor of as much as1,000. Therefore, valid methods for reducing concentration are necessary. 7.2 Dilution of Validated Moisture Standards If a moisture standard validated in accordance with 6.3 or is diluted with a zero gas stream satisfying the criteria of 5.3, then the resultant diluted standard may be considered valid and may be used for calibration of analyzers, such as APIMS. 7.3 Consideration of Background Moisture In any ppb or lower moisture measurement, it is necessary to consider the background moisture level due to outgassing in the sampling system and residual moisture in the generator + analyzer, and the moisture level of any carrier gas diluting the standard. Often the background will be sufficiently large that it must be taken into account explicitly. The background moisture level is the moisture concentration measured in the absence of a moisture source (i.e., when the driest carrier gas available is fed to the analyzer using the same flow rate and flow path as is used for the sample gas during analysis) It should be noted that the importance of the background level increases for measurements at low concentrations, and that the background level is sensitive to the materials of construction, to the design of the moisture generator, and to its operating temperature If the background moisture concentration is B (ppb), the concentration delivered by the moisture standard is C (ppb) and the dilution factor x is given by: then c, the delivered moisture concentration is given (in ppb) by: (1) The accuracy of calibration will reflect the combined accuracy of the standard and the dilution system, together with the accuracy of the background determination; all must be taken into account in any statement of analytical uncertainty. 7.4 Determining the Background Concentration - The background concentration B should be determined for each calibration. Depending on the design of the moisture generator and sample system B can be difficult (or impossible) to determine as an independent value. For ppb and lower concentrations the system should allow the moisture source to be added or removed without opening the system to the atmosphere while maintaining both the system and source at constant temperature and pressure. Figure 1 shows a schematic of a suitable arrangement. (2) Page 4

7 MATRIX IN PRESSURE UNMETERED CARRIER FLOW (During Zero) FI DILUTION FLOW METERED CARRIER FLOW (During Span) FC CARRIER FLOW FC PERMEATION OVEN BACK PRESSURE ZERO/SPAN SWITCHING BACK PRESSURE ZERO/SPAN GAS OUT (During Zero) DISCARD GAS TO VENT Figure 1 PPB Moisture Permeation Tube System Allowing Background Moisture Correction When the system is in operation with no added moisture standard the operation is designated zero mode. Operation when moisture standard is being added is designated span mode. The following procedure can be used to determine the background concentration, validate a generated moisture standard, validate a secondary hygrometer or calibrate a moisture monitor. If the moisture generator uses a permeation or diffusion tube, finding the background concentration is very simple, even with an uncalibrated hygrometer Install the permeation (or diffusion) tube in the generator. Using the driest carrier/dilution gas available establish flow through all paths in the generator and allow the system to dry down and stabilize. Note that this might take several days Connect to the hygrometer to be calibrated and allow the hygrometer and interconnecting tubing to stabilize again. Use clean, electropolished tubing and fittings, preferably predried In the Zero mode, introduce the carrier/dilution gas through the moisture generator as zero reference, or background gas and observe the response R 0. Use several values of Background flow through the system. Use the value of R0 observed at the lowest flow used for generating the moisture standards for any estimate of accuracy. If the hygrometer is a primary standard, R 0 is the background concentration. For an uncalibrated hygrometer continue Switch to the Span mode and introduce a level of moisture, C 1. When stable, read the response R 1. For a permeation or diffusion tube the concentration is given by: C = P F k where P is the emission rate of water from the certified permeation or diffusion tube (nanograms per minute), F is the flow rate of dilution gas in ml/min, k converts P to nanoliters per minute. The factor k is the molar volume of gas at a reference temperature divided by the molecular weight of the permeating compound. For water (Mol. Wt. 18), when the reference temperature is 0 C, k=1.24. At reference temperature 25 C the value is Change the flow F to generate a new moisture level, C 2. Again, when stable read the response R Calculate the sensitivity of response to the known change in moisture (3) Page 5

8 Calculate the concentration background residual moisture C 0. S = R 2 - R 1 C 2 - C 1 (4) C 0 = R 0 S Add C 0 to C 1 and C 2 to get real calibration values C a and C b Adjust the calibration reading (or calibration correction curve) to indicate concentration C a for R 1 response. 7.5 Changing the Range of Performance of a Moisture Standard If a moisture standard is based on some device which is believed to deliver moisture at a constant rate, such as a permeation or diffusion tube, the concentration range delivered by the moisture standard may be changed by delivering a substantially different flow of carrier gas. This usually requires changing a mass flow controller or other flow control device inside the standard for a flow controller of a different range. This may be done provided the new flow controller's performance is verified by comparison with a reliable flow standard. 7.5 The definition of dilution factor is revised to: (5) 7.6 (6) 7.7 The background, B, is determined by removing the permeation or diffusion tube from the system and capping off its point of connection, or by preventing the source from delivering moisture by some other means. The same equation for c applies as does the statement regarding analytical uncertainty The change in range of performance can also be accomplished by a secondary dilution of the standard where a higher range standard is dynamically made, then a small alliquot flow of that standard is dynamically rediluted to form a new, much lower concentration flowing standard. This may be done provided the performance of the flow controllers used to control both the alliquot flow and the secondary dilution flow is verified by comparison with a reliable flow standard. In this case the background moisture can be determined by measuring only the secondary dilution gas. Using this technique both the original standard (using no secondary dilution flow) and the lowest concentration are available to the same hygrometer without opening the system through the same flow path and without opening the system to the atmosphere Validation at Intermediate Concentrations It may be desirable to validate a moisture standard at a concentration below the detection limit of the primary hygrometer, if that standard is to be used for very low-level generation. For example, if a standard based on a permeation device is intended to generate levels between 0.5 and 5 ppb at flows of 1 to 10 slm, it could be validated in the 0.5 to 5 ppm range using a frost-point hygrometer by replacing the flow controller with one operating between 1 and 10 sccm. However, such a flow controller may not be readily available and is difficult to calibrate in any case. Instead, it is preferable to use a flow controller operating between 50 and 500 sccm to generate concentrations between 0.1 and 1.0 ppm together with a secondary hygrometer having a detection limit no higher than 50 ppb. This procedure is acceptable, provided that: the secondary hygrometer has been validated with a primary hygrometer at least at one point in the range to be used for validation of the moisture standard, the moisture concentrations generated by the standard and that observed by the secondary hygrometer agree throughout the range of validation of the standard. This approach could lead to errors if the hygrometer and the standard each exhibited a deviation from predicted performance, but these deviations would have to be the same and cancel, which is extremely unlikely In the case of operation in this mode, it will be necessary to know the background level of the system and use this as an input to the calculation of generated moisture levels. To continue the example of a permeation based system, if the permeation rate determined by weight loss is P (ng/min), the flow rate of carrier gas is F (sccm), K is a factor to convert ng/min to sccm moisture, and B is the experimentally determined background, then the generated moisture level, c gen, is calculated according to: Page 6

9 For other moisture generation systems, it is similarly possible to calculate the generated moisture level while taking into account the background level of the system. This assumes that the background moisture concentration is constant, which is only approximately true. Thus, in applying this approach, in addition to the sources of error mentioned above, the estimate of analytical uncertainty must also include the variation in background moisture. 8 Validation Precision and Accuracy 8.1 This procedure does not explicitly consider the estimation of the accuracy of a moisture standard in detail, because such a calculation can be made by applying procedures described elsewhere. The accuracy required in validation will vary with the proposed application of the moisture standard and may be left to the discretion of the user of the procedure. It is recommended that a propagation of errors calculation be carried out to estimate the accuracy of the validation. If no such calculation is made, and the minimum criteria of the procedure are followed, it is estimated that a validated moisture generator may output moisture levels which differ from the actual moisture level by up to 20%. NOTICE: SEMI makes no warranties or representations as to the suitability of the Standards and Safety Guidelines set forth herein for any particular application. The determination of the suitability of the Standard or Safety Guideline is solely the responsibility of the user. Users are cautioned to refer to manufacturer s instructions, product labels, product data sheets, and other relevant literature, respecting any materials or equipment mentioned herein. Standards and Safety Guidelines are subject to change without notice. By publication of this Standard or Safety Guideline, SEMI takes no position respecting the validity of any patent rights or copyrights asserted in connection with any items mentioned in this Standard or Safety Guideline. Users of this Standard or Safety Guideline are expressly advised that determination of any such patent rights or copyrights and the risk of infringement of such rights are entirely their own responsibility. (7) Page 7

10 SEMI Draft Document #5765 Revision to SEMI C TEST METHOD FOR ppm AND ppb HUMIDITY STANDARDS *Copy of Intended Final Version* 1 Purpose 1.1 This test will determine whether or not the quantity of moisture delivered by a gaseous moisture standard is in agreement with that predicted for the standard on the basis of physical principles. It is expected that this method will be used to validate moisture standards before they are first placed in use, when deviation from expected performance is likely or suspected, and at other times as seems necessary. 1.2 The test method assumes the existence of a reliable moisture analyzer. Although extensive precautions are described to ensure the validity of the analyzer, it is always possible that the test could yield a faulty result through some unforeseen defect in the analytical equipment. 1.3 Given that moisture generation is subject to many pitfalls, it will be required that the predicted moisture concentration delivered by the standard and the measurement of that level by the analyzer agree. The level of agreement can vary depending on the degree of precision claimed for the moisture standard, but in any case the measured and predicted results should be within 10% over the entire range of the moisture standard. If not, then the validation should be repeated after verifying the physical measurement upon which the prediction is based and any other parameters deemed suspect. 2 Scope 2.1 This method is intended to be applicable to any type of gaseous standard delivering a quantity of moisture in the ppm range or lower, provided the delivered moisture concentration is predictable on the basis of fundamental principles of physics. Thus, any standards which rely solely on characterization by analysis are specifically excluded. 2.2 As part of this test, a procedure is described for qualifying certain moisture analyzers considered suitable for use in qualifying moisture standards. Moisture analyzers intended for other applications may need to satisfy different criteria. 2.3 As the most accurate and reliable moisture analyzers currently available operate primarily in the ppm range, this test focuses on validation of moisture standards in this range. The need for ppb moisture standards is addressed by specifying procedures for reducing the output of ppm moisture standards to the ppb range. NOTICE: SEMI Standards and Safety Guidelines do not purport to address all safety issues associated with their use. It is the responsibility of the users of the Documents to establish appropriate safety and health practices, and determine the applicability of regulatory or other limitations prior to use. 3 Limitations 3.1 If no higher level of accuracy is specified by the user, then a moisture standard shown to be valid by this method will generate moisture levels which deviate from the expected values by no more than 20%. The method leaves open to the user the option of using sound statistical methods to specify that a given moisture standard will generate levels showing a closer agreement with expected values. 3.2 Validation based on this test method is good for a limited time. The acceptable interval between validations depends on the nature of the standard and is not addressed by this method. Thus any citation of validation results should be accompanied by the date(s) on which validation was performed. 4 Referenced Standards and Documents 4.1 This method is based upon principles outlined in F. Mermoud, M.D. Brandt, and J.J.F. McAndrew, Low Level Moisture Generation. Analytical Chemistry, (1991): pp Page 8

11 5 Device Under Test (Test Specimen) 5.1 Definition of a Moisture Standard A moisture standard is defined to be any device capable of delivering a flow of humidified gas at controlled pressure, with no input being provided by the user except nitrogen of UHP grade (moisture <1 ppm) or air of equivalent purity. Any device, such as a permeation tube, which can provide a predictable amount of moisture but does not include a means to deliver gas to and from it, will not be considered a moisture standard by itself. A device which requires gas of higher purity than UHP grade will include a purifier capable of purifying UHP nitrogen to this level. 5.2 Examples of Moisture Standards Some examples of moisture standards and the principles upon which they are based are as follows: Permeation and Diffusion Tube Standards These must include purification means and some means of regulating the outlet pressure. The moisture delivery rate can be calculated based on the weight loss of the tube. Cylinder Standards The standard will include a regulator specified for use with the cylinder. The moisture concentration delivered can be calculated based on that added to the cylinder in preparation. A minimum use pressure must be specified. Methods based on saturation of gas with water vapor at a fixed temperature and pressure. The moisture concentration in the gas may then be calculated from a knowledge of the saturation vapor pressure of water over a plane of the pure phase of ice at the saturation temperature and of the interaction virial coefficients of the gasvapor mixture. The two-pressure and two-temperature methods are refinements of this approach requiring additional chambers whose temperature and pressure must be known. 5.3 Dilution of Standards For all moisture generation methods, lower concentrations can be generated by dynamic dilution (i.e., by combining a known flow of the standard gas with a known flow of dilution gas). A diluted standard is acceptable provided: The standard is validated at high concentration (with the lowest concentration validated being no more than 10,000 times the use concentration), The dilution gas has a moisture level below the stated precision of the analysis (to be verified using the same flow path as during the subsequent analysis, and at the lowest flow rate to be used), The absolute accuracies of the dilution system components are verified by comparison with a reliable flow standard, The linearity of the dilution system can be demonstrated over the entire range of operation. The last criterion is particularly important whenever some portion of the combined flow is discarded, as mixing problems can easily arise at large dilution factors. 6 Procedure 6.1 Validation will be performed using a hygrometer whose output can be directly related to the moisture concentration on the basis of physical laws or using an analyzer which has recently been calibrated by comparison with such an analyzer. 6.2 Hygrometer Qualification Primary Hygrometers Hygrometers can be certified by the National Institute for Standards and Technology (NIST) in the U.S., and similar certification is available in other countries, although the lowest concentration at which certification is available will vary. Repeated certification at yearly or longer intervals can be used to establish reliability. A hygrometer which has been certified by a national standards laboratory to 1 ppm (or lower) moisture in air or nitrogen, and for which reliability has been established over a period greater than or equal to that which has elapsed since certification occurred, is acceptable for validation of a moisture standard and will be referred to as a primary hygrometer Because hygrometers which are suitable for use as primary hygrometers may be less convenient or less readily available than other hygrometers, the use of other hygrometers for validation is also acceptable, provided adequate precautions are taken to ensure that they are operating correctly. These precautions (to be described below) require Page 9

12 using a moisture source to compare a secondary hygrometer with the primary hygrometer. The moisture source need not have been validated in this case Validation of Secondary Hygrometers Secondary hygrometers may be validated by comparing their output with a primary hygrometer when connected in parallel to the same moisture source. The degree of agreement required can vary depending upon the precision to be claimed, but in any case the difference in reading between the two hygrometers should be no more than 10% at any point. Comparison should be made at four moisture concentrations or at two per decade of proposed operation, whichever is less. Half of the comparisons should be made while increasing concentration and half while decreasing, including at least one comparison at the highest point of the concentration range. The first and last comparisons should be at the lowest point of the concentration range. For example, in order to validate a hygrometer for operation between 1 and 100 ppm, it would be acceptable to generate moisture levels at 1, 30, 100, 50, 1 ppm (in that order) and compare the primary with the secondary hygrometer. Comparison of the measured level between the two 1 ppm tests provides a ready indication of hysteresis in the system. If the secondary hygrometer requires calibration using its own standard, calibration should be effected before validation. However, it is acceptable to adjust the calibration in order to improve agreement with the primary hygrometer Frequency of Hygrometer Validation The frequency of validation required for a secondary hygrometer will vary dependent upon the performance established for hygrometers of the same general type. If three successive monthly validations show continuing agreement (within 10%) with the primary hygrometer without calibration adjustment, the validation interval may be extended to three months. Similar extensions of validation interval to six months and one year may be made if no drift is apparent and no calibration adjustments are necessary to bring the secondary within 10% of the primary at all points. 6.3 Validation Procedure for Moisture Standards Validation Within the Range of an Available Primary Hygrometer If a primary hygrometer is available, and its detection limit is no higher than the lowest concentration at which it is desired to use the moisture standard, this is the simplest case. Use the standard to generate four concentration levels or two per decade (whichever is less) in which the standard will be used, half of the concentrations generated while increasing concentration, half while decreasing, including at least one comparison at the highest point of the concentration range. The first and last comparisons should be at the lowest point of the concentration range. If the generated levels, calculated according to the basic properties of the generator (e.g., weight loss of a permeation tube) agree with the measured levels to within 10%, the standard may be considered validated with an accuracy of 10%. Higher validation accuracy requires better agreement. It has been assumed that the precision of the primary hygrometer, as determined by a national standards laboratory, is much better than 10% and may be neglected for validation at the 10% level. Validation at higher accuracy requires explicit consideration of the certification precision If a standard generates only one level, connect it to the hygrometer and allow to come to equilibrium. Assuming the equilibrium level agrees with the calculated level of the generator, disconnect the hygrometer and bring it to equilibrium with either dry nitrogen or ambient air. Then reconnect the moisture standard and reestablish equilibrium between the standard and the hygrometer. Disconnect again and measure a third time. If the three measurements agree within 10% among themselves and with the generated level, the standard is validated It is implicit in the above that the background moisture level of the system be less than 50 ppb so that it can be neglected for all measurements above 1 ppm with an error no larger than 5%. The background moisture can usually be neglected when validating moisture standards in this concentration range Validation Using Secondary Hygrometers If no primary hygrometer is available, then validation can be performed using a secondary hygrometer. If the lowest concentration to be generated using the standard is no higher than the detection limit of the primary hygrometer used for validation of the secondary hygrometer, then the procedure is as above, except that the secondary must first have been validated over the entire concentration range which the standard will be used to generate. (A secondary hygrometer and a moisture standard can be validated simultaneously if the primary and secondary hygrometers are connected in parallel to the moisture standard.) When assessing the accuracy of validation using a secondary hygrometer, it is necessary to take into account the precision of the comparison of the primary hygrometer with the secondary hygrometer as well as the precision of the comparison of the generator with the secondary hygrometer. Page 10

13 7 Practice for Generating ppb Moisture Standards 7.1 The detection limit of the primary hygrometer will generally be on the order of 1 ppm, whereas it will frequently be necessary to use the moisture standard at concentrations below this level, by a factor of as much as1,000. Therefore, valid methods for reducing concentration are necessary. 7.2 Dilution of Validated Moisture Standards If a moisture standard validated in accordance with 6.3 or is diluted with a zero gas stream satisfying the criteria of 5.3, then the resultant diluted standard may be considered valid and may be used for calibration of analyzers, such as APIMS. 7.3 Consideration of Background Moisture In any ppb or lower moisture measurement, it is necessary to consider the background moisture level due to outgassing in the sampling system and residual moisture in the generator + analyzer, and the moisture level of any carrier gas diluting the standard. Often the background will be sufficiently large that it must be taken into account explicitly. The background moisture level is the moisture concentration measured in the absence of a moisture source (i.e., when the driest carrier gas available is fed to the analyzer using the same flow rate and flow path as is used for the sample gas during analysis) It should be noted that the importance of the background level increases for measurements at low concentrations, and that the background level is sensitive to the materials of construction, to the design of the moisture generator, and to its operating temperature If the background moisture concentration is B (ppb), the concentration delivered by the moisture standard is C (ppb) and the dilution factor x is given by: then c, the delivered moisture concentration is given (in ppb) by: (1) The accuracy of calibration will reflect the combined accuracy of the standard and the dilution system, together with the accuracy of the background determination; all must be taken into account in any statement of analytical uncertainty. 7.4 Determining the Background Concentration - The background concentration B should be determined for each calibration. Depending on the design of the moisture generator and sample system B can be difficult (or impossible) to determine as an independent value. For ppb and lower concentrations the system should allow the moisture source to be added or removed without opening the system to the atmosphere while maintaining both the system and source at constant temperature and pressure. Figure 1 shows a schematic of a suitable arrangement. (2) Page 11

14 MATRIX IN PRESSURE UNMETERED CARRIER FLOW (During Zero) FI DILUTION FLOW METERED CARRIER FLOW (During Span) FC CARRIER FLOW FC PERMEATION OVEN BACK PRESSURE ZERO/SPAN SWITCHING BACK PRESSURE ZERO/SPAN GAS OUT (During Zero) DISCARD GAS TO VENT Figure 1 PPB Moisture Permeation Tube System Allowing Background Moisture Correction When the system is in operation with no added moisture standard the operation is designated zero mode. Operation when moisture standard is being added is designated span mode. The following procedure can be used to determine the background concentration, validate a generated moisture standard, validate a secondary hygrometer or calibrate a moisture monitor. If the moisture generator uses a permeation or diffusion tube, finding the background concentration is very simple, even with an uncalibrated hygrometer Install the permeation (or diffusion) tube in the generator. Using the driest carrier/dilution gas available establish flow through all paths in the generator and allow the system to dry down and stabilize. Note that this might take several days Connect to the hygrometer to be calibrated and allow the hygrometer and interconnecting tubing to stabilize again. Use clean, electropolished tubing and fittings, preferably predried In the Zero mode, introduce the carrier/dilution gas through the moisture generator as zero reference, or background gas and observe the response R 0. Use several values of Background flow through the system. Use the value of R0 observed at the lowest flow used for generating the moisture standards for any estimate of accuracy. If the hygrometer is a primary standard, R 0 is the background concentration. For an uncalibrated hygrometer continue Switch to the Span mode and introduce a level of moisture, C 1. When stable, read the response R 1. For a permeation or diffusion tube the concentration is given by: C = P F k where P is the emission rate of water from the certified permeation or diffusion tube (nanograms per minute), F is the flow rate of dilution gas in ml/min, k converts P to nanoliters per minute. The factor k is the molar volume of gas at a reference temperature divided by the molecular weight of the permeating compound. For water (Mol. Wt. 18), when the reference temperature is 0 C, k=1.24. At reference temperature 25 C the value is Change the flow F to generate a new moisture level, C 2. Again, when stable read the response R Calculate the sensitivity of response to the known change in moisture (3) Page 12

15 Calculate the concentration background residual moisture C 0. S = R 2 - R 1 C 2 - C 1 (4) C 0 = R 0 S Add C 0 to C 1 and C 2 to get real calibration values C a and C b Adjust the reading (or calibration correction curve) to indicate concentration C a for R 1 response Changing the Range of Performance of a Moisture Standard If a moisture standard is based on some device which is believed to deliver moisture at a constant rate, such as a permeation or diffusion tube, the concentration range delivered by the moisture standard may be changed by delivering a substantially different flow of carrier gas. This usually requires changing a mass flow controller or other flow control device inside the standard for a flow controller of a different range. This may be done provided the new flow controller's performance is verified by comparison with a reliable flow standard. The change in range of performance can also be accomplished by a secondary dilution of the standard where a higher range standard is dynamically made, then a small alliquot flow of that standard is dynamically re-diluted to form a new, much lower concentration flowing standard. This may be done provided the performance of the flow controllers used to control both the alliquot flow and the secondary dilution flow is verified by comparison with a reliable flow standard. In this case the background moisture can be determined by measuring only the secondary dilution gas. Using this technique both the original standard (using no secondary dilution flow) and the lowest concentration are available to the same hygrometer without opening the system through the same flow path and without opening the system to the atmosphere. 7.5 Validation at Intermediate Concentrations It may be desirable to validate a moisture standard at a concentration below the detection limit of the primary hygrometer, if that standard is to be used for very low-level generation. For example, if a standard based on a permeation device is intended to generate levels between 0.5 and 5 ppb at flows of 1 to 10 slm, it could be validated in the 0.5 to 5 ppm range using a frost-point hygrometer by replacing the flow controller with one operating between 1 and 10 sccm. However, such a flow controller may not be readily available and is difficult to calibrate in any case. Instead, it is preferable to use a flow controller operating between 50 and 500 sccm to generate concentrations between 0.1 and 1.0 ppm together with a secondary hygrometer having a detection limit no higher than 50 ppb. This procedure is acceptable, provided that: the secondary hygrometer has been validated with a primary hygrometer at least at one point in the range to be used for validation of the moisture standard, the moisture concentrations generated by the standard and that observed by the secondary hygrometer agree throughout the range of validation of the standard. This approach could lead to errors if the hygrometer and the standard each exhibited a deviation from predicted performance, but these deviations would have to be the same and cancel, which is extremely unlikely In the case of operation in this mode, it will be necessary to know the background level of the system and use this as an input to the calculation of generated moisture levels. To continue the example of a permeation based system, if the permeation rate determined by weight loss is P (ng/min), the flow rate of carrier gas is F (sccm), K is a factor to convert ng/min to sccm moisture, and B is the experimentally determined background, then the generated moisture level, c gen, is calculated according to: (5) For other moisture generation systems, it is similarly possible to calculate the generated moisture level while taking into account the background level of the system. This assumes that the background moisture concentration is constant, which is only approximately true. Thus, in applying this approach, in addition to the sources of error mentioned above, the estimate of analytical uncertainty must also include the variation in background moisture. (7) Page 13