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Background Statement for SEMI Draft Document 6003A
REVISION TO SEMI C60-0305 (REAPPROVED 0211), SPECIFICATIONS AND GUIDELINES FOR NITROUS OXIDE (N2O)
Notice: 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.
Notice: 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.
Background
Document 6003, line item ballot, was approved for ballot to correct the nonconforming title in Cycle 4-16. Unrelated comments were received from the LI ballot, which required failing of the Document and sending it for full Letter Ballot after re-work. This major revision incorporates and addresses the negatives and comments along with the changes required to correct the nonconforming title.
Notice: Additions are indicated by underline and deletions are indicated by strikethrough.
Review and Adjudication Information
Task Force Review / Committee AdjudicationGroup: / Gases Specification Task Force / Facilities & GasesNA TC Chapter
Date: / November 7, 2016 / November 8, 2016
Time & Timezone: / 13:00– 14:00 PDT / 9:00 –12:00 Noon PDT
Location: / SEMI Headquarters
3081 Zanker Road / SEMI Headquarters
3081 Zanker Road
City, State/Country: / San Jose, CA/USA / San Jose, CA/USA
Leader(s)/Authors: / Mohamed Saleem (Fujikin)
Matthew Milburn (UCT)
Thomas Fritz (WIKA) / Mohamed Saleem (Fujikin)
Steve Lewis (LPCiminelli)
Standards Staff: / Laura Nguyen ( ) / Laura Nguyen ( )
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.
Check on calendar of event for the latest meeting schedule.
SEMI Draft Document 6003A
REVISION TO SEMI C60-0305 (REAPPROVED 0211), SPECIFICATIONS AND GUIDELINES FOR NITROUS OXIDE (N2O)
This Standard was technically approved by the global Gases Committee. This edition was approved for publication by the global Audits & Reviews Subcommittee on December 21, 2010. Available at and in February 2011; originally published March 2005.
1 Purpose
1.1 The purpose of this Document is to provide a series of specifications for different grades of Nitrous Oxide (N2O) that are used in the semiconductor industry.
2 Scope
2.1 This Document covers requirements for all grades of nitrous oxide used in the semiconductor industry.
2.2 If analytical methods are not complete, the requirements are presented as a guideline.
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 Description
3.1 Nitrous oxide is an oxidizing, colorless, liquefied gas with a sweetish odor. It is a simple asphyxiant. Vapor pressure is about 745 psig at 70°F.
4 Limitations
4.1 None.
5 Referenced Standards
5.1 SEMI Standardsand Safety Guidelines
SEMI C1 — Guide for the Analysis of Liquid Chemicals
SEMI C3 — Specifications for Gases
NOTICE: Unless otherwise indicated, all documents cited shall be the latest published versions.
6 Terminology
6.1 Terminology appropriate to this Standard is defined in SEMIC3.
7 Requirements
7.1 Purity and other requirements for the various grades of nitrous oxide are given in Table1.
Table 1Impurity and Other Requirements for Various Grades of Nitrous Oxide
Previous SEMI Reference # / C3.13-1000(Specification) / C3.50-1000
(Guideline)
Grade / 4.7 / 5.4
Purity / 99.997%#2,#3 / 99.9994%#2, #3
Impurities / Maximum Acceptable Level (ppm)#1 / Maximum Acceptable Level (ppm)#1
Ammonia (NH3) / 5 / 0.1
Carbon Dioxide (CO2) / 2 / 0.5
Carbon monoxide (CO) / 1 / 0.1
Hydrocarbons C1-C5 / 1 / 0.1 (as C1)
Nitric Oxide (NO) / 1 / 0.1
Nitrogen (N2) / 10 / 3
Nitrogen dioxide (NO2) / 1 / 0.1
Oxygen (O2) / 2 / N/A
Oxygen (O2) + Argon (Ar) / N/A / 0.5
Water (H2O) (v/v) / 3 / 1.0
TOTAL SPECIFIED IMPURITIES / 26 / 5.5
#1An analysis of significant figures has not been considered. The number of significant figures is based on analytical accuracy and the precision of the provided procedure.
#2This Specification applies to the gas phase of the cylinder as delivered.
#3It is recommended that the user discontinue use of the cylinder prior to complete consumption of the liquid phase. The contents of cylinders should be determined by weight, not pressure.
8 Physical Constants
8.1 The physical constants of nitrous oxide are given in Table2(for information only).
Table 2Physical Constants of Nitrous Oxide (for information only)
Metric Units / US UnitsMolecular weight / 44.01 / 44.01
CAS Number / 10024-97-2 / 10024-97-2
Boiling point at 1 atm / −88.5°C / −127.4°F
Density of gas at 70°F (21.1°C)
and 1 atm / 1.947 g/L / 0.1160 lb/ft3
Specific gravity of gas / 1.53 / 1.53
Critical pressure / 71.46 atm / 1052 psia
Critical temperature / 36.4°C / 97.6°F
9 Analytical Procedures for Grade 4.7 Nitrous Oxide (See Appendix 1)
NOTE 1:Rapid withdrawal of gaseous nitrous oxide from a liquified source (e.g., cylinder) can result in a significant cooling effect which may condense the nitrous oxide in the sampling lines.
9.1 Ammonia — This procedure is for the determination of ammonia in nitrous oxide using an apparatus employing a detector tube filled with a color-reactive chemical.
9.1.1 Detection Limit — 0.2 ppm (mol/mol).
9.1.2 Apparatus
9.1.2.1 Pressure Regulator— Outlet Pressure Range 0 to 30 psig.
9.1.2.2 Flowmeter— Range 0 to 200 mL/min.
9.1.2.3 Detector Tube— Range 2 to 30 ppm.
9.1.2.4 Stop watch.
9.1.2.5 6 mm (1/4 in.) flexible tubing.
9.1.3 Operating Procedure
9.1.3.1 Attach a suitable regulator to the cylinder outlet.
9.1.3.2 Connect the flowmeter to the regulator using flexible tubing.
9.1.3.3 Open the cylinder valve and purge the flowmeter with nitrous oxide.
9.1.3.4 After the line is thoroughly purged, stop the flow of nitrous oxide and attach the detector tube to the outlet of the flowmeter.
9.1.3.5 Start the flow of nitrous oxide and set the flow rate to 100 mL/min. The pressure and temperature of the sample must be within the tolerances specified by the manufacturer.
9.1.3.6 Pass 100 mL of nitrous oxide through the detector tube.
9.1.3.7 Determine the concentration of ammonia according to the detector tube manufacturer’s instructions. The concentration may not exceed the specification in Table1 of this standard.
9.2 Carbon Monoxide and Carbon Dioxide — This procedure is for the determination of carbon monoxide and carbon dioxide in nitrous oxide using a gas chromatograph with a flame ionization detector and methanizer with back flush (see Figure A1-1).
NOTE 2:In order to prevent nitrous oxide interference, a helium backflush to vent is needed for 3 to 5 times the analysis time (estimated to be 3 to 5 minutes). Because nitrous oxide is converted into ammonia in the methanizer, stainless steel (ss) is required; copper tubing and fittings are not used. The backflush removes the nitrous oxide from Column No. 1 preparing the column for the next sample.Careful timing is required to identify carbon monoxide and carbon dioxide distinguishing both from the time methane would appear, if present. Carbon monoxide and carbon dioxide are converted to methane in the methanizer; therefore, both will be detected by the FID detector at the specific times determined by the analytical sequence of the standard.
9.2.1 Detection Limit — 1 ppm (mol/mol), (50 ppb depending on conditions).
9.2.2 Instrument Parameters
9.2.2.1 Columns
- Column 1 — Porapak® QS, 4.6 m (15 ft.) by 5 mm (3/16 in.) or equivalent.
- Column 2 — Molecular sieve 5A, 1.97 m (6 ft.) by 5 mm (3/16 in.), 80/100 mesh (reference only) or equivalent.
- Carrier Flow — 30 mL/min helium.
- Sample Volume — 0.5 to 2.0 mL.
- Temperatures
- Detector — 35°C
- Column Oven — 35°C
- Methanizer — 500°C
- Calibration Standard — 1 to 5 ppm (mol/mol) carbonmonoxide, 1 to 5 ppm (mol/mol) carbondioxide, balance nitrousoxide.
- Operating Procedure
- Inject the calibration standard into the column using a gas sampling valve. Record the retention times and peak areas. The order of elution is carbon monoxide, methane, carbon dioxide, and nitrous oxide. Back flush 18 minutes.
- Inject the sample to be tested in same manner as the calibration standard. Record the retention times and peak areas.
- Repeat ¶9.2.4.1.
- Compare the average peak areas of the calibration standard to that of the nitrous oxide sample being tested. Calculate the concentrations of carbon monoxide and carbon dioxide, using the formula below. The result may not exceed the specification in Table1 of this Standard.
(1)
9.3 Hydrocarbons C1 – C5 — This procedure is for the determination of hydrocarbons C1 to C5 in nitrous oxide using a gas chromatograph with a flame ionization detector.
9.3.1 Methane Determination
9.3.1.1 Detection Limit — 0.1 ppm (mol/mol).
9.3.1.2 Instrument Parameters
9.3.1.2.1 Column — 5A molecular sieve, 1.9 m (6 ft.) by 6.4 mm (1/4 in.) OD by 5.3 mm (0.210 in.) ID stainless steel or equivalent.
9.3.1.2.2 Carrier Flow — 25 mL/min helium.
9.3.1.2.3 Sample Volume — 5.0 mL.
9.3.1.2.4 Temperatures
- Detector — 150°C
- Column Oven — 30°C
- Ethane Determination
- Detection Limit — 0.3 ppm (mole/mole).
- Instrument Parameters
- Column — Porapak® Q, 1.9 m (6 ft.) by 6.4 mm (1/4 in.) OD by 5.3 mm (0.210 in.) ID stainless steel or equivalent.
- Carrier Flow — 50 mL/min helium.
- Sample Volume — 1.0 mL.
- Temperatures
- Detector — 150°C
- Column Oven — 60°C
- Ethylene, Propane, Acetylene, Propylene, n-butane, and n-pentaneDetermination
- Detection Limit — 0.1 ppm (mole/mole).
- Instrument Parameters
- Column — Phenylisocyanate/Porasil C, 3 m (10 ft.) by 4.8 mm (3/16 in.) OD by 3.7 mm (0.147 in.) ID stainless steel or equivalent.
- Carrier Flow — 25 mL/min helium.
- Sample Volume — 1.0 mL.
- Temperatures
- Detector — 150°C
- Column Oven — 30°C
- Calibration Standards — 1 to 5 ppm (mol/mol) methane in helium, 1 to 5 ppm (mol/mol) ethane in helium, 1 to 5 ppm (mol/mol) ethylene, 1 to 5 ppm (mol/mol) propane, 1 to 5 ppm (mol/mol) acetylene, 1 to 5 ppm (mol/mol) propylene, 1 to 5 ppm (mol/mol) n-butane, and 1 to 5 ppm (mol/mol) n-pentane, balance in helium.
- OperatingProcedure
- Inject the calibration standard into the column using a gas sampling valve. Record the retention time and peak area.
- Inject the sample to be tested in same manner as the calibration standard. Record the retention times and peak areas.
- Repeat ¶9.3.5.1.
- Compare the average peak area of the calibration standard to that of the nitrous oxide sample being tested. Calculate the concentration of hydrocarbons C1 to C5, using the formula below. The result may not exceed the specification in Table1 of this Standard.
(2)
9.4 Nitric Oxide — This procedure is for the determination of nitric oxide in nitrous oxide using chemiluminescence. The detector shall have a photomultiplier tube capable of sensing the light emission of the decaying nitrous oxide. The detector shall have variable attenuation, zero and span adjustments, display, and an onboard ozone generator.
NOTE 3:This method does not determine nitrous oxide impurities.
9.4.1 Detection Limit — 0.1 ppm (mol/mol).
9.4.2 Instrument Parameters
9.4.2.1 Flow Requirements — Set the zero gas, span gas, and sample gas in accordance with the instrument manufacturer’s instructions.
9.4.3 Calibration Standards
9.4.3.1 Zero argon (99.99% minimum) with less than 0.1 ppm nitric oxide.
9.4.3.2 The upper level argon span gas (99.99% minimum) not exceeding 5 times the concentration of the specification.
9.4.3.3 The oxygen supplied to the ozone generator will contain less than 0.1 ppm nitric oxide.
9.4.4 Operating Procedure
9.4.4.1 Introduce the zero argon and set the instrument to zero with the zero adjust knob.
9.4.4.2 Introduce the span gas in argon and, using the span adjust knob, set the output reading to match the level of nitric oxide in the span gas.
9.4.4.3 Repeat ¶9.4.4.1 and ¶9.4.4.2 until reproducibility of readings is better than 1% full scale.
9.4.4.4 Introduce the nitrous oxide sample into the analyzer and read the quantity of nitric oxide. The result may not exceed the specification in Table1 of this Standard.
9.5 Nitrogen and Oxygen — This procedure is for the determination of nitrogen and oxygen in nitrous oxide using a gas chromatograph with a helium ionization detector.
9.5.1 Detection Limit — 0.5 ppm (mol/mol).
9.5.2 Instrument Parameters
9.5.2.1 Columns
- Column 1 — Porapak® Q, 1.9 m (6 ft.) by 3.2 mm (1/8 in.) OD by 2.2 mm (0.085 in.) ID stainless steel, or equivalent.
- Column 2 — Molecular sieve 5A, 2.4 m (8 ft.) by 3.2 mm (1/8 in.) OD by 2.2 mm (0.085 in.) ID stainless steel, or equivalent.
- Carrier Flow —50 mL/min helium.
- Sample Volume —1.0 to 3.0 mL.
- Temperatures
- Detector — 125°C
- Column Temperature — 65°C
- Calibration Standards — 5 to 20 ppm (mol/mol) nitrogen in helium and 1 to 5 ppm (mol/mol) oxygen in helium.
- Operating Procedure
- Inject the calibration standard into the column using a gas sampling valve. Record the retention time and peak area.
- Inject the sample to be tested in same manner as the calibration standard. Record the retention times and peak areas.
- Repeat ¶9.5.4.1.
- Compare the average peak area of the calibration standard to that of the nitrous oxide sample being tested. Calculate the concentrations of nitrogen and oxygen, using the formula below. The result may not exceed the specification in Table1 of this Standard.
(2)
9.6 Nitrogen Dioxide — This procedure is for the determination of nitrogen dioxide in nitrous oxide using an apparatus employing a detector tube filled with a color-reactive chemical.
9.6.1 Detection Limit — 0.05 ppm.
9.6.2 Apparatus
9.6.2.1 Pressure Regulator — Outlet Pressure Range 0 to 30 psig.
9.6.2.2 Flowmeter — Range 0 to 200 mL/min.
9.6.2.3 Detector Tube — Range 0.2 to 6 ppm.
9.6.2.4 StopWatch.
9.6.2.5 6 mm (1/4 in.) flexible tubing.
9.6.3 Operating Procedure
9.6.3.1 Attach a suitable regulator to the cylinder outlet.
9.6.3.2 Connect the flowmeter to the regulator using flexible tubing.
9.6.3.3 Open the cylinder valve and purge the flowmeter with nitrous oxide.
9.6.3.4 After the line is thoroughly purged, stop the flow of nitrous oxide and attach the detector tube to the outlet of the flowmeter.
9.6.3.5 Start the flow of nitrous oxide and set the flow rate to 100 mL/min. The pressure and temperature of the sample must be within the tolerance specified by the manufacturer.
9.6.3.6 Pass 800 mL of gas through the detector tube.
9.6.3.7 Determine the concentration of nitrogen dioxide according to the detector tube manufacturer’s instructions. The concentration may not exceed the specification in Table1 of this standard.
9.7 Water — This procedure is for the determination of trace moisture (water) in nitrous oxide using a piezoelectronic hygrometer.
9.7.1 Detection Limit — 1.0 ppm (vol/vol).
9.7.2 Flow Requirements — Follow the flow requirements specified in the manufacturer’s instrument operation manual.
9.7.3 Calibration Standards — Construct a calibration curve which contains at least three points covering the range of interest. The standards employed will be verified independently by another analytical method.
NOTE 4: Other hygrometers may also be used, for example, CRDS, FTIR, TDLAS, and vibrating quartz.
9.7.4 Sample System and Proper Operation
9.7.4.1 The sample system shall be as shown in Figure A1-2.
9.7.4.2 Attach sample system to nitrous oxide cylinder.
9.7.4.3 Partially open valve 2.
9.7.4.4 Open valve 1 and adjust pressure to 50 psig, ±5 psig.
9.7.4.5 Adjust valve 2 until a flow of 500 mL/min, ±50 mL/min is venting.
9.7.4.6 Tubing, valves and fittings are to be cleaned and passivated 316 stainless steel.
9.7.4.7 Keep tubing lengths to a minimum.
9.7.5 Operating Procedure
9.7.5.1 Follow the procedures outlined in the instrument manufacturer’s manual.
9.7.5.2 Allow the system to run until a stable reading is obtained for ten minutes.
9.7.5.3 Read the quantity of water on the analyzer meter. The result may not exceed the specification in Table1 of this Standard.
APPENDIX 1
GENERAL ANALYTICAL PRACTICES
NOTICE: The material in this appendix is an official part of SEMI C59 and was approved by full letter ballot procedures on December 21, 2010.
A1-1 Introduce the calibration standard as many times as necessary to achieve the desired precision.
A1-2 All the gases used in the analysis of the sample should not contain more than 10% of the specified value at the component of interest, unless otherwise specified.
Figure A1-1
Valving Arrangement
Figure A1-2
Nitrous Oxide Cylinder Sample System
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