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SEMI C30-1101 © SEMI 1978, 2001 HYDRO GEN PEROXIDE 2 8.4 TOC 8.4.1 Equipment 8.4.1.1 T OC analyzer capable of analyzing total organic carbon in water. 8.4.1.2 P latinum sheet 1 × 1 in ch, heated in a muffle oven at 800 °…
HYDROGEN PEROXIDE SEMI C30-1101 © SEMI 1978, 20011
SEMI C30-1101
SPECIFICATIONS AND GUIDELINES FOR HYDROGEN PEROXIDE
These specifications and guidelines were technically approved by the Global Process Chemicals Committee
and are the direct responsibility of the North American Process Chemicals Committee. Current edition
approved by the North American Regional Standards Committee on August 27, 2001. Initially available at
www.semi.org September 2001; to be published November 2001. This document replaces SEMI C1.9, C7.5,
C8.5, C11.4, and C12.4 in their entirety. Originally published in 1978, 1990, 1992, 1994, and 1995
respectively; previously published March 2001.
1 Purpose
1.1 The purpose of this document is to standardize
requirements for hydrogen peroxide used in the
semiconductor industry and testing procedures to
support those standards. Test methods have been shown
to give statistically valid results. This document also
provides guidelines for grades of hydrogen peroxide for
which a need has been identified. In the case of the
guidelines, the test methods may not have been
statistically validated yet.
2 Scope
2.1 The scope of this document is all grades of
hydrogen peroxide used in the semiconductor industry.
2.2 The VLSI grade purity level is typically required
by semiconductor devices with geometries of 0.8–1.2
microns.
2.3 This standard does not purport to address safety
issues, if any, associated with its use. It is the
responsibility of the users of this standard to establish
appropriate safety and health practices and determine
the applicability of regulatory limitations prior to use.
3 Limitations
3.1 The specification for VLSI grade hydrogen
peroxide is only applicable for materials that remain
below 25°C during transport and storage.
4 Referenced Standards
4.1 SEMI Standards
SEMI C1 — Specifications for Reagents
4.2 ASTM Standards
1
ASTM D 5127 — Standard Guide for Ultra Pure Water
Used in the Electronics and Semiconductor Industry
NOTE 1: Unless otherwise indicated, all documents cited
shall be the latest published versions.
1 American Society for Testing and Materials, 100 Barr Harbor
Drive, West Conshohocken, Pennsylvania 19428-2959, USA.
Telephone: 610.832.9585, Fax: 610.832.9555 Website:
www.astm.org
5 Terminology
5.1 None.
6 Physical Property (for information only)
Density at 25°C
1.11 g/mL
7 Requirements
7.1 The requirements for hydrogen peroxide for Grades
1, 2, 3, 4, 5, and VLSI Grade are listed in Table 1.
8 Grade 1 Procedures
NOTE 2: When hydrogen peroxide is added to water, there is
no spattering. This happens only when the order of addition is
reversed.
NOTE 3: Each laboratory is responsible for verifying the
validity of the method within its own operation.
8.1 Assay — Accurately weigh about 1 mL of sample
in a tared 100 mL volumetric flask, dilute to volume
with water, and mix thoroughly. Transfer exactly 20.0
mL of this solution to a 250 mL conical flask, add 20
mL of dilute sulfuric acid (1 + 15), and titrate with
standardized 0.1 N (0.02 M) potassium permanganate
to a pink color that persists for 15 seconds.
%Assay
=
mL
×
N
of KMnO
4
×
8.500
Weight of sample g
()
8.2 Color — Dilute 2.0 mL of platinum-cobalt stock
solution (APHA No. 500) to 100 mL with water.
Compare this standard (APHA No. 10) with 100 mL of
sample in Nessler tubes. View vertically over a white
background. The sample must be no darker than the
standard.
8.3 Free Acid — Dilute 9 mL (10 g) of sample with 90
mL of freshly boiled and cooled carbon dioxide-free
water. Add 0.15 mL of methyl red indicator solution
and titrate with 0.01 N sodium hydroxide. The volume
of sodium hydroxide solution consumed should not be
more than 0.6 mL greater than the volume required for
a blank test on 90 mL of the water used for dilution.
SEMI C30-1101 © SEMI 1978, 2001 HYDROGEN PEROXIDE2
8.4 TOC
8.4.1 Equipment
8.4.1.1 TOC analyzer capable of analyzing total
organic carbon in water.
8.4.1.2 Platinum sheet 1 × 1 inch, heated in a muffle
oven at 800°C for 15 minutes.
8.4.2 Special Reagents
8.4.2.1 Water — The water used for all of the dilution,
calibration, and standards should meet, at a minimum,
the criteria for Type E1.1 in ASTM D 5127 in regard to
TOC analysis.
8.4.2.2 1000 mg/mL TOC Standard (prepare fresh
weekly) — Weigh accurately 0.2128 g of potassium
acid phthalate into a 100 mL volumetric flask, add
water, shake to dissolve, dilute to volume, and mix
well. Lower standards (prepare fresh daily) can be
made by diluting an aliquot of the 1000 mg/mL to the
appropriate volume.
8.4.3 Sample Preparation — Weigh 50 g of hydrogen
peroxide, to the nearest 0.01 g, into a 400 mL beaker.
Add the platinum sheet to the sample, cover the beaker
with a Teflon watch glass, and allow the reaction to go
overnight (12 hours minimum). Transfer the solution to
a 50 mL volumetric flask, and dilute with water
meeting the criteria for Type E1.1 in ASTM D 5127 to
a final volume of 50 mL.
8.4.4 Analysis — Using the prepared solutions, analyze
TOC by the total organic carbon analyzer after the
instrument has been calibrated with 0, 4, 10, and 20
µg/mL of TOC standards.
8.5 Chloride — Dilute 4.5 mL (5 g) of sample with 15
mL of water. Filter, if necessary, through a chloride-
free filter. Add 1 mL of nitric acid and 1 mL of silver
nitrate reagent solution. Any turbidity produced should
be no greater than that produced when 0.01 mg of
chloride ion (Cl) is treated as the sample.
8.6 Sulfate — To 9 mL (10 g) of sample, add 10 mL of
sodium carbonate reagent solution and evaporate to
dryness in a hood. Dissolve the residue in 10 mL of
water and 1 mL of dilute hydrochloric acid (1 + 19);
filter if necessary. Add 1 mL of barium chloride reagent
solution, mix, and allow to stand for 10 minutes. Any
turbidity developed should be no greater than that
produced when 0.05 mg of sulfate ion (SO
4
) is treated
as the sample.
8.7 Phosphate — Evaporate 4.5 mL (5 g) of sample to
dryness on the steam bath and dissolve the residue in 25
mL of 0.5 N sulfuric acid. Add 1 mL of ammonium
molybdate reagent solution and 1 mL of p-
(methylamino)phenol sulfate reagent solution. Allow to
stand for 2 hours at room temperature. Any blue color
should not exceed that produced in a standard of equal
volume containing 0.01 mg of phosphate ion (PO
4
) and
the quantities of reagents used in the sample.
8.8 Arsenic and Antimony (as As) — To 180 mL (200
g) of sample in a 400 mL beaker, add 5 mL of sulfuric
acid and evaporate to dense fumes of sulfur trioxide in a
hood. Cool, cautiously add 10 mL of water, and again
evaporate to dense fumes of sulfur trioxide. Cool, and
cautiously wash into a generator flask with water to
make a volume of 35 mL. Proceed as described in
General Method for Arsenic (and Antimony) under
SEMI C1, Section 3.4.5, starting with the first sentence
which begins: “Swirl the flask....” Any red color in the
silver diethyldithiocarbamate solution from the sample
should be no greater than that of the standard
containing 0.002 mg of arsenic (As).
8.9 Trace Metal Analysis — The following method has
given satisfactory results in determining trace metal
impurities at the value specified for each of the
following trace metals: aluminum (Al), boron (B),
calcium (Ca), chromium (Cr), copper (Cu), gold (Au),
iron (Fe), lead (Pb), magnesium (Mg), manganese
(Mn), nickel (Ni), potassium (K), sodium (Na), tin (Sn),
titanium (Ti), and zinc (Zn). Alternate methods may be
used as long as appropriate studies demonstrate
recovery between 75–125% of a known sample spike
for half of the value of each specified element.
8.9.1 Special Reagents
8.9.1.1 Nitric Acid, Ultra Pure — Use nitric acid
specified for ultra low metal ion content.
8.9.1.2 Hydrochloric Acid, Ultra Pure — Use
hydrochloric acid specified for ultra low metal ion
content.
8.9.2 Sample Preparation
8.9.2.1 Sodium and Potassium — In a clean
environment, place 10.0 mL of water in a clean
platinum crucible. Slowly add 5.0 mL of hydrogen
peroxide. Allow to stand at room temperature until the
effervescence ceases (approximately 20 minutes).
Swirl. If swirling does not produce any more bubbles,
proceed with analysis. If bubbles remain, allow to stand
for 5 minutes and repeat the swirl until no bubbles are
produced. Run a water blank.
8.9.2.2 Other Elements — Two separate samples of
hydrogen peroxide are acidified to 2% with
hydrochloric acid for the analysis of tin and to 2% with
nitric acid for the analysis of (specified elements).
Standard additions of tin to the matrix acidified with
hydrochloric acid and standard additions of other
specified elements to the matrix acidified with nitric
acid are added to determine the response for each
HYDROGEN PEROXIDE SEMI C30-1101 © SEMI 1978, 20013
element in the peroxide matrix. Aqueous acidified
standards for tin in 2% hydrochloric acid and other
specified elements in 2% nitric acid should be used to
determine instrument responses.
8.9.3 Analysis
8.9.3.1 Using the solution from Section 8.9.2.1,
analyze for specified group 1 elements by flame atomic
absorption spectroscopy. All other elements analyzed
by plasma emission spectroscopy.
9 Grade 2 Procedures
NOTE 4: Each laboratory is responsible for verifying the
validity of the method within its own operation.
9.1 Non-Metal Impurities
9.1.1 See Section 8, which contains procedures for the
following tests:
Assay
Color (APHA)
Free Acid
9.2 TOC
9.2.1 Equipment
9.2.1.1 TOC analyzer capable of analyzing total
organic carbon in water.
9.2.1.2 Platinum sheet 1 × 1 inch, heated in a muffle
oven at 800°C for 15 minutes.
9.2.2 Special Reagents
9.2.2.1 Water — The water used for all of the dilution,
calibration, and standards should meet, at a minimum,
the criteria for Type E1.1 in ASTM D 5127 in regard to
TOC analysis.
9.2.2.2 1000 mg/mL TOC Standard (prepare fresh
weekly) — Weigh accurately 0.2128 g of potassium
acid phthalate into a 100 mL volumetric flask, add
water, shake to dissolve, dilute to volume, and mix
well. Lower standards (prepare fresh daily) can be
made by diluting an aliquot of the 1000 mg/mL to the
appropriate volume.
9.2.3 Sample Preparation
9.2.3.1 Weigh 50 g of hydrogen peroxide, to the
nearest 0.01 g, into a 400 mL beaker. Add the platinum
sheet to the sample, cover the beaker with a Teflon
watch glass, and allow the reaction to go overnight (12
hours minimum). Transfer the solution to a 50 mL
volumetric flask, dilute with water, meeting the criteria
for Type E1.1 in ASTM D 5127, to a final volume of 50
mL.
9.2.4 Analysis
9.2.4.1 Using the prepared solutions, analyze TOC by
the total organic carbon analyzer after the instrument
has been calibrated with 0, 4, 10, and 20 µg/mL of TOC
standards.
9.3 Anions
9.3.1 The following method has given satisfactory
results in determining anion impurities at the values
specified for each of the following anions: chloride
(Cl), phosphate (PO
4
), nitrate (NO
3
), and sulfate (SO
4
).
Alternate methods may be used as long as appropriate
studies demonstrate a recovery between 75–125% of a
known sample spike for half of the value of each
specified anion.
9.3.2 Special Reagents
9.3.2.1 Eluent — Prepare an eluent solution that is 2.2
mM sodium carbonate (Na
2
CO
3
) and 0.75 mM sodium
bicarbonate (NaHCO
3
) in deionized water meeting the
criteria for Type E1.1 in ASTM D 5127. Store eluent
under a helium gas blanket.
9.3.2.2 Regenerant — Prepare a 0.025 N sulfuric acid
(H
2
SO
4
) in deionized water meeting the criteria for
Type E1.1 in ASTM D 5127.
9.3.2.3 Potassium Carbonate Solution — Prepare a
solution containing 500 mg of reagent grade potassium
carbonate (K
2
CO
3
) into 100 mL of water meeting the
criteria for Type E1.1 in ASTM D 5127.
9.3.3 Sample Preparation
9.3.3.1 In a clean environment, place 40 g of sample
into a clean beaker. Add 1 mL of a 5 mg/mL potassium
carbonate solution and evaporate carefully (at 100°C) to
a volume of 0.5 mL. Dilute with water meeting the
criteria for Type E1.1 in ASTM D 5127 to a final
volume of 20 mL.
NOTE 5: For safety purposes, a decomposition aid such as a
platinum strip should be used.
9.3.4 Analysis
9.3.4.1 Using the prepared solutions and blanks,
analyze chloride, nitrate, phosphate, and sulfate by ion
chromatography. Run a reagent blank. Samples and
reagent blanks should be prepared and analyzed in
triplicate.
9.3.4.2 Columns — Precolumn should be AG4-A
(Dionex) or equivalent and Separation column should
be AS4-A (Dionex) or equivalent.
9.4 Trace Metals Analysis
9.4.1 The following method has given satisfactory
results in determining metal ion impurities at the values