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SEMI C27-0301 © SEMI 1978, 2001 HYDROCH LORIC ACID 2 Chrom o sorb P (80/ 100), 3 m × 3 mm stainless st eel or glass; injection port at 280 ° C with glass insert; column temperature initially 65 ° C, programme d at 6 ° C/…
HYDROCHLORIC ACID SEMI C27-0301 © SEMI 1978, 20011
SEMI C27-0301
SPECIFICATIONS AND GUIDELINES FOR HYDROCHLORIC ACID
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 by letter ballot dated October 17, 1999.
Initially available at www.semi.org February 2001; to be published March 2001. This document replaces
SEMI C1.7, C7.2, C8.2, C11.6, and C12.2 in their entirety. Originally published in 1978, 1990, 1992, 1996,
and 1995 respectively; previously published June 2000.
1 Purpose
1.1 The purpose of this document is to standardize
requirements for hydrochloric acid 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 hydrochloric acid 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
hydrochloric acid 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 These specifications and guidelines do not purport
to address safety issues, if any, associated with their
use. It is the responsibility of the users of these
specifications and guidelines to establish appropriate
safety and health practices and determine the
applicability of regulatory limitations prior to use.
3 Limitations
3.1 None.
4 Referenced Standards
4.1 SEMI Standards
SEMI C1 — Specifications for Reagents
4.2 ASTM Standards
1
ASTM D5127 — Standard Guide for Ultra Pure Water
Used in the Electronics and Semiconductor Industry
NOTE 1: As listed or revised, all documents cited shall be the
latest publications of adopted standards.
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
1.19 g/mL
7 Requirements
7.1 The requirements for hydrochloric acid for Grades
1 and 2, VLSI Grade, and Tiers B and C are listed in
Table 1.
8 Grade 1 Procedures
NOTE 2: Each laboratory is responsible for verifying the
validity of the method within its own operation.
8.1 Assay — Accurately weigh a glass-stoppered
conical flask containing about 30 mL of water. Deliver
from a pipet about 3 mL of sample near the water
surface, stopper immediately, and reweigh. Dilute to
about 50 mL with water, add methyl orange indicator
solution, and titrate with standardized 1 N sodium
hydroxide to a red-to-yellow color change.
%Assa
y
=
mL
×
N
of NaOH
×
3.646
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 Extractable Organic Substances — Cool 110 mL
of sample in an ice bath. Add 5 mL of 2,2,4-
trimethylpentane and 100 mL of water to each of two
250 mL separatory funnels. To a third funnel add 100
mL of water and 5 mL of the standard (see below). To
the first funnel add 100 mL of the cooled sample, and
100 mL of water to each of the remaining two. Stopper,
shake well, and allow the layers to separate. Inject 1.0
µL of each of the 2,2,4-trimethylpentane extracts into a
gas chromatograph with a flame ionization detector.
The following conditions have been found to be
satisfactory: Column — 20% Carbowax 20 M on
SEMI C27-0301 © SEMI 1978, 2001 HYDROCHLORIC ACID2
Chromosorb P (80/100), 3 m × 3 mm stainless steel or
glass; injection port at 280°C with glass insert; column
temperature initially 65°C, programmed at 6°C/min up
to 140°C; carrier gas — nitrogen at 40 mL/min; signal
adjusted to give an 80% full-scale deflection; and
preferably, electronic integration of peak areas. For
DDT: Column — 5% silicone gum SESE-30 on
Chromosorb W (60/80), 1.5 × 3 mm, injection port —
as above; column temperature — isothermal at 205°C;
carrier gas — nitrogen at 75 mL/min, and preferably,
electronic integration of peak areas. The order of
elution is 2,2,4-trimethylpentane, carbon tetrachloride,
benzene, chloroform, 2,2,4-trimethylpentane impurity,
1,2-dichloroethane, chlorobenzene, and dichloro-
benzene. The total area under the impurity peaks from
the sample should be no greater than that from the
blank (extract from second funnel) by more than one-
half the total area under the peaks from the standard
(third funnel), also corrected for the blank.
8.3.1 Standard — Use a syringe to add the volumes of
liquid listed in Table 2 into 300 mL of 2,2,4-
trimethylpentane. Add 25 mg of DDT to the solution.
Dilute to 500 mL with 2,2,4-trimethylpentane. The
2,2,4-trimethylpentane used for both the standard and
the analysis should be free from impurities that interfere
with the chromatographic analysis.
8.4 Free Halogen (as Cl
2
) — Mix 100 mL of sample
and 100 mL of freshly boiled water and cool. Add 0.1
mL of 2% potassium iodide reagent solution and 1 mL
of carbon disulfide, and mix. The carbon disulfide
should not acquire a pink color in one-half minute.
8.5 Phosphate — To 170 mL (200 g) of sample, add
10 mL of sodium carbonate reagent solution and
evaporate to dryness on a steam bath in a hood.
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 solution. Allow to
stand at room temperature for 2 hours. Any blue color
produced should be no greater than that produced when
0.01 mg of phosphate ion (PO
4
) is treated like the
sample.
8.6 Sulfate — To 84 mL (100 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 10 minutes.
Any turbidity should be no greater than that produced
when 0.05 mg of sulfate ion (SO
4
) is treated as the
sample.
8.7 Sulfite — Add 1 mL of 10 percent potassium
iodide reagent solution, 5 mL of hydrochloric acid, and
2 mL of starch indicator solution to 400 mL of oxygen-
free water. Add 0.01 N iodine until a faint permanent
blue color is produced. Add 85 mL of the sample and
titrate with 0.01 N iodine to the same endpoint. Not
more than 0.20 mL should be required.
8.8 Arsenic and Antimony (as As) — To 168 mL (200
g) of sample in a 400 mL beaker, add 10 mL of nitric
acid and 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 the General Method for Arsenic
(and Antimony) under SEMI C1, Section 3.4.5, starting
with tile 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 0.001 mg of arsenic (As).
8.9 Trace Metal Analysis — The following method
has given satisfactory results in determing 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 item.
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 2% Nitric Acid Solution — Dilute 20 mL of
ultra pure nitric acid to 1 L using water meeting the
criteria for Type E1.1 in ASTM D5127.
8.9.2 Sample Preparation
8.9.2.1 In a clean environment, place 250 mL of
sample in a PTFE evaporating dish. Slowly evaporate
on a hot plate, avoiding loss of sample by effervescence
or spattering until approximately 2 mL of liquid
remains. Note: Evaporation typically requires 2 1/2 to 4
hours. Cool. Transfer quantitatively to a 50 mL
volumetric flask using 2% nitric acid for rinsing and
dilution to volume. Run a reagent blank.
8.9.3 Analysis
8.9.3.1 Using the acid sample and reagent blank,
analyze group 1 elements by flame atomic absorption
spectroscopy and all other elements by plasma emission
spectroscopy.
HYDROCHLORIC ACID SEMI C27-0301 © SEMI 1978, 20013
9 Grade 2 Procedures
NOTE 2: Each laboratory is responsible for verifying the
validity of the method within its own operation.
9.1 Non-Metal Impurities — See Section 8, which
contains procedures for the following tests:
Assay
Color (APHA)
Free Halogen
Phosphate
Sulfate
Sulfite
9.2 Trace Metals Analysis
9.2.1 The following method has given satisfactory
results in determining metal ion impurities at the values
specified for each of the following metals: aluminum
(Al), antimony (Sb), arsenic (As) barium (Ba),
beryllium (Be), bismuth (Bi), boron (B), calcium (Ca),
chromium (Cr), cobalt (Co), copper (Cu), gallium (Ga),
germanium (Ge), gold (Au), iron (Fe), lead (Pb),
lithium (Li), magnesium (Mg), manganese (Mn),
molybdenum (Mo), nickel (Ni), niobium (Nb),
potassium (K), silver (Ag), sodium (Na), strontium (Sr),
tantalum (Ta), tin (Sn), titanium (Ti), vanadium (V),
zinc (Zn), and zirconium (Zr). 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 element.
9.2.2 Special Reagents
9.2.2.1 Hydrochloric Acid, Ultrapure — Use
hydrochloric acid specified for low metal ion content.
9.2.2.2 3.7% Hydrochloric Acid Solution — Dilute 20
g of ultrapure hydrochloric acid to 200 g using water
meeting the criteria for Type E1.1 in ASTM D5127.
9.2.2.3 Nitric Acid, Ultrapure — Use nitric acid
specified for low metal ion content.
9.2.2.4 1% Nitric Acid Solution — Dilute 10 mL of
ultrapure nitric acid to 1 L using water meeting the
criteria for Type E1.1 in ASTM D5127.
9.2.2.5 Water — The water used for all the dilution,
calibration and standards should meet at a minimum the
criteria for Type E1.1 in ASTM D5127 in regard to
cation analysis.
9.2.2.6 Rhodium Internal Standard — Make up the
internal standard solution to a concentration of 20
µg/mL (ppm) from the appropriate concentrated
standard rhodium solution.
9.2.3 Sample Preparation
9.2.3.1 In a clean environment, place 2.00 g of sample
into a tared FEP bottle (30 mL), dilute with “attainable”
water to a final weight of 20.0 g. Add 20 µL of the
rhodium internal standard solution. Run a reagent
blank.
9.2.3.2 Vanadium — In a clean environment, place
20.0 g of sample into a clean PTFE dish. Slowly
evaporate on a hot plate to dryness avoiding loss of
sample by effervescence or spattering. Dissolve the
residue with 5 mL of the 1% nitric acid solution by
heating on a hot plate at low temperature for several
minutes. Cool to room temperature, dilute to 20 g with
1% nitric acid, add 20 µL of the rhodium internal
standard, mix well. Run a reagent blank.
9.2.4 Analysis
9.2.4.1 Using the prepared solutions and blanks,
analyze sodium, potassium, calcium and iron by
graphite furnace atomic absorption (GFAA) and the
remaining elements by inductively coupled plasma
mass spectrometry (ICP/MS). For calibration, the
standards are made up with the 3.7% hydrochloric acid
solution and the rhodium internal standard except for
the analysis of vanadium which is performed using 1%
nitric acid as the matrix. All standards must contain 10
ng/g of rhodium as the internal standard.
10 Grade 3 Procedures
10.1 This section does not apply to this chemical.
11 Grade 4 Procedures
11.1 This section does not apply to this chemical.
12 Grade 5 Procedures
12.1 This section does not apply to this chemical.
13 VLSI Grade Procedures
13.1 Specific procedures for this grade do not exist.
Refer to Sections 8 and 9 for available procedures.
14 Tier A Procedures
14.1 This section does not apply to this chemical.
15 Tier B Procedures
15.1 Standardized test methods are being developed
for all parameters at the purity levels indicated. Until
standardized test methods are published, test
methodology shall be determined by user and supplier.
The Process Chemicals Committee considers a test
method to be valid only if there is a documented
recovery study showing a recovery of 75−125%.