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SEMI C33-0301 © SEMI 1986, 2001 n-METHYL 2-PYRROLIDONE 2 8.3 Wate r — Add 25 mL of m etha n o l to a dry titration flask and add Karl Fischer (KF) reagent to a visually or electrometri cally determined en dpoint that per…
n-METHYL 2-PYRROLIDONE SEMI C33-0301 © SEMI 1986, 20011
SEMI C33-0301
SPECIFICATIONS FOR n-METHYL 2-PYRROLIDONE
These specifications 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 October 17, 1999. Initially available at www.semi.org
February 2001; to be published March 2001. This document replaces SEMI C1.25, C7.16, and C8.11 in their
entirety. Originally published in 1986, 1992, and 1998 respectively; previously published June 1999.
1 Purpose
1.1 The purpose of this document is to standardize
requirements for n-methyl 2-pyrrolidone 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 n-methyl 2-
pyrrolidone 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 n-
methyl 2-pyrrolidone used in the semiconductor
industry.
2.2 These standards do not purport to address safety
issues, if any, associated with their use. It is the
responsibility of the user of these standards 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.
5 Terminology
5.1 None.
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
6 Physical Property (for information only)
Density at 25°C
1.03 g/mL
7 Requirements
7.1 The requirements for n-methyl 2-pyrrolidone for
Grades 1, 2, and 3 are listed in Table 1.
8 Grade 1 Procedures
NOTE 2: Due to the uncertainty of acid concentration in the
liquid residue, the final concentration can be estimated to be
approximately 2% (v/v).
NOTE 3: Each laboratory is responsible for verifying the
validity of the method within its own operation.
8.1 Assay — Analyze the sample by gas
chromatography (see SEMI C1, Section 3.1, Guidelines
for Assay by Wide Bore Column Gas
Chromatography). The parameters cited have given
satisfactory results.
Column: 30 × 530 micron I.D. fused silica capillary,
coated with 5 micron film of DB-1 or equivalent (100%
methyl silicone which has been surface bonded and
cross linked).
Column Temperature:
100°C isothermal
Injector Temperature:
250°C
Detector Temperature:
300°C
Sample Size:
0.2 µL splitless
Carrier Gas: Helium at 5 mL/min
Detector: Thermal
Conductivity
Approximate Retention Times (min):
Butyrolactone 15.2
1-Methyl 2-Pyrrolidone 20.2
Methyl Homologue 21.2
Methyl Homologue 23.0
8.2 Color — Dilute 10.0 mL of platinum-cobalt stock
solution (APHA No. 500) with water. Compare this
standard (APHA No. 50) with 100 mL of sample in
Nessler tubes. View vertically over a white background.
The sample must be no darker than the standard.
SEMI C33-0301 © SEMI 1986, 2001 n-METHYL 2-PYRROLIDONE2
8.3 Water — Add 25 mL of methanol to a dry titration
flask and add Karl Fischer (KF) reagent to a visually or
electrometrically determined endpoint that persists for
30 seconds. Add 98 mL (100 g) of sample, taking care
to protect the sample and contents of the flask from
moisture. Stir vigorously and titrate with Karl Fischer
reagent to the same endpoint.
% Water H
2
O
()
=
mL KF rea
g
ent
×
KF facto
r
g
H
2
OmL
()
×
100
Wei
g
ht of sam
p
le
g
()
8.4 Free Amines — Weigh 63 mL (65 g) of sample
into a 500 mL beaker. Add 100 mL of 2-propanol and
mix thoroughly. Into the solution, insert a pH and
reference electrodes connected to a pH meter set to the
direct voltage mode. Titrate potentiometrically with
0.05 N hydrochloric acid in 2-propanol. Express the
result in terms of methylamine:
% Free Amines as CH
3
N
H
2
()
=
mL
×
N
of HCl
×
3.10
Weight of sample g
(
)
8.5 Chloride — In a 50 mL glass-stoppered graduated
cylinder, dilute 24.5 mL (25 g) of sample with water to
volume. Place a 10 mL aliquot of this solution into a 50
mL Nessler tube and a 30 mL aliquot into a second
tube. To the first tube add 0.01 mg of chloride standard
and mix. Dilute the contents of each tube to about 45
mL with water, mix, add 1 mL of nitric acid and 1 mL
of silver nitrate reagent solution, mix thoroughly, and
allow to stand for 10 minutes. Any turbidity produced
by the sample should be no greater than that of the 0.01
mg standard.
8.6 Phosphate — Add 20 mL (20) of sample to 100
mL of dilute ammonium hydroxide (1 + 4). Prepare a
standard containing 0.1 mg of phosphate ion (PO
4
) in
100 mL of dilute ammonium hydroxide. Proceed as
follows with each of the two solutions.
8.6.1 Add, while stirring vigorously, 3.5 mL of a 10%
solution of ferric nitrate 9-hydrate. Allow to stand for
15 minutes. If the precipitate has not coagulated by this
time, warm gently (avoid boiling). Filter and wash the
precipitate on the filter with several portions of quite
dilute ammonium hydroxide (1 + 9). Discard the filtrate
and washings. Dissolve the precipitate on the filter with
50 mL nitric acid (1 + 3) added in small portions. Catch
the filtrate in a 250 mL glass-stoppered conical flask.
Add 13 mL of ammonium hydroxide (28-32% NH
3
) to
the flask while swirling and continue agitation until any
precipitate redissolves. Warm the solution to 40°C and
add 50 mL of ammonium molybdate-nitric acid reagent
solution. Shake vigorously for 5 minutes and allow to
stand at 40°C for 2 hours. The precipitate, if any, for
the sample should be no greater than that for the
standard.
8.6.2 Ammonium Molybdate-Nitric Acid Reagent
Solution — Mix thoroughly 100 g of molybdate acid,
85%, with 240 mL of water and 140 mL of ammonium
hydroxide (28 - 32% NH
3
). Filter and add 60 mL of
nitric acid. Cool and while stirring continually, pour
into a cooled mixture of 400 mL of nitric acid and 960
mL of water. Add 0.1 g of ammonium phosphate,
monobasic, NH
4
H
2
PO
4
, allow to stand 24 hours and
filter through glass wool.
8.7 Arsenic and Antimony (as As) — Evaporate 20 mL
(20 g) of sample in a 150 mL beaker to a small volume
on a hot plate. Cool, add carefully 15 mL of nitric acid
and 5 mL of sulfuric acid, and evaporate to dense fumes
of sulfur trioxide. Add 10 mL of nitric acid and again
evaporate to dense fumes. If carbon is still present,
cool, add 1 mL of 30% hydrogen peroxide, and
evaporate to dense fumes of sulfur trioxide. Repeat this
step with hydrogen peroxide addition until carbon has
been removed completely. Cool, and cautiously wash
the colorless residue 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 the sentence that
begins “Swirl the flask...”. Any red color in the silver
diethyldithiocarbamate solution of the sample should be
no greater than that of the standard containing 0.002 mg
of arsenic (As).
8.8 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 item.
8.8.1 Special Reagents
8.8.1.1 Hydrochloric Acid, Ultra Pure — Use
hydrochloric acid specified for ultra low metal ion
content.
8.8.1.2 Mannitol Powder — Use mannitol specified
for reagent grade (A.C.S.) and determined, via the
reagent blank, to be ultra metal ion content.
8.8.1.3 5% Mannitol Solution — Dissolve and dilute 5
g of mannitol to 100 mL using water meeting the
criteria for Type E1.1 in ASTM D5127.
8.8.1.4 2% (v/v) Hydrochloric Acid Solution — Dilute
20 mL of ultra pure, 12 M hydrochloric acid to 1 L
using water meeting the criteria for Type E1.1 in
ASTM D5127.
n-METHYL 2-PYRROLIDONE SEMI C33-0301 © SEMI 1986, 20013
8.8.2 Sample Preparation
8.8.2.1 In a clean environment, place 250 g of solvent
in a PTFE dish. Add 0.5 mL of freshly prepared 5%
mannitol solution. Slowly evaporate on a hot plate,
avoiding loss of sample by effervescence or spattering
until approximately 1 mL of liquid remains. Take up
liquid and all visible residue (from walls of dish) with 1
mL ultra pure, 12 M hydrochloric acid and continue
heating until approximately 0.5 mL of liquid remains.
No undissolved particulate matter should be observed.
Otherwise, repeat the addition of hydrochloric acid until
all particulate matter is dissolved. Transfer
quantitatively to a 50 mL volumetric flask using 2%
(v/v) hydrochloric acid and adjust liquid level to mark.
Prepare a reagent blank using the same reagents and in
the same manner as for the sample concentration.
8.8.3 Analysis
8.8.3.1 Using the prepared sample and reagent blank,
analyze group 1 elements potassium (K) and sodium
(Na) by atomic absorption spectroscopy and all other
elements by plasma emission spectrometry. Apply, if
necessary, a reagent blank correction to the final
determined value of the sample.
9 Grade 2 Procedures
9.1 Non-Metal Impurities — See Section 8, which
contains procedures for the following tests:
Assay
Color (APHA)
Water (H
2
O)
9.2 Methyl Amines
9.2.1 The following method has given satisfactory
results in determining methyl amine impurities at the
values specified for each of the following methyl
amines: mono-methylamine (MMA), di-methylamine
(DMA), and tri-methylamine (TMA). Alternative
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 Eluent — Prepare 0.025 N hydrochloric (HCl)
solution in deionized water meeting the criteria for
Type E1.1 in ASTM D5127.
9.2.2.2 Regenerant — Prepare a 0.1 M tetrabutyl-
ammonium hydroxide (TBAOH) solution in deionized
water meeting the criteria for Type E1.1 in ASTM
D5127.
9.2.3 Sample Preparation — Sample is injected neat.
9.2.4 Analysis
9.2.4.1 Using the prepared solutions and blanks,
analyze mono-methylamine, di-methylamine, and tri-
methylamine by ion chromatography. Run a reagent
blank. Samples and reagent blanks should be prepared
and analyzed in triplicate.
9.2.4.2 Columns — Precolumn should be CG2
(Dionex) or equivalent and separation column should
be a CS2 (Dionex) or equivalent.
9.3 Anions
9.3.1 The following method has given satisfactory
results in determining various anions at the values
specified for each of the following anions: chloride
(Cl), nitrate (NO
3
), phosphate (PO
4
), 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 a solution containing 0.38 g
of sodium carbonate (Na
2
CO
3
) and 0.29 g of sodium
bicarbonate (NaHCO
3
) in 2 liters of deionized water
meeting the criteria for Type E1.1 in ASTM D5127.
9.3.2.2 Regenerant — Deionized water meeting the
criteria for Type E1.1 in ASTM D5127.
9.3.3 Sample Preparation
9.3.3.1 20 mL of NMP is added to a 100 mL plastic
volumetric flask and is filled to the mark using
deionized water meeting the criteria for Type E1.1 in
ASTM D5127.
9.4 Analysis
9.4.1 Using the prepared solutions and blanks, analyze
chloride, nitrate, phosphate, and sulfate by ion
chromatography. Run a reagent blank. Samples and
blanks should be prepared in triplicate.
9.4.2 Columns — Precolumn should be AG3 (Dionex)
or equivalent and the separation column should be AS3
(Dionex) or equivalent.
9.5 Trace Metals Analysis
9.5.1 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), boron (B), cadmium
(Cd), calcium (Ca), chromium (Cr), cobalt (Co), copper
(Cu), gold (Au), iron (Fe), lead (Pb), lithium (Li),
magnesium (Mg), manganese (Mn), nickel (Ni),
potassium (K), silver (Ag), sodium (Na), strontium (Sr),