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SEMI C25-0699 E © SEMI 19 78, 2000 DICHLOROMETHANE (METHYLENE CHLO RIDE) 2 moisture. Stir vigorously and titrate with Karl Fischer reagent t o the same endpoin t. % Water H 2 O () = mL KF reagent × KF factor (g H 2 O/mL)…

DICHLOROMETHANE (METHYLENE CHLORIDE) SEMI C25-0699

SEMI C25-0699

SPECIFICATION FOR DICHLOROMETHANE (METHYLENE CHLORIDE)

This specification was technically approved by the Global Process Chemicals Committee and is the direct

responsibility of the North American Process Chemicals Committee. Current edition approved by the North

American Regional Standards Committee on April 23, 1999. Initially available on SEMI OnLine May 1999;

to be published June 1999. This document replaces SEMI C1.6 in its entirety. Originally published in 1978.

This document was editorially modified in March 2000. Changes were made to the note following Table 1.

1 Purpose

1.1 The purpose of this document is to standardize

requirements for dichloromethane (methylene chloride)

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

dichloromethane 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

dichloromethane used in the semiconductor industry.

3 Limitations

3.1 None.

4 Referenced Documents

SEMI C1 — Specifications for Reagents

5 Terminology

5.1 None.

6 Physical Property (for information only)

Density at 25°C 1.32 g/mL

Boiling Point 39.8°C

7 Requirements

7.1 The requirements for dichloromethane for Grade 1

are listed in Table 1.

8 Grade 1 Procedures

NOTE 1: 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 meter × 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: 40°C isothermal for 5 minutes,

then programmed to 200°C at 10°C/min.

Injector Temperature: 150°C

Detector Temperature: 250°C

Sample Size:

0.2 µL splitless

Carrier Gas: Helium at 3 mL/min

Detector: Thermal Conductivity

Approximate Retention Times (min):

Dichloromethane 6.0

Chloroform 11.0

Carbon Tetrachloride 14.0

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 Acidity — To 25 mL of water in a glass-stoppered

flask, add 10 mL of sample and 0.1 mL of

phenolphthalein indicator solution. Add 0.01 N sodium

hydroxide until a slight pink color persists after shaking

for one-half minute. Add 38 mL (50 g) of the sample,

mix well, and titrate with 0.01 N sodium hydroxide

until the pink color is reproduced. Not more than 1.0

mL of the sodium hydroxide solution should be

required.

8.4 Residue After Evaporation — Evaporate 76 mL

(100 g) of sample to dryness. Dry at 105°C for 30

minutes, cool in a desiccator, and weigh (see SEMI C1,

Section 3.3, Determination of Residue After

Evaporation).

8.5 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 76 mL (100 g) of sample, taking care

to protect the sample and contents of the flask from

SEMI C25-0699

moisture. Stir vigorously and titrate with Karl Fischer

reagent to the same endpoint.

% Water H

()

mL KF reagent × KF factor (g H

O/mL) × 100

Weight of sample (g)

8.6 Chloride — To a 100 mL separatory funnel, add

30 mL (40 g) of sample and 40 mL of water. Shake

well for 30 seconds and allow the two layers to

separate. Discard the sample (lower) layer. To a 20 mL

portion of the water layer add 1 mL of nitric acid and 1

mL of silver nitrate reagent solution. Any turbidity

produced should be no greater than that of a standard

containing 0.01 mg of chloride ion (Cl) in an equal

volume of solution containing the amounts of reagents

used.

8.7 Phosphate — To 7.5 mL (10 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 sulfate reagent 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

) is treated as the sample.

8.8 Heavy Metals (as Pb) — Evaporate 75 mL (100 g)

of sample to dryness on a steam bath in a hood.

Dissolve the residue in 3 mL of diluted hydrochloric

acid (1 + 1) and dilute with water to 15 mL. If

necessary, filter through a small filter and wash the

evaporating dish and the filter with 10 mL of water.

Dilute to 25 mL with water. For the standard, dilute a

solution containing 0.02 mg of lead ion (Pb) and 3 mL

of diluted hydrochloric acid (1 + 1) to 25 mL with

water. Adjust the pH of both solutions to between 3 and

4 with diluted ammonium hydroxide (10% NH

) or

with acetic acid, and dilute with water to 40 mL. To

each solution, add 10 mL of freshly prepared hydrogen

sulfide water and compare. The sample solution should

be no darker than the standard.

8.9 Arsenic and Antimony (as As) — Evaporate 152

mL (200 g) of sample in a 400 mL beaker to a small

volume in a hood. Add 50 mL of water and again

evaporate to a small volume. Repeat the evaporation

with water addition. Do not allow to go to dryness. Add

5 mL of nitric of sulfur trioxide. 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 the sentence which 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).

8.10 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.

8.10.1 Special Reagents

8.10.1.1 Mixed Acid — Mix one volume of ultra pure

70% nitric acid with four volumes of ultra pure 37%

hydrochloric acid.

8.10.1.2 Standards — Composite standards containing

0.5 ppm of each element in 10% v/v mixed acid

solution are stable for at least 60 days.

8.10.2 Sample Preparation — Place 2.5 mL of mixed

acid into a clean 400 mL PTFE beaker. Weigh in 200 g

of sample. Put a PTFE-coated stir bar in the solution

and put the beaker in a hood. Evaporate the sample

under a current of air, meeting class 100 cleanroom

specifications, with stirring to ensure continuous

contact of the acid and sample. Do not heat the sample

to minimize the loss of volatile organo-metallics.

Continue to evaporate until near dryness. Add 2.5 mL

of mixed acid, mix carefully, and transfer the solution

to a 25 mL volumetric flask. Rinse the beaker and

dilute to volume with water.

8.10.3 Analysis

8.10.3.1 Analyze the sample by plasma emission

spectrometry except sodium and potassium by atomic

absorption or flame emission within 24 hours of

dilution using matrix matched standards. Run a reagent

blank and correct the data as necessary.

NOTE 2: The trace metal analysis procedure is provisional,

pending second source verification of recovery data. To be

completed.

9 Grade 2 Procedures

9.1 This section does not apply to this chemical.

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.

DICHLOROMETHANE (METHYLENE CHLORIDE) SEMI C25-0699

12 Grade 5 Procedures

12.1 This section does not apply to this chemical.

13 VLSI Grade Procedures

13.1 This section does not apply to this chemical.

14 Tier A Procedures

14.1 This section does not apply to this chemical.

15 Tier B Procedures

15.1 This section does not apply to this chemical.

16 Tier C Procedures

16.1 This section does not apply to this chemical.

17 Tier D Procedures

17.1 This section does not apply to this chemical.

Table 1 Impurity Limits and Other Requirements

for Dichloromethane (Methylene Chloride)

Previous SEMI Reference # C1.6-96

Grade 1

(Specification)

Assay (CH

) 98.0% min

Color (APHA) 10 max

Acidity

0.2 µeq/g

Residue after Evaporation 10 ppm max

Chloride (Cl) 0.5 ppm max

Heavy Metals (as Pb) 0.2 ppm max

Phosphate (PO

) 1 ppm max

Water (H

O) 0.01% max

Aluminum (Al) 1 ppm max

Arsenic and Antimony (as As) 0.01 ppm max

Barium (Ba) 1 ppm max

Boron (B) 0.2 ppm max

Cadmium (Cd) 1 ppm max

Calcium (Ca) 1 ppm max

Chromium (Cr) 0.5 ppm max

Cobalt (Co) 0.1 ppm max

Copper (Cu) 0.1 ppm max

Gallium (Ga) 0.5 ppm max

Germanium (Ge) 1 ppm max

Gold (Au) 0.5 ppm max

Iron (Fe) 1 ppm max

Previous SEMI Reference # C1.6-96

Grade 1

(Specification)

Lithium (Li) 1 ppm max

Magnesium (Mg) 1 ppm max

Manganese (Mn) 1 ppm max

Nickel (Ni) 0.1 ppm max

Potassium (K) 1 ppm max

Silicon (Si) 1 ppm max

Silver (Ag) 0.5 ppm max

Sodium (Na) 1 ppm max

Strontium (Sr) 1 ppm max

Tin (Sn) 1 ppm max

Zinc (Zn) 1 ppm max

NOTE: Dichloromethane contains 0.0025−0.05% ethanol,

cyclohexane, or mixed pentenes as stabilizer.

NOTICE: 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.

SEMI makes no warranties or representations as to the

suitability of the standards set forth herein for any

particular application. The determination of the

suitability of the standard 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

mentioned herein. These standards are subject to

change without notice.

The user’s attention is called to the possibility that

compliance with this standard may require use of

copyrighted material or of an invention covered by

patent rights. By publication of this standard, SEMI

takes no position respecting the validity of any patent

rights or copyrights asserted in connection with any

item mentioned in this standard. Users of this standard

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.

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