BACKGROUND STATEMENT FOR SEMI DRAFT DOCUMENT 4543A
REVISION TO SEMI C20-1101, SPECIFICATION AND GUIDELINES FOR
AMMONIUM FLUORIDE 40%, WITH TITLE CHANGE TO:
SPECIFICATION AND GUIDE FOR AMMONIUM FLUORIDE 40%
Notice: This background statement is not part of the balloted item. It is provided solely to assist the recipient in
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Background
SEMI C20 is due for 5-year review. As a result of the review process, this ballot proposes changes for consistency
with other SEMI Standards on liquid chemicals. These changes are marked by strikethrough for deletions and
underlines for additions.
Review and Adjudication Information
Task Force Review
Analytical Methods TF
Group:
Monday 02 April 2012
Date:
Time & Timezone: 13:00-15:00 (PST)
SEMI HQ
Location:
City, State/Country: San Jose, CA
Frank Flowers (FMC)
Leader(s):
Standards Staff:
Michael Tran (SEMI NA)
408.943.7019
mtran@semi.org
Committee Adjudication
NA Liquid Chemicals Committee
Tuesday 03 April 2012
09:00-12:00 (PST)
SEMI HQ
San Jose, CA
Frank Flowers (FMC)
Frank Parker (ICL)
Michael Tran (SEMI NA)
408.943.7019
mtran@semi.org
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.
Notice: Additions are indicated by underline and deletions are indicated by strikethrough.
Semiconductor Equipment and Materials International
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SEMI DRAFT DOCUMENT 4543A
REVISION TO SEMI C20-1101, SPECIFICATION AND GUIDELINES FOR
AMMONIUM FLUORIDE 40%, WITH TITLE CHANGE TO:
SPECIFICATION AND GUIDE FOR AMMONIUM FLUORIDE 40%
1 Purpose
1.1 The purpose of this standard is to standardize requirements for ammonium fluoride 40% used in the
semiconductor industry and testing procedures to support those standards. Test methods have been shown to give
statistically valid results. This standard also provides guidelines for grades of ammonium fluoride 40% 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 ammonium fluoride 40% used in the semiconductor industry.
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 Limitations
3.1 None.
4 Referenced Standards and Documents
4.1 SEMI Standard
SEMI C1 — Guide for the Analysis of Liquid Chemicals
NOTICE: Unless otherwise indicated, all documents cited shall be the latest published versions.
5 Terminology
5.1 None.
6 Properties
Table 1 Properties of Ammonium Fluoride 40%
Chemical Formula
NH4F
CAS Number
12125-01-8
Density at 25°C
1.11 g/ml
7 Requirements and Suggested Values
7.1 The requirements for ammonium fluoride 40% for Grade 1, and suggested values for Tiers A and B are listed in
Table 2.
8 Grade 1 Procedures
8.1 Assay — Accurately weigh 3 g of sample in a polyethylene weighing bottle. Transfer with water to a
polyethylene beaker and dilute to 100 mL. Add 40 mL of neutralized formaldehyde solution and stir magnetically
for 15 minutes or allow to stand for 1/2 hour. Titrate with standardized 1 N sodium hydroxide to a slight pink color.
This is a Draft Document of the SEMI International Standards program. No material on this page is to be construed as an official or adopted Standard or Safety Guideline.
Permission is granted to reproduce and/or distribute this document, in whole or in part, only within the scope of SEMI International Standards committee (document
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Doc. 4543A  SEMI
LETTER (YELLOW) BALLOT
DRAFT
Document Number: 4543A
Date: 2/6/2016
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𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑁𝑎𝑂𝐻 (𝑚𝑙) × 𝑁𝑜𝑟𝑚𝑎𝑙𝑖𝑡𝑦 𝑜𝑓 𝑁𝑎𝑂𝐻 × 3.704
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑆𝑎𝑚𝑝𝑙𝑒 (𝑔)
(1)
NOTE 1: Neutralized formaldehyde solution: Dilute 20 mL of 37% formaldehyde solution with 20 mL of water, add 0.1 mL of
phenolphthalein indicator solution, and titrate with 0.1 N sodium hydroxide to a slight pink color.
8.2 pH of a 1% Solution — Dilute 2.5 mL (2.8 g) of sample to 100 mL with carbon dioxide- and ammonia-free
water. Using a pH meter determine the pH at 25C 1 to 2 minutes after immersion of electrodes. The pH range
6.0–7.5 corresponds to 0.2% free hydrogen fluoride (HF) to 0.2% ammonium hydroxide (NH4OH) in the original
solution.
8.3 Chloride — Mix 2.2 mL (2.5 g) of sample with 20 mL of water containing 0.5 g of boric acid. Add 1 mL of
nitric acid and 1 mL of silver nitrate reagent solution and allow to stand for 5 minutes. Any turbidity produced shall
be no greater than that produced when 0.01 mg of chloride ion (Cl) is treated as the sample.
8.4 Nitrate — To 2 mL of water in a white plastic beaker, add 0.9 mL (1 g) of sample, 1 mL of sulfuric acid, 0.05
mL of 0.01 N (0.002 M) potassium permanganate, mix, and decolorize with sodium arsenite reagent solution (see
SEMI C1). Dilute to 50 mL with brucine sulfate reagent solution (see SEMI C1) and mix. Heat the solution in a
preheated (boiling water) bath for 10 minutes. Cool rapidly in an ice bath to room temperature. The yellow color of
the sample shall be no greater than that produced when 0.01 mg of nitrate ion (NO 3) is treated as the sample.
8.5 Phosphate — To a 9 mL (10 g) sample in a platinum dish, add 1 mL of sodium carbonate reagent solution and
40 mL of nitric acid. Evaporate carefully, to prevent spattering, to near dryness. Cool, wash down the sides of the
dish with 5 mL of nitric acid, and evaporate to dryness. Repeat the evaporation with nitric acid two more times to
ensure complete removal of all the fluoride. To the cooled dish, add 25 mL of 0.5 N sulfuric acid to dissolve the
residue, warming if necessary. Cool, transfer to a color comparison tube, and add 1 mL of ammonium molybdate
reagent solution (see SEMI C1), 1 mL of p-(methylamino)phenol sulfate reagent solution(see SEMI C1) and allow
to stand at room temperature for 2 hours. Any blue color shall be no greater than that produced when 0.01 mg of
phosphate ion (PO4) is treated as the sample.
8.6 Sulfate — To 23 mL (25 g) of sample, add 10 mL of sodium carbonate reagent solution (see SEMI C1) and heat
gently until sample has been volatilized. To the residue add 5 mL of hydrochloric acid 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 (see SEMI C1) mix, and allow to stand for 10 minutes. Any turbidity
developed shall be no greater than that produced when 0.05 mg of sulfate ion (SO 4) solution is treated as the sample.
8.7 Arsenic and Antimony (as As) — To 30 mL (33 g) in a fluoroplastic beaker, add 20 mL of nitric acid and 5 mL
of hydrochloric acid, and evaporate to dryness in a sand bath in a hood. Completely volatilize the ammonium
fluoride, but do not bake. Add 10 mL of water and 5 mL of sulfuric acid and evaporate to dense fumes 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 SEMI C1
under section, “Trace Arsenic (and Antimony) determination”, starting with the sentence that begins, “Swirl the
flask....”. Any red color in the silver diethyldithiocarbamate solution of the sample shall be no greater than that of
the standard containing 0.001 mg of arsenic (As).
8.8 Trace Element Contents — By a suitable emission spectrometry procedure (see SEMI C1) and determine for
each of the specified trace elements that its content is not greater than the stated specification limit.
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.
This is a Draft Document of the SEMI International Standards program. No material on this page is to be construed as an official or adopted Standard or Safety Guideline.
Permission is granted to reproduce and/or distribute this document, in whole or in part, only within the scope of SEMI International Standards committee (document
development) activity. All other reproduction and/or distribution without the prior written consent of SEMI is prohibited.
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LETTER (YELLOW) BALLOT
% 𝐴𝑠𝑠𝑎𝑦 =
DRAFT
Document Number: 4543A
Date: 2/6/2016
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3081 Zanker Road
San Jose, CA 95134-2127
Phone: 408.943.6900, Fax: 408.943.7943
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 Tier A Procedures
13.1 Standardized test methods are being developed for all parameters at the purity levels indicated. Methods must
comply with SEMI C1 requirements for method validation.
14 Tier B Procedures
14.1 Standardized test methods are being developed for all parameters at the purity levels indicated. Methods must
comply with SEMI C1 requirements for method validation.
15 Tier C Procedures
15.1 This section does not apply to this chemical.
16 Tier D Procedures
16.1 This section does not apply to this chemical.
Table 2 Impurity Limits, Suggested Values and Other Requirements for Ammonium Fluoride 40%
Previous SEMI Reference #
SEMI C1.3-95
SEMI C7.18-95
--
Grade 1
Tier A
Tier B
(Guide)
(Guide)
(Specification)
Assay (NH4F)
39.0%–41.0%
pH (1% solution at 25C)
6.0–7.5
)
39.0%–41.0% 39.0%–41.0%
.
6.0–7.5
6.0–7.5
2 ppm max.
2 ppm max.
3 ppm max.
3 ppm max.
Chloride (Cl)
4 ppm max.
Nitrate (NO3)
10 ppm max.
Phosphate (PO4)
1 ppm max.
Sulfate (SO4)
2 ppm max.
.
2 ppm max.
2 ppm max.
Aluminum (Al)
0.2 ppm max.
.
10 ppb max.
1 ppb max.
Antimony (Sb)
--
10 ppb max.
1 ppb max.
Arsenic (As)
--
10 ppb max.
1 ppb max.
Barium (Ba)
--
10 ppb max.
1 ppb max.
10 ppb max.
1 ppb max.
0.5 ppm max. 0.5 ppm max.
.
.
.
Boron (B)
0.2 ppm max.
.
Cadmium (Cd)
--
10 ppb max.
1 ppb max.
Calcium (Ca)
0.2 ppm max.
10 ppb max.
1 ppb max.
This is a Draft Document of the SEMI International Standards program. No material on this page is to be construed as an official or adopted Standard or Safety Guideline.
Permission is granted to reproduce and/or distribute this document, in whole or in part, only within the scope of SEMI International Standards committee (document
development) activity. All other reproduction and/or distribution without the prior written consent of SEMI is prohibited.
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LETTER (YELLOW) BALLOT
DRAFT
Document Number: 4543A
Date: 2/6/2016
Semiconductor Equipment and Materials International
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Phone: 408.943.6900, Fax: 408.943.7943
Table 2 Impurity Limits, Suggested Values and Other Requirements for Ammonium Fluoride 40%
Previous SEMI Reference #
SEMI C1.3-95
SEMI C7.18-95
--
Grade 1
Tier A
Tier B
(Guide)
(Guide)
10 ppb max.
1 ppb max.
10 ppb max.
1 ppb max.
(Specification)
)
Chromium (Cr)
0.1 ppm max.
Copper (Cu)
0.1 ppm max.
Iron (Fe)
0.2 ppm max.
10 ppb max.
1 ppb max.
Lead (Pb)
0.3 ppm max.
10 ppb max.
1 ppb max.
.
Lithium (Li)
--
10 ppb max.
1 ppb max.
Magnesium (Mg)
0.2 ppm max.
10 ppb max.
1 ppb max.
Manganese (Mn)
0.2 ppm max.
10 ppb max.
1 ppb max.
.
Nickel (Ni)
0.3 ppm max.
10 ppb max.
1 ppb max.
Potassium (K)
0.3 ppm max.
10 ppb max.
1 ppb max.
Sodium (Na)
0.3 ppm max.
10 ppb max.
1 ppb max.
.
Tin (Sn)
0.2 ppm max.
10 ppb max.
1 ppb max.
Titanium (Ti)
0.3 ppm max.
10 ppb max.
1 ppb max.
Vanadium (V)
--
10 ppb max.
1 ppb max.
Zinc (Zn)
0.2 ppm max.
10 ppb max.
1 ppb max.
Particles in bottles: size, #/mL
#1
#1
#1
.
#1 Due to the limitations of current particle counters, particle size and number are to be agreed upon between supplier
and user. See “Calibration and Measurement Method for Particles in Liquids” in SEMI C1.
NOTICE: Semiconductor Equipment and Materials International (SEMI) makes no warranties or representations as
to the suitability of the Standards and Safety Guidelines set forth herein for any particular application. The
determination of the suitability of the Standard or Safety Guideline 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 or equipment mentioned herein. Standards and Safety Guidelines are subject to change
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rights or copyrights asserted in connection with any items mentioned in this Standard or Safety Guideline. Users of
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and the risk of infringement of such rights are entirely their own responsibility.
This is a Draft Document of the SEMI International Standards program. No material on this page is to be construed as an official or adopted Standard or Safety Guideline.
Permission is granted to reproduce and/or distribute this document, in whole or in part, only within the scope of SEMI International Standards committee (document
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Document Number: 4543A
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LETTER (YELLOW) BALLOT
DRAFT
Document Number: 4543A
Date: 2/6/2016
This is a Draft Document of the SEMI International Standards program. No material on this page is to be construed as an official or adopted Standard or Safety Guideline.
Permission is granted to reproduce and/or distribute this document, in whole or in part, only within the scope of SEMI International Standards committee (document
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