Background Statement for SEMI Draft Document 4589A
REVISION TO SEMI C62-1107
SPECIFICATION FOR POROGEN PRECURSORS USED IN LOW K CVD
PROCESSES
Note: This background statement is not part of the balloted item. It is provided solely to assist the recipient in
reaching an informed decision based on the rationale of the activity that preceded the creation of this document.
Note: Recipients of this document are invited to submit, with their comments, notification of any relevant patented
technology or copyrighted items of which they are aware and to provide supporting documentation. In this context,
“patented technology” is defined as technology for which a patent has issued or has been applied for. In the latter
case, only publicly available information on the contents of the patent application is to be provided.
Porogen precursors are required to deposit porous low k dielectric layers for the 45 nm node and beyond.
At the present time there is no standardization on either the specification for the materials or the analytical
methods used to certify these materials. The standard will be useful for all materials suppliers to this
market. The draft was balloted and approved as the Guideline at SEMICON West, July 2007.
This ballot is being proposed to validate analytical methodologies since these test methods have been
shown to give statistically valid results.
Data to support validated methodologies may be reviewed at the following website at
http://teams.semi.org/stds_chem
This letter ballot will be reviewed by the Analytical Methods Task Force and adjudicated by the Liquid
Chemicals Committee at their meetings at SEMI HQ in San Jose, CA, during the week of 3rd November,
2008.
Note: Additions are indicated by underline and deletions are indicated by strikethrough
Semiconductor Equipment and Materials International
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DRAFT
SEMI Draft Document 4589A
REVISION TO SEMI C62-1107
SPECIFICATION FOR POROGEN PRECURSORS USED IN LOW K CVD
PROCESSES
1 Purpose
1.1 The purpose of this document is to provide specifications for porogen precursors used in Low K CVD processes
for which a need has been identified.
2 Scope
2.1 The scope of this document lists the proposed impurity limits for porogen precursors (e.g., Alpha-Terpinine,
Limonene, Bicycloheptadiene, and Cyclooctane) used in the semiconductor industry.
NOTICE: 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 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 Physical Property (for information only)
Alpha-Terpinine
Limonene
Bicycloheptadiene
Cyclooctane
Chemical Formula
C10H16
C10H16
C7H8
C8H16
CAS#
99-86-5
138-86-3
121-46-0
292-64-8
Appearance
Clear liquid
Clear liquid
Clear Liquid
Clear Liquid
0.845 gm/mL
0.840 gm/mL
0.906 gm/mL
0.834 gm/mL
Mol. Wt
136 g/mol
136.23 g/mol
92.14 g/mol
112.21 g/mol
Boiling Point
172–175ºC
175–176ºC
88–90ºC
151–153ºC
Density
7 Requirements
7.1 The requirements for porogen precursors for Grade 1 are listed in Table 1.
8 Grade 1 Procedures
8.1 Assay — The following method has given satisfactory results in determining assay at the value specified in
these chemicals. Alternative methods may be used as long as appropriate method validation as per SEMI C1 can be
demonstrated.
This is a draft document of the SEMI International Standards program. No material on this page is to be construed as an offi cial or adopted standard. 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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Document Number: 4589A
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8.1.1 Since most impurities in each of these porogens have the same empirical formula as the main component, the
concentration of each component is directly proportional to the peak areas and no external calibration is necessary.
8.1.2 Program a gas chromatograph fitted with a 30m long x 250 m ID x 0.5 m 5% phenyl – 95%
polydimethylsiloxane film column, a split injection port, and a flame ionization detector (FID) according to the
parameters in the Table.
Parameter
Oven
Initial Temp [C]
Initial Time [min]
Ramp1 [C/min]
Temp1 [C]
Time1 [min]
Ramp2 [C/min]
Temp2 [C]
Time2 [min]
Column
Flow
Setting
60
2
4
100
2
15
250
2
Parameter
Inlet
Temperature [C]
Mode
Split Ratio
Detector (FID)
Temperature [C]
Hydrogen Flow [mL/min]
Air Flow [mL/min]
Mode
Makeup Flow [mL/min]
Setting
200
Split
50-1
260
40
450
Const Makeup
45
1.3 mL/min
8.1.3 Identify the retention time of eucalyptol (CAS# 470-82-6) or any other oxygen-containing impurity using
these conditions. Oxygen compounds are NOT to be included in the assay
8.1.4 Inject 0.1 L of neat liquid.
8.1.5 For alpha-terpinene, sum the area of all peaks eluting between 10 and 15 minutes (monoterpenes with formula
C10H16, similar vapor pressure). Subtract the area of eucalyptol which elutes in this time range. Divide the area of
the monoterpenes by the total area of all compounds detected and multiply by 100% to calculate the ATRP assay.
8.1.6 For other porogens, establish the retention time range which includes all the isomers of the main component
and sum all these peaks. Subtract the area of any oxygen-containing impurity which may elute in this time range.
Divide the area of the porogens by the total area of all compounds detected and multiply by 100% to calculate the
porogen assay.
8.2 Water — The following method has given satisfactory results in determining water at the value specified in
these chemicals. Alternative methods may be used as long as appropriate method validation as per SEMI C1 can be
demonstrated.
8.2.1 Prepare and operate a Karl Fischer coulometric titrator according to the manufacturer’s instructions. Insure
that there is minimal background drift due to moisture permeating into the titration cell.
8.2.2 Using a dry syringe, draw 1 mL of sample and inject into the titration cell.
8.2.3 Calculate the sample weight from the density and volume of liquid delivered to the cell.
8.2.4 Divide the g of water found by the sample weight to calculate the water content in ppmw.
8.3 Chloride — The following method has given satisfactory results in determining chloride at the value specified
in these chemicals. Alternative methods may be used as long as appropriate method validation as per SEMI C1 can
be demonstrated.
8.3.1 Accurately weigh and transfer approximately 50 g of chemical into a separatory funnel. Add 10 mL of
distilled deionized water to the separatory funnel and shake thoroughly to extract the hydrolysable chloride from the
sample. Vigorous manual shaking for 5 minutes is sufficient. An automatic shaker may also be used. If an
automatic shaker is used, shake at a minimum speed of 120 RPM for a minimum of 15 minutes.
8.3.2 Analyze the aqueous layer by ion chromatography (see SEMI C1) using conditions suitable to separate the
chloride peak from other anionic peaks in the sample
8.4 Trace Metal Analysis — The following method has given satisfactory results in determining trace metal
impurities at the value specified for the following trace metals: aluminum (Al), antimony (Sb), arsenic (As), barium
(Ba), boron (B), cadmium (Cd), calcium (Ca), chromium (Cr), copper (Cr), iron (Fe), lead (Pb), lithium (Li),
magnesium (Mg), manganese (Mn), nickel (Ni), potassium (K), sodium (Na), tin (Sn), titanium (Ti), vanadium (V),
and zinc (Zn). Alternative methods may be used as long as appropriate method validation as per SEMI C1 can be
This is a draft document of the SEMI International Standards program. No material on this page is to be construed as an offi cial or adopted standard. 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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demonstrated. Since the metals are not expected to exist in organic forms in these chemicals, spiking with metal
salts is satisfactory.
8.4.1 Transfer 50-100g of porogen from the bubbler to a separatory funnel. Add 10 mL of DDI water to a
separatory funnel.
8.4.2 Agitate the separatory funnel for 10-20 minutes at about 125 rpm. Allow phases to separate.
8.4.3 Remove aqueous (bottom) layer into a 15 mL centrifuge tube that has been acid-soaked, rinsed with UPW.
8.4.4 Analyze the aqueous layer for metals and boron by ICP-MS. Due to the potential presence of dissolved
organic compounds in the aqueous phase, the addition of oxygen to the nebulizer gas to combust organic compounds
and keep the ICP-MS cones free of carbon is recommended.
.
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.
12 Grade 5 Procedures
12.1 This section does not apply to this chemical.
13 Tier A Procedures
13.1 This section does not apply to this chemical.
14 Tier B Procedures
14.1 This section does not apply to this chemical.
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 1 Impurity Limits and Other Requirements for Porogen Precursors
Grade 1
(Specification)
99.5%
Assay
This is a draft document of the SEMI International Standards program. No material on this page is to be construed as an offi cial or adopted standard. 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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Water
50 ppm max
Chloride
1 ppm max
Aluminum (Al)
1 ppb max
Antimony (Sb)
1 ppb max
Arsenic (As)
1 ppb max
Barium (Ba)
1 ppb max
Boron (B)
1 ppb max
Cadmium (Cd)
1 ppb max
Calcium (Ca)
2 ppb max
Chromium (Cr)
1 ppb max
Copper (Cu)
1 ppb max
Iron (Fe)
2 ppb max
Lead (Pb)
1 ppb max
Lithium (Li)
1 ppb max
Magnesium (Mg)
2 ppb max
Manganese (Mn)
1 ppb max
Nickel (Ni)
1 ppb max
Potassium (K)
1 ppb max
Sodium (Na)
5 ppb max
Tin (Sn)
1 ppb max
Titanium (Ti)
1 ppb max
Vanadium (V)
1 ppb max
Zinc (Zn)
2 ppb max
Particles in bottles:
size, #/mL
LETTER (YELLOW) BALLOT
Document Number: 4589A
Date: 3/9/2016
Note 1
Note 1: Due to the limitations of current particle counters, particle size and number are to be agreed
upon between supplier and user. See SEMI C1, “Calibration and Measurement Method for Particles
in Liquids.”
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