Background Statement for SEMI Draft Document #5328
NEW STANDARD: GUIDE FOR TETRAKIS(DIMETHYLAMINO) SILANE
(TDMAS)
Notice: 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.
Notice: 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.
1 Introduction
As the semi-conductor industry continues in its efforts to follow Moore’s Law many new materials have been
introduced and continue to be introduced into electronic devices. The introduction of new materials being used
covers all areas of the integrated circuit, including, but not limited to, high-k dielectric layers, barrier layers, metal
interconnects, electrical contacts and low-k dielectric layers. Many of these new materials are deposited from liquid
or solid chemicals by means of chemical vapour deposition or increasingly by atomic layer deposition. Therefore,
there are now chemicals currently being used or could potentially be used in the future for which there are no SEMI
guides or standards.
The Precursor Specification Task Force held its first meeting at SEMICON Europa in 2004 to identify new
chemicals currently being used and to draft guides for these chemicals.
2 Steps taken
With input from ITRS representatives The Precursor Specification Task Force initially examined which chemicals
are currently being used or could potentially be used in the future for which there are no SEMI guides. The task
force also examined the properties of these chemicals that are important for the deposition process and whether these
could be included in a guideline. The Precursor Specification Task Force then selected a couple of chemicals to
focus on initially with the aim of producing guides. TDMAS has been investigated for several different applications
including silicon oxide and silicon nitride deposition. However, the most relevant application is its use in the
deposition of silicates, for example HfSiOx and ZrSiOx for use as high-k dielectric layers. An initial draft of the
guide was produced based on task force discussions; this was then revised following comments from chemical
manufactures, tool manufactures and end users.
3 Ballot Adjudication Information
Group:
Date:
Time & Timezone:
Location:
City, State/Country:
Leader(s):
Standards Staff:
Task Force Review
Precursor Specifications TF
Wednesday, October 10, 2012
10:00 - 11:15 CEST
SEMICON Europa
Dresden, Germany
Jean-Marie Collard (jeanmarie.collard@solvay.com)
Gummaar De Vos
(gummaar_devos@fujifilm-ffem.com)
Michael Tran
408.943.7019 /mtran@semi.org
Committee Adjudication
EU Gases and Liquid Chemicals Committee
Wednesday, October 10, 2012
14:00 - 17:00 CEST
SEMICON Europa
Dresden, Germany
Jean-Marie Collard (jeanmarie.collard@solvay.com)
Gummaar De Vos
(gummaar_devos@fujifilm-ffem.com)
Gordon Ferrier (ferrieg@airproducts.com)
Michael Tran
408.943.7019 /mtran@semi.org
This ballot and all responses to it will be adjudicated at the next meeting of the Europe Gases and Liquid Chemicals
Committee, to be held in Dresden, Germany, on Wednesday October 10th, 2012 (in conjunction with SEMICON
Europa).
This meeting’s details are subject to change, and additional review sessions may be scheduled if necessary. Contact
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.
Semiconductor Equipment and Materials International
3081 Zanker Road
San Jose, CA 95134-2127
Phone: 408.943.6900, Fax: 408.943.7943
SEMI Draft Document #5328
NEW STANDARD: GUIDE FOR TETRAKIS(DIMETHYLAMINO) SILANE
(TDMAS)
1 Purpose
1.1 The purpose of this document is to provide a guide for tetrakis(dimethylamino) silane for which a need has been
identified.
2 Scope
2.1 The scope of this document covers high purity tetrakis(dimethylamino) silane which is used in the
semiconductor industry for the deposition of silicon oxide and silicon nitride based layers by atomic layer deposition.
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 Referenced Standards
3.1 SEMI Standard
SEMI C1  Guide for the Analysis of Liquid Chemical.
3.2 ASTM Standards1
ASTM D5127 — Standard Guide for Ultra Pure Water Used in the Electronics and Semiconductor Industry
NOTICE: Unless otherwise indicated, all documents cited shall be the latest published versions.
4 Terminology
4.1 Acronyms
4.1.1 TDMAS — tetrakis(dimethylamino) silane
4.1.2 NMR — nuclear magnetic resonance
4.1.3 TMS — tetramethylsilane
5 Properties
Table 1 Properties of TDMAS
Molecular Formula
Si[N(CH3)2]4
Molecular Weight
204.45 g/mol
CAS Number
1624-01-7
Boiling Point
196 °C
Vapor Pressure
(P=mmHg, T=K)
log10P = 7.037-1969.5/T
Melting Point
16-18°C
Solubility in Water
Reacts
Appearance
Colourless liquid
6 Suggested Values
6.1 The suggested values for tetrakis(dimethylamino) silane for Tier A are listed in Table 2.
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
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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7 Grade 1 Procedures
7.1 This section does not apply to this chemical.
8 Grade 2 Procedures
8.1 This section does not apply to this chemical.
9 Grade 3 Procedures
9.1 This section does not apply to this chemical.
10 Grade 4 Procedures
10.1 This section does not apply to this chemical.
11 Tier A Procedures
NOTE 1: Standardized test methods are being developed for all parameters at the purity level indicated. Until standardized test
methods are published, test methodology shall be determined by user and producer.
11.1 Trace Metals Analysis
11.1.1 Mixed Acid  Prepared by dilution of ultrapure 49% HF, ultrapure 70% HNO 3 and ultrapure 31 % H 2O2
with ultrapure water in the following ratio: 25 mL of HF, 10 mL of HNO3 and 10 mL of H2O2 to 500 mL with water.
11.1.2 Standards  Prepare multi-element standard solutions (calibration standards and quality control check
standards) by diluting with mixed acid described in §11.1.1 of appropriate weights for ICP-MS.
11.1.3 Sample Preparation  Dispense approximately 0.1 mL of the tetrakis(dimethylamino) silane sample into a
dry and clean PFA sample bottle and record the weight to at least 3 decimal places. Under hood, add 49% HF
dropwise into the sample aliquot. The sample will react vigorously with the HF; allow the reaction to proceed until
it subsides before adding the next drop. Repeat until 2 mL of HF have been added. Dilute the sample with the acid
mixture containing H2O2, HNO3 and HF (§11.1.1). The final dilution factor of the sample should be appropriate to
minimize the space charge effects in the ICP-MS measurement of the sample. This dilution factor will be dependent
on the type of ICP-MS used.
11.1.4 Analysis  Analyze the samples by inductively couple plasma mass spectrometry (ICP-MS). Highresolution ICP-MS is suggested. It is recommended to run each sample in duplicate. In addition prepare a sample
preparation blank for each analysis. It is also recommended to use an internal standard or a spiked sample solution to
correct for the matrix effect.
11.2 Hydrocarbons Analysis  The following method has provided satisfactory results in determining total
hydrocarbons at the specified value using H-NMR.
11.2.1 Sample Preparation  Under an inert atmosphere transfer 0.2 mL of tetrakis(dimethylamino) silane into an
NMR tube. Add 1 mL of a solution of the internal standard (TMS) in deuterated benzene.
11.2.2 Analysis  Calculate hydrocarbons from the integrations of peaks in the hydrocarbon region with that of
the internal standard. For convenience hydrocarbons may be calculated as hexane.
11.2.3 Assay by NMR  Ratio of the integration peaks from tetrakis(dimethylamino) silane to total integration of
all peaks in the range -0.5 to 8 ppm.
11.3 Chloride Analysis
11.3.1 Chloride can be determined by direct injection of a sample aliquot into a Total Organic Halogen analyzer.
Calibration is made using an inorganic Chloride standard solution.
12 Tier B Procedures
12.1 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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13 Tier C Procedures
13.1 This section does not apply to this chemical.
14 Tier D Procedures
14.1 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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Phone: 408.943.6900, Fax: 408.943.7943
Table 2 Impurity Limits and Other Suggested Values for Tetrakis(dimethylamino) Silane
Previous SEMI Reference #
-Tier A
(Guide)
Assay
(1H
NMR)
≥99.9%
Hydrocarbons (1H NMR)
≤0.1%
Aluminium (Al)
<100 (ppb)
Antimony (Sb)
<5 (ppb)
Arsenic (As)
<5 (ppb)
Barium (Ba)
<5 (ppb)
Boron (B)
<5 (ppb)
Cadmium (Cd)
<5 (ppb)
Calcium (Ca)
<20 (ppb)
Chromium (Cr)
<5 (ppb)
Copper (Cu)
<5 (ppb)
Iron (Fe)
<5 (ppb)
Lead (Pb)
<5 (ppb)
Lithium (Li)
<5 (ppb)
Magnesium (Mg)
<5 (ppb)
Manganese (Mn)
<5 (ppb)
Nickel (Ni)
<5 (ppb)
Potassium (K)
<5 (ppb)
Sodium (Na)
<5 (ppb)
Tin (Sn)
<5 (ppb)
Titanium (Ti)
<5 (ppb)
Vanadium (V)
<5 (ppb)
Zinc (Zn)
<5 (ppb)
Chloride
<10 (ppm)
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
without notice.
By publication of this Standard or Safety Guideline, SEMI takes no position respecting the validity of any patent
rights or copyrights asserted in connection with any items mentioned in this Standard or Safety Guideline. Users of
this Standard or Safety Guideline 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.
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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