Semiconductor Equipment and Materials International
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Phone:408.943.6900, Fax: 408.943.7943
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Background Statement for SEMI Draft Document #5329
NEW STANDARD: GUIDE FOR tRis(dimethylamino) silanE (3DMAS)
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 vapor 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.3DMAS 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
Task Force Review / Committee AdjudicationGroup: / Precursor Specifications TF / EU Gases and Liquid Chemicals Committee
Date: / Wednesday, October 10, 2012 / Wednesday, October 10, 2012
Time & Timezone: / 10:00 - 11:15CEST / 14:00 - 17:00 CEST
Location: / SEMICON Europa / SEMICON Europa
City, State/Country: / Dresden, Germany / Dresden, Germany
Leader(s): / Jean-Marie Collard ()
GummaarDe Vos () / Jean-Marie Collard ()
Gummaar De Vos ()
GordonFerrier ()
Standards Staff: / Michael Tran
408.943.7019 / / Michael Tran
408.943.7019 /
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.
Page 1Doc. 5329 SEMI
Semiconductor Equipment and Materials International
3081 Zanker Road
San Jose, CA95134-2127
Phone:408.943.6900, Fax: 408.943.7943
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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.
SEMI Draft Document #5329
NEW STANDARD: GUIDE FOR tRis(dimethylamino) silane (3DMAS)
1 Purpose
1.1 The purpose of this document is to provide a guide for tris(dimethylamino) silane for which a need has been identified.
2 Scope
2.1 The scope of this document covers high purity tris(dimethylamino) silane which is used in the semiconductor industry for the deposition of silicon oxide, 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 Standards[1]
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 3DMAS—tris(dimethylamino) silane
4.1.2 NMR—nuclear magnetic resonance
4.1.3 TMS—tetramethylsilane
5 Properties
Table 1Properties of 3DMASMolecular Formula / HSi[N(CH3)2]3
Molecular Weight / 161.37 g/mol
CAS Number / 15112-89-7
Boiling Point / 145 °C
Vapor Pressure(P=mmHg, T=K) / log10P = 8.220-2210/T
Solubility in Water / Reacts
Appearance / Colourless liquid
6 Suggested Values
6.1 The suggested values for tris(dimethylamino) silane for Tier A are listed in Table 2.
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% HNO3and ultrapure 31 % H2O2with 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 tris(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). High-resolution 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 0.2mL of tris(dimethylamino) silane into an NMR tube. Add 1mL 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 Assayby NMR Ratio of the integration peaks from tris(dimethylamino) silane to total integration of all peaks in the range -0.5 to 8ppm.
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.
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.
Table 2Impurity Limits and Other Suggested Values for Tris(dimethylamino) Silane
Previous SEMI Reference # / --Tier A
(Guide)
Assay (GC) / ≥99.9%
Hydrocarbons (1H NMR) / ≤0.1%
Aluminium (Al) / <5 (ppb)
Antimony (Sb) / <5 (ppb)
Arsenic (As) / <5 (ppb)
Barium (Ba) / <5 (ppb)
Boron (B) / <5 (ppb)
Cadmium (Cd) / <5 (ppb)
Calcium (Ca) / <10 (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 (Cl) / <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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[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: