skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Aspects of nitrogen surface chemistry relevant to TiN chemical vapor deposition

Abstract

NH{sub 3} is an important component of many chemical vapor deposition (CVD) processes for TiN films, which are used for diffusion barriers and other applications in microelectronic circuits. In this study, the interaction of NH{sub 3} with TiN surfaces is examined with temperature programmed desorption (TPD) and Auger electron spectroscopy. NH{sub 3} has two adsorption states on TiN: a chemisorbed state and a multilayer state. A new method for analyzing TPD spectra in systems with slow pumping speeds yields activation energies for desorption for the two states of 24 kcal/mol and 7.3 kcal/mol, respectively. The sticking probability into the chemisorption state is {approximately}0.06. These results are discussed in the context of TiN CVD. In addition, the high temperature stability of TiN is investigated. TiN decomposes to its elements only after heating to 1300 K, showing that decomposition is unlikely to occur under CVD conditions.

Authors:
; ;
Publication Date:
Research Org.:
Sandia Labs., Livermore, CA (United States)
Sponsoring Org.:
USDOE Office of Energy Research, Washington, DC (United States)
OSTI Identifier:
415355
Report Number(s):
SAND-96-8580
ON: DE97050468; TRN: 97:000103
DOE Contract Number:
AC04-94AL85000
Resource Type:
Technical Report
Resource Relation:
Other Information: PBD: Aug 1996
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 40 CHEMISTRY; 42 ENGINEERING NOT INCLUDED IN OTHER CATEGORIES; TITANIUM NITRIDES; CHEMICAL VAPOR DEPOSITION; SURFACE PROPERTIES; AMMONIA; ADSORPTION; AUGER ELECTRON SPECTROSCOPY; CHEMISORPTION; DESORPTION; MICROELECTRONIC CIRCUITS; STABILITY; ACTIVATION ENERGY

Citation Formats

Schulberg, M.T., Allendorf, M.D., and Outka, D.A.. Aspects of nitrogen surface chemistry relevant to TiN chemical vapor deposition. United States: N. p., 1996. Web. doi:10.2172/415355.
Copy to clipboard
Schulberg, M.T., Allendorf, M.D., & Outka, D.A.. Aspects of nitrogen surface chemistry relevant to TiN chemical vapor deposition. United States. doi:10.2172/415355.
Copy to clipboard
Schulberg, M.T., Allendorf, M.D., and Outka, D.A.. Thu . "Aspects of nitrogen surface chemistry relevant to TiN chemical vapor deposition". United States. doi:10.2172/415355. https://www.osti.gov/servlets/purl/415355.
Copy to clipboard
@article{osti_415355,
title = {Aspects of nitrogen surface chemistry relevant to TiN chemical vapor deposition},
author = {Schulberg, M.T. and Allendorf, M.D. and Outka, D.A.},
abstractNote = {NH{sub 3} is an important component of many chemical vapor deposition (CVD) processes for TiN films, which are used for diffusion barriers and other applications in microelectronic circuits. In this study, the interaction of NH{sub 3} with TiN surfaces is examined with temperature programmed desorption (TPD) and Auger electron spectroscopy. NH{sub 3} has two adsorption states on TiN: a chemisorbed state and a multilayer state. A new method for analyzing TPD spectra in systems with slow pumping speeds yields activation energies for desorption for the two states of 24 kcal/mol and 7.3 kcal/mol, respectively. The sticking probability into the chemisorption state is {approximately}0.06. These results are discussed in the context of TiN CVD. In addition, the high temperature stability of TiN is investigated. TiN decomposes to its elements only after heating to 1300 K, showing that decomposition is unlikely to occur under CVD conditions.},
doi = {10.2172/415355},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Thu Aug 01 00:00:00 EDT 1996},
month = {Thu Aug 01 00:00:00 EDT 1996}
}
Copy to clipboard
Technical Report:
View Technical Report (1.89 MB)
DOI:  10.2172/415355
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

  • ; ; - Journal of Vacuum Science and Technology, A
    NH{sub 3} is an important component of many chemical vapor deposition (CVD) processes for TiN films, which are used for diffusion barriers and other applications in microelectronic circuits. In this study, the interaction of NH{sub 3} with TiN surfaces is examined with temperature programmed desorption (TPD) and Auger electron spectroscopy. NH{sub 3} has two adsorption states on TiN: a chemisorbed state and a multilayer state. A new method for analyzing TPD spectra in systems with slow pumping speeds yields activation energies for desorption for the two states of 24 kcal/mol and 7.3 kcal/mol, respectively. The sticking probability into the chemisorptionmore » state is {approximately}0.06. These results are discussed in the context of TiN CVD. In addition, the high temperature stability of TiN is investigated. TiN decomposes to its elements only after heating to 1300 K, showing that decomposition is unlikely to occur under CVD conditions. {copyright} {ital 1996 American Vacuum Society}« less

  • ; ; ; ...
    The purpose of the work reported here was to develop special chemical vapor deposition (CVD) methods to produce self-lubricating ceramic coatings in which the lubricating and structural phases were co-deposited on Ti-6Al-4V alloy substrates. These novel composite coatings are based on a system containing titanium nitride and molybdenum disulfide. The method for producing these coatings and their sliding behavior against silicon nitride counterfaces, in the temperature range 20--700 C in air, are described. The initial sliding friction coefficients for the composite coatings at room temperature were 0.07--0.30, but longer-term transitions to higher friction occurred, and specimen-to-specimen test variations suggested thatmore » further developments of the deposition process are required to assure repeatable friction and wear results. Friction and wear tests at 300 and 700 C produced encouraging results, but tests run at an intermediate temperate of 400 C exhibited friction coefficients of 1.0 or more. Oxidation and a change in the nature of the debris layers formed during sliding are believed to be responsible for this behavior.« less

  • ; ; ; ...
    Atmospheric pressure chemical vapor deposition (APCVD) of tin oxide is a very important manufacturing technique used in the production of low-emissivity glass. It is also the primary method used to provide wear-resistant coatings on glass containers. The complexity of these systems, which involve chemical reactions in both the gas phase and on the deposition surface, as well as complex fluid dynamics, makes process optimization and design of new coating reactors a very difficult task. In 2001 the U.S. Dept. of Energy Industrial Technologies Program Glass Industry of the Future Team funded a project to address the need for more accuratemore » data concerning the tin oxide APCVD process. This report presents a case study of on-line APCVD using organometallic precursors, which are the primary reactants used in industrial coating processes. Research staff at Sandia National Laboratories in Livermore, CA, and the PPG Industries Glass Technology Center in Pittsburgh, PA collaborated to produce this work. In this report, we describe a detailed investigation of the factors controlling the growth of tin oxide films. The report begins with a discussion of the basic elements of the deposition chemistry, including gas-phase thermochemistry of tin species and mechanisms of chemical reactions involved in the decomposition of tin precursors. These results provide the basis for experimental investigations in which tin oxide growth rates were measured as a function of all major process variables. The experiments focused on growth from monobutyltintrichloride (MBTC) since this is one of the two primary precursors used industrially. There are almost no reliable growth-rate data available for this precursor. Robust models describing the growth rate as a function of these variables are derived from modeling of these data. Finally, the results are used to conduct computational fluid dynamic simulations of both pilot- and full-scale coating reactors. As a result, general conclusions are reached concerning the factors affecting the growth rate in on-line APCVD reactors. In addition, a substantial body of data was generated that can be used to model many different industrial tin oxide coating processes. These data include the most extensive compilation of thermochemistry for gas-phase tin-containing species as well as kinetic expressions describing tin oxide growth rates over a wide range of temperatures, pressures, and reactant concentrations.« less

  • Chemical vapor deposition of silicon carbide from gaseous mixtures of CH/sub 3/SiCl/sub 3/,H/sub 2/,SiCl/sub 4/ and (CH/sub 3/)/sub 3/SiCl/sub 3/ was examined at temperatures ranging from 1200 to 1750/sup 0/C. The coating rate was observed to increase with temperature, CH/sub 3/SiCl/sub 3/ concentration and CH/sub 3/SiCl/sub 3//SiCl/sub 4/ ratios. In addition, the codeposition of condensed phases from CH/sub 3/SiCl/sub 3/ and AlCl/sub 3/.NH/sub 3/ gases were examined at 1200/sup 0/C as a function of CH/sub 3/SiCl/sub 3//AlCl/sub 3/.NH/sub 3/ (MTS/ACN) mole ratio. Nomially pure AlN could be formed for ratios of MTS/ACN less than or equal to 0.1. Mixtures ofmore » AlN and polycrystalline ..cap alpha..-Si/sub 3/N/sub 4/ formed for gas mixtures of 0.1 less than or equal to MTS/ACN less than or equal to 1. Amorphous Si/sub 3/N/sub 4/ (with traces of free silicon) formed for cases where 1 less than or equal to MTS/ACN less than or equal to 10. Finally, mixtures of free silicon and ..beta..-SiC were found for gas mixtures of MTS/ACN less than or equal to 10. AlN which has the 2H wurtzite structure serves to nucleate ..cap alpha..-Si/sub 3/N/sub 4/ which otherwise forms as an amorphous deposit.« less

  • The chemical vapor deposition of SiC from methyltrichlorosilane was studied using a combination of measurement and analytical techniques. Equilibrium analysis and mass spectrometric measurements were used to identify gas-phase species and determine their concentrations. Analysis of kinetic data coupled with a thermokinetic assessment allowed determination of rate-limiting mechanisms. The preparation of a two-phase coating of B/sub 4/C-BN was addressed as a potential wear coating, because of its likelihood of having a high fracture toughness resulting from its composite nature and inherent lubrication resulting from the presence of BN. Equilibrium analysis identified appropriate deposition conditions; however, deposited coatings were found tomore » be single-phase BN with a high degree of substitution of carbon for nitrogen. 9 refs., 10 figs., 3 tabs.« less