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Title: Application of time-of-flight secondary ion mass spectrometry to the detection of surface intermediates during the first cycle of atomic layer deposition (ALD) of platinum on silica surfaces

Abstract

Atomic layer deposition (ALD) has become the method of choice for many applications requiring the controlled growth of thin films on solid surfaces. Yet, the use of metalorganic precursors typical in these depositions adds significant complexity to the chemistry involved. Unfortunately, it is difficult to obtain direct information about the surface species that participate in the reaction mechanisms of ALD. Here we illustrate the value of using time-of-flight secondary ion mass spectrometry (ToF-SIMS) for this purpose. A specific example is provided, a study of the first cycle of deposition of platinum using trimethyl(methylcyclopentadienyl)platinum (IV), or MeCpPt(CH3)3, on silicon oxide surfaces. In previous investigations of this process, we have determined that the low reactivity of the MeCpPt(CH3)3 precursor, which hinders fast deposition, can be partially overcome by gas-phase electron-impact activation. What has not been clear is what chemical species form on the solid surface as a result of such activation. Here we show that the MeCp ligand is quite stable and that it remains intact and coordinated to the Pt atoms upon adsorption on the surface. It was also established that some of the methyl groups may remain bound to the Pt center: the main species detected on the silicon oxidemore » surfaces were MeCpPt and MeCpPt(CH3). On the other hand, it appears that no Pt intermediates without MeCp ligands are formed during this initial adsorption. Finally, O2 treatment of these surfaces at elevated temperature to complete the first ALD cycle leads to the complete removal of all the organic ligands: no evidence for MeCp or methyl groups is seen in the ToF-SIMS traces from the final samples.« less

Authors:
 [1];  [2];  [2];  [1]
+ Show Author Affiliations
  1. Univ. of Delaware, Newark, DE (United States)
  2. Univ. of California, Riverside, CA (United States)
Publication Date:
Research Org.:
Univ. of California, Riverside, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; National Science Foundation (NSF); USDOE
OSTI Identifier:
1593409
Alternate Identifier(s):
OSTI ID: 1701976
Grant/Contract Number:  
SC0001839; DMR-1609973
Resource Type:
Accepted Manuscript
Journal Name:
Applied Surface Science
Additional Journal Information:
Journal Volume: 488; Journal Issue: C; Journal ID: ISSN 0169-4332
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; ALD; Platinum; ToF-SIMS

Citation Formats

Konh, Mahsa, Lien, Clinton, Zaera, Francisco, and Teplyakov, Andrew V. Application of time-of-flight secondary ion mass spectrometry to the detection of surface intermediates during the first cycle of atomic layer deposition (ALD) of platinum on silica surfaces. United States: N. p., 2019. Web. doi:10.1016/j.apsusc.2019.05.209.
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Konh, Mahsa, Lien, Clinton, Zaera, Francisco, & Teplyakov, Andrew V. Application of time-of-flight secondary ion mass spectrometry to the detection of surface intermediates during the first cycle of atomic layer deposition (ALD) of platinum on silica surfaces. United States. https://doi.org/10.1016/j.apsusc.2019.05.209
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Konh, Mahsa, Lien, Clinton, Zaera, Francisco, and Teplyakov, Andrew V. Sun . "Application of time-of-flight secondary ion mass spectrometry to the detection of surface intermediates during the first cycle of atomic layer deposition (ALD) of platinum on silica surfaces". United States. https://doi.org/10.1016/j.apsusc.2019.05.209. https://www.osti.gov/servlets/purl/1593409.
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@article{osti_1593409,
title = {Application of time-of-flight secondary ion mass spectrometry to the detection of surface intermediates during the first cycle of atomic layer deposition (ALD) of platinum on silica surfaces},
author = {Konh, Mahsa and Lien, Clinton and Zaera, Francisco and Teplyakov, Andrew V.},
abstractNote = {Atomic layer deposition (ALD) has become the method of choice for many applications requiring the controlled growth of thin films on solid surfaces. Yet, the use of metalorganic precursors typical in these depositions adds significant complexity to the chemistry involved. Unfortunately, it is difficult to obtain direct information about the surface species that participate in the reaction mechanisms of ALD. Here we illustrate the value of using time-of-flight secondary ion mass spectrometry (ToF-SIMS) for this purpose. A specific example is provided, a study of the first cycle of deposition of platinum using trimethyl(methylcyclopentadienyl)platinum (IV), or MeCpPt(CH3)3, on silicon oxide surfaces. In previous investigations of this process, we have determined that the low reactivity of the MeCpPt(CH3)3 precursor, which hinders fast deposition, can be partially overcome by gas-phase electron-impact activation. What has not been clear is what chemical species form on the solid surface as a result of such activation. Here we show that the MeCp ligand is quite stable and that it remains intact and coordinated to the Pt atoms upon adsorption on the surface. It was also established that some of the methyl groups may remain bound to the Pt center: the main species detected on the silicon oxide surfaces were MeCpPt and MeCpPt(CH3). On the other hand, it appears that no Pt intermediates without MeCp ligands are formed during this initial adsorption. Finally, O2 treatment of these surfaces at elevated temperature to complete the first ALD cycle leads to the complete removal of all the organic ligands: no evidence for MeCp or methyl groups is seen in the ToF-SIMS traces from the final samples.},
doi = {10.1016/j.apsusc.2019.05.209},
journal = {Applied Surface Science},
number = C,
volume = 488,
place = {United States},
year = {Sun May 19 00:00:00 EDT 2019},
month = {Sun May 19 00:00:00 EDT 2019}
}
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https://doi.org/10.1016/j.apsusc.2019.05.209
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Works referenced in this record:

Atomic Layer Deposition: An Overview
journal, January 2010

  • George, Steven M.
  • Chemical Reviews, Vol. 110, Issue 1, p. 111-131
  • DOI: 10.1021/cr900056b

Atomic layer deposition for nanomaterial synthesis and functionalization in energy technology
journal, January 2017

  • Meng, Xiangbo; Wang, Xinwei; Geng, Dongsheng
  • Materials Horizons, Vol. 4, Issue 2
  • DOI: 10.1039/C6MH00521G

Nanoengineering Heterogeneous Catalysts by Atomic Layer Deposition
journal, June 2017

The Surface Chemistry of Atomic Layer Depositions of Solid Thin Films
journal, May 2012

  • Zaera, Francisco
  • The Journal of Physical Chemistry Letters, Vol. 3, Issue 10
  • DOI: 10.1021/jz300125f

Mechanisms of surface reactions in thin solid film chemical deposition processes
journal, December 2013

In Situ Studies on Reaction Mechanisms in Atomic Layer Deposition
journal, January 2013

The Chemistry of Inorganic Precursors during the Chemical Deposition of Films on Solid Surfaces
journal, February 2018

Patterning of Solid Films via Selective Atomic Layer Deposition Based on Silylation and UV/Ozonolysis
journal, July 2016

  • Guo, Lei; Lee, Ilkeun; Zaera, Francisco
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 30
  • DOI: 10.1021/acsami.6b07192

Chemical Treatment of Low-k Dielectric Surfaces for Patterning of Thin Solid Films in Microelectronic Applications
journal, February 2016

  • Guo, Lei; Qin, Xiangdong; Zaera, Francisco
  • ACS Applied Materials & Interfaces, Vol. 8, Issue 9
  • DOI: 10.1021/acsami.6b00495

Atomic Layer Deposition of Platinum Thin Films
journal, May 2003

  • Aaltonen, Titta; Ritala, Mikko; Sajavaara, Timo
  • Chemistry of Materials, Vol. 15, Issue 9, p. 1924-1928
  • DOI: 10.1021/cm021333t

Low-Temperature Atomic Layer Deposition of Platinum Using (Methylcyclopentadienyl)trimethylplatinum and Ozone
journal, September 2013

  • Dendooven, Jolien; Ramachandran, Ranjith K.; Devloo-Casier, Kilian
  • The Journal of Physical Chemistry C, Vol. 117, Issue 40
  • DOI: 10.1021/jp403455a

Direct-Write Atomic Layer Deposition of High-Quality Pt Nanostructures: Selective Growth Conditions and Seed Layer Requirements
journal, May 2013

  • Mackus, A. J. M.; Thissen, N. F. W.; Mulders, J. J. L.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 20
  • DOI: 10.1021/jp402260j

Atomic Layer Deposition of Noble Metals and Their Oxides
journal, September 2013

  • Hämäläinen, Jani; Ritala, Mikko; Leskelä, Markku
  • Chemistry of Materials, Vol. 26, Issue 1
  • DOI: 10.1021/cm402221y

Deposition of metal films by the controlled decomposition of organometallic compounds on surfaces
journal, April 1980

Electron-beam-induced deposition of platinum at low landing energies
journal, November 2008

  • Botman, A.; de Winter, D. A. M.; Mulders, J. J. L.
  • Journal of Vacuum Science & Technology B: Microelectronics and Nanometer Structures, Vol. 26, Issue 6
  • DOI: 10.1116/1.2976576

A critical literature review of focused electron beam induced deposition
journal, October 2008

  • van Dorp, W. F.; Hagen, C. W.
  • Journal of Applied Physics, Vol. 104, Issue 8
  • DOI: 10.1063/1.2977587

Creating pure nanostructures from electron-beam-induced deposition using purification techniques: a technology perspective
journal, August 2009

Activation of Metal–Organic Precursors by Electron Bombardment in the Gas Phase for Enhanced Deposition of Solid Films
journal, August 2012

  • Sun, Huaxing; Qin, Xiangdong; Zaera, Francisco
  • The Journal of Physical Chemistry Letters, Vol. 3, Issue 17
  • DOI: 10.1021/jz3011332

X-ray-Initiated Metal-Promoted Thin Film Growth
journal, April 2012

  • Kim, Taeseung; Zaera, Francisco
  • The Journal of Physical Chemistry C, Vol. 116, Issue 15
  • DOI: 10.1021/jp2123339

The role of low-energy electrons in focused electron beam induced deposition: four case studies of representative precursors
journal, January 2015

  • Thorman, Rachel M.; Kumar T. P., Ragesh; Fairbrother, D. Howard
  • Beilstein Journal of Nanotechnology, Vol. 6
  • DOI: 10.3762/bjnano.6.194

Gas-Phase Electron-Impact Activation of Atomic Layer Deposition (ALD) Precursors: MeCpPtMe 3
journal, August 2018

Mechanism-based design of precursors for focused electron beam-induced deposition
journal, April 2018

  • Carden, Will G.; Lu, Hang; Spencer, Julie A.
  • MRS Communications, Vol. 8, Issue 02
  • DOI: 10.1557/mrc.2018.77

Organometallic chemical vapor deposition of platinum. Reaction kinetics and vapor pressures of precursors
journal, January 1992

  • Xue, Ziling; Thridandam, Hareesh; Kaesz, Herbert D.
  • Chemistry of Materials, Vol. 4, Issue 1
  • DOI: 10.1021/cm00019a032

Surface reactions during atomic layer deposition of Pt derived from gas phase infrared spectroscopy
journal, July 2009

  • Kessels, W. M. M.; Knoops, H. C. M.; Dielissen, S. A. F.
  • Applied Physics Letters, Vol. 95, Issue 1
  • DOI: 10.1063/1.3176946

In Vacuo Photoemission Studies of Platinum Atomic Layer Deposition Using Synchrotron Radiation
journal, December 2012

  • Geyer, Scott M.; Methaapanon, Rungthiwa; Shong, Bonggeun
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 1
  • DOI: 10.1021/jz301475z

Selective area platinum silicide film deposition using a molecular precursor chemical beam source
journal, November 1995

Studies of metallic thin film growth in an atomic layer epitaxy reactor using M(acac)2 (M=Ni, Cu, Pt) precursors
journal, April 2000

  • Utriainen, Mikko; Kröger-Laukkanen, Minna; Johansson, Leena-Sisko
  • Applied Surface Science, Vol. 157, Issue 3
  • DOI: 10.1016/S0169-4332(99)00562-0

Atomic Layer Deposition of Platinum Oxide and Metallic Platinum Thin Films from Pt(acac) 2 and Ozone
journal, November 2008

  • Hämäläinen, Jani; Munnik, Frans; Ritala, Mikko
  • Chemistry of Materials, Vol. 20, Issue 21
  • DOI: 10.1021/cm801187t

Electron induced reactions in gas phase MeCpPtMe 3 and Pd(hfac) 2
journal, November 2012

Platinum and Palladium Films Obtained by Low-Temperature MOCVD for the Formation of Small Particles on Divided Supports as Catalytic Materials
journal, February 2000

  • Hierso, Jean-Cyrille; Feurer, Roselyne; Kalck, Philippe
  • Chemistry of Materials, Vol. 12, Issue 2
  • DOI: 10.1021/cm990406e

Electron-beam induced initial growth of platinum films using Pt(PF[sub 3])[sub 4]
journal, January 2004

  • Wang, S.; Sun, Y. -M.; Wang, Q.
  • Journal of Vacuum Science & Technology B: Microelectronics and Nanometer Structures, Vol. 22, Issue 4
  • DOI: 10.1116/1.1761266

Continuous and ultrathin platinum films on graphene using atomic layer deposition: a combined computational and experimental study
journal, January 2016

  • Karasulu, Bora; Vervuurt, René H. J.; Kessels, Wilhelmus M. M.
  • Nanoscale, Vol. 8, Issue 47
  • DOI: 10.1039/C6NR07483A

Reaction Mechanism Studies on Atomic Layer Deposition of Ruthenium and Platinum
journal, January 2003

  • Aaltonen, Titta; Rahtu, Antti; Ritala, Mikko
  • Electrochemical and Solid-State Letters, Vol. 6, Issue 9
  • DOI: 10.1149/1.1595312

Mass Spectrometry Study of the Temperature Dependence of Pt Film Growth by Atomic Layer Deposition
journal, January 2012

  • Erkens, I. J. M.; Mackus, A. J. M.; Knoops, H. C. M.
  • ECS Journal of Solid State Science and Technology, Vol. 1, Issue 6
  • DOI: 10.1149/2.006206jss

Catalytic Combustion and Dehydrogenation Reactions during Atomic Layer Deposition of Platinum
journal, May 2012

  • Mackus, Adriaan J. M.; Leick, Noémi; Baker, Layton
  • Chemistry of Materials, Vol. 24, Issue 10
  • DOI: 10.1021/cm203812v

Controlling Nanoscale Properties of Supported Platinum Catalysts through Atomic Layer Deposition
journal, January 2015

  • Gould, Troy D.; Lubers, Alia M.; Corpuz, April R.
  • ACS Catalysis, Vol. 5, Issue 2
  • DOI: 10.1021/cs501265b

Reaction of Methylcyclopentadienyl Manganese Tricarbonyl on Silicon Oxide Surfaces: Implications for Thin Film Atomic Layer Depositions
journal, September 2014

  • Bouman, Menno; Qin, Xiangdong; Doan, Vananh
  • Organometallics, Vol. 33, Issue 19
  • DOI: 10.1021/om5006269

Mechanistic studies for depositing highly dispersed Pt nanoparticles on carbon by use of trimethyl(methylcyclopentadienyl)platinum(IV) reactions with O2 and H2
journal, April 2015

  • Lubers, Alia M.; Muhich, Christopher L.; Anderson, Kelly M.
  • Journal of Nanoparticle Research, Vol. 17, Issue 4
  • DOI: 10.1007/s11051-015-2982-9

Surface Infrared Spectroscopy during Low Temperature Growth of Supported Pt Nanoparticles by Atomic Layer Deposition
journal, December 2015

  • Bosch, Roger H. E. C.; Bloksma, Frank L.; Huijs, Jochem M. M.
  • The Journal of Physical Chemistry C, Vol. 120, Issue 1
  • DOI: 10.1021/acs.jpcc.5b10839

Dynamics and fragmentation mechanism of (C 5 H 4 CH 3 )Pt(CH 3 ) 3 on SiO 2 surfaces
journal, January 2018

  • Muthukumar, Kaliappan; Jeschke, Harald O.; Valentí, Roser
  • Beilstein Journal of Nanotechnology, Vol. 9
  • DOI: 10.3762/bjnano.9.66

High-resolution secondary ion mass spectrometry depth profiling of nanolayers: Depth profiling of nanolayers by high-resolution SIMS
journal, August 2012

  • Baryshev, Sergey V.; Zinovev, Alexander V.; Tripa, C. Emil
  • Rapid Communications in Mass Spectrometry, Vol. 26, Issue 19
  • DOI: 10.1002/rcm.6344

Atomic layer deposition of aluminum-free silica onto patterned carbon nanotube forests in the preparation of microfabricated thin-layer chromatography plates
journal, June 2014

  • Kanyal, Supriya; Jensen, David; Dadson, Andrew
  • Journal of Planar Chromatography – Modern TLC, Vol. 27, Issue 3
  • DOI: 10.1556/JPC.27.2014.3.1

Structure of a thin barrier film deposited from tetrakis-(dimethylamino)-titanium onto a Si(100)-2×1 substrate
journal, January 2005

Adsorption of C 60 Buckminster Fullerenes on an 11-Amino-1-undecene-Covered Si(111) Substrate
journal, February 2008

  • Zhang, Xiaochun; Teplyakov, Andrew V.
  • Langmuir, Vol. 24, Issue 3
  • DOI: 10.1021/la702631g

Attachment Chemistry of PCBM to a Primary-Amine-Terminated Organic Monolayer on a Si(111) Surface
journal, April 2014

  • Miller, Timothy; Teplyakov, Andrew V.
  • Langmuir, Vol. 30, Issue 18
  • DOI: 10.1021/la404798k

Monolayer of Hydrazine Facilitates the Direct Covalent Attachment of C 60 Fullerene to a Silicon Surface
journal, February 2017

Carbon Nanotubes Covalently Attached to Functionalized Surfaces Directly through the Carbon Cage
journal, November 2016

In situ investigation of organic ligand displacement processes on ZnO powder surface
journal, November 2014

Surface Chemistry in the Atomic Layer Deposition of TiN Films from TiCl 4 and Ammonia
journal, July 2006

  • Tiznado, Hugo; Zaera, Francisco
  • The Journal of Physical Chemistry B, Vol. 110, Issue 27
  • DOI: 10.1021/jp062019f

Chemical Vapor Deposition of Manganese Metallic Films on Silicon Oxide Substrates
journal, October 2012

  • Sun, Huaxing; Zaera, Francisco
  • The Journal of Physical Chemistry C, Vol. 116, Issue 44
  • DOI: 10.1021/jp309083a

Platinum atomic layer deposition on metal substrates: A surface chemistry study
journal, November 2018

Spatial resolution in thin film deposition on silicon surfaces by combining silylation and UV/ozonolysis
journal, November 2014

Gwyddion: an open-source software for SPM data analysis
journal, January 2012

Computational investigation of surface reactivity of functionalized silicon surfaces in deposition processes
journal, October 2013

Room-Temperature Atomic Layer Deposition of Platinum
journal, April 2013

  • Mackus, Adriaan J. M.; Garcia-Alonso, Diana; Knoops, Harm C. M.
  • Chemistry of Materials, Vol. 25, Issue 9
  • DOI: 10.1021/cm400274n
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