Effect of Backbone Chemistry on the Structure of Polyurea Films Deposited by Molecular Layer Deposition
Abstract
An experimental investigation into the growth of polyurea films by molecular layer deposition was performed by examining trends in the growth rate, crystallinity, and orientation of chains as a function of backbone flexibility. Growth curves obtained for films containing backbones of aliphatic and phenyl groups indicate that an increase in backbone flexibility leads to a reduction in growth rate from 4 to 1 Å/cycle. Crystallinity measurements collected using grazing incidence X-ray diffraction and Fourier transform infrared spectroscopy suggest that some chains form paracrystalline, out-of-plane stacks of polymer segments with packing distances ranging from 4.4 to 3.7 Å depending on the monomer size. Diffraction intensity is largely a function of the homogeneity of the backbone. Near-edge X-ray absorption fine structure measurements for thin and thick samples show an average chain orientation of ~25° relative to the substrate across all samples, suggesting that changes in growth rate are not caused by differences in chain angle but instead may be caused by differences in the frequency of chain terminations. In conclusion, these results suggest a model of molecular layer deposition-based chain growth in which films consist of a mixture of upward growing chains and horizontally aligned layers of paracrystalline polymer segments.
- Authors:
-
[1];
[1]
- Stanford Univ., CA (United States). Dept. of Chemical Engineering
- Stanford Univ., CA (United States). Dept. of Chemistry
- SLAC National Accelerator Lab., Menlo Park, CA (United States)
- Stanford Univ., CA (United States). Dept. of Materials Science and Engineering
- Publication Date:
- Research Org.:
- SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- OSTI Identifier:
- 1353178
- Grant/Contract Number:
- CHE-1213879; CHE-1607339; AC02-76SF00515
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemistry of Materials
- Additional Journal Information:
- Journal Volume: 29; Journal Issue: 3; Journal ID: ISSN 0897-4756
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Bergsman, David S., Closser, Richard G., Tassone, Christopher J., Clemens, Bruce M., Nordlund, Dennis, and Bent, Stacey F. Effect of Backbone Chemistry on the Structure of Polyurea Films Deposited by Molecular Layer Deposition. United States: N. p., 2017.
Web. doi:10.1021/acs.chemmater.6b04530.
Bergsman, David S., Closser, Richard G., Tassone, Christopher J., Clemens, Bruce M., Nordlund, Dennis, & Bent, Stacey F. Effect of Backbone Chemistry on the Structure of Polyurea Films Deposited by Molecular Layer Deposition. United States. https://doi.org/10.1021/acs.chemmater.6b04530
Bergsman, David S., Closser, Richard G., Tassone, Christopher J., Clemens, Bruce M., Nordlund, Dennis, and Bent, Stacey F. Sun .
"Effect of Backbone Chemistry on the Structure of Polyurea Films Deposited by Molecular Layer Deposition". United States. https://doi.org/10.1021/acs.chemmater.6b04530. https://www.osti.gov/servlets/purl/1353178.
@article{osti_1353178,
title = {Effect of Backbone Chemistry on the Structure of Polyurea Films Deposited by Molecular Layer Deposition},
author = {Bergsman, David S. and Closser, Richard G. and Tassone, Christopher J. and Clemens, Bruce M. and Nordlund, Dennis and Bent, Stacey F.},
abstractNote = {An experimental investigation into the growth of polyurea films by molecular layer deposition was performed by examining trends in the growth rate, crystallinity, and orientation of chains as a function of backbone flexibility. Growth curves obtained for films containing backbones of aliphatic and phenyl groups indicate that an increase in backbone flexibility leads to a reduction in growth rate from 4 to 1 Å/cycle. Crystallinity measurements collected using grazing incidence X-ray diffraction and Fourier transform infrared spectroscopy suggest that some chains form paracrystalline, out-of-plane stacks of polymer segments with packing distances ranging from 4.4 to 3.7 Å depending on the monomer size. Diffraction intensity is largely a function of the homogeneity of the backbone. Near-edge X-ray absorption fine structure measurements for thin and thick samples show an average chain orientation of ~25° relative to the substrate across all samples, suggesting that changes in growth rate are not caused by differences in chain angle but instead may be caused by differences in the frequency of chain terminations. In conclusion, these results suggest a model of molecular layer deposition-based chain growth in which films consist of a mixture of upward growing chains and horizontally aligned layers of paracrystalline polymer segments.},
doi = {10.1021/acs.chemmater.6b04530},
journal = {Chemistry of Materials},
number = 3,
volume = 29,
place = {United States},
year = {Sun Jan 01 00:00:00 EST 2017},
month = {Sun Jan 01 00:00:00 EST 2017}
}
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Works referenced in this record:
Molecular Layer Deposition of Nanoscale Organic Films for Nanoelectronics Applications
journal, August 2014
- Bergsman, D.; Zhou, H.; Bent, S. F.
- ECS Transactions, Vol. 64, Issue 9
Molecular Layer Deposition of Functional Thin Films for Advanced Lithographic Patterning
journal, January 2011
- Zhou, Han; Bent, Stacey F.
- ACS Applied Materials & Interfaces, Vol. 3, Issue 2
Highly Sensitive, Patternable Organic Films at the Nanoscale Made by Bottom-Up Assembly
journal, March 2013
- Zhou, Han; Blackwell, James M.; Lee, Han-Bo-Ram
- ACS Applied Materials & Interfaces, Vol. 5, Issue 9
Improving Area-Selective Molecular Layer Deposition by Selective SAM Removal
journal, October 2014
- Prasittichai, Chaiya; Pickrahn, Katie L.; Minaye Hashemi, Fatemeh Sadat
- ACS Applied Materials & Interfaces, Vol. 6, Issue 20
Structure and Reactivity of Alucone-Coated Films on Si and Li x Si y Surfaces
journal, May 2015
- Ma, Yuguang; Martinez de la Hoz, Julibeth M.; Angarita, Ivette
- ACS Applied Materials & Interfaces, Vol. 7, Issue 22
Reversible High-Capacity Si Nanocomposite Anodes for Lithium-ion Batteries Enabled by Molecular Layer Deposition
journal, December 2013
- Piper, Daniela Molina; Travis, Jonathan J.; Young, Matthias
- Advanced Materials, Vol. 26, Issue 10
Surface-Coating Regulated Lithiation Kinetics and Degradation in Silicon Nanowires for Lithium Ion Battery
journal, April 2015
- Luo, Langli; Yang, Hui; Yan, Pengfei
- ACS Nano, Vol. 9, Issue 5
Stabilizing Ni Catalysts by Molecular Layer Deposition for Harsh, Dry Reforming Conditions
journal, July 2014
- Gould, Troy D.; Izar, Alan; Weimer, Alan W.
- ACS Catalysis, Vol. 4, Issue 8
An overview of highly porous oxide films with tunable thickness prepared by molecular layer deposition
journal, April 2015
- Liang, Xinhua; Weimer, Alan W.
- Current Opinion in Solid State and Materials Science, Vol. 19, Issue 2
Fabrication of organic interfacial layers by molecular layer deposition: Present status and future opportunities
journal, July 2013
- Zhou, Han; Bent, Stacey F.
- Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 31, Issue 4
Polymer films formed with monolayer growth steps by molecular layer deposition
journal, July 1991
- Yoshimura, Tetsuzo; Tatsuura, Satoshi; Sotoyama, Wataru
- Applied Physics Letters, Vol. 59, Issue 4
Atomic layer deposition of polyimide thin films
journal, January 2007
- Putkonen, Matti; Harjuoja, Jenni; Sajavaara, Timo
- J. Mater. Chem., Vol. 17, Issue 7
Layer-by-Layer Growth on Ge(100) via Spontaneous Urea Coupling Reactions
journal, March 2005
- Kim, Ansoon; Filler, Michael A.; Kim, Sehun
- Journal of the American Chemical Society, Vol. 127, Issue 16
Formation of Organic Nanoscale Laminates and Blends by Molecular Layer Deposition
journal, December 2009
- Loscutoff, Paul W.; Zhou, Han; Clendenning, Scott B.
- ACS Nano, Vol. 4, Issue 1
Molecular Layer Deposition of Poly( p -phenylene terephthalamide) Films Using Terephthaloyl Chloride and p -Phenylenediamine
journal, March 2008
- Adamczyk, N. M.; Dameron, A. A.; George, S. M.
- Langmuir, Vol. 24, Issue 5
Molecular Layer Deposition of Nylon 66 Films Examined Using in Situ FTIR Spectroscopy
journal, June 2007
- Du, Y.; George, S. M.
- The Journal of Physical Chemistry C, Vol. 111, Issue 24
Synthesis of Zeolite As Ordered Multicrystal Arrays
journal, August 2003
- Lee, J. S.
- Science, Vol. 301, Issue 5634
Deposition of Ultrathin Polythiourea Films by Molecular Layer Deposition
journal, October 2010
- Loscutoff, Paul W.; Lee, Han-Bo-Ram; Bent, Stacey F.
- Chemistry of Materials, Vol. 22, Issue 19
Orientation-controlled molecule-by-molecule polymer wire growth by the carrier-gas-type organic chemical vapor deposition and the molecular layer deposition
journal, July 2007
- Yoshimura, Tetsuzo; Ito, Shinji; Nakayama, Tomohiro
- Applied Physics Letters, Vol. 91, Issue 3
Molecular layer deposition of polyethylene terephthalate thin films
journal, January 2012
- Ivanova, Tatyana V.; Maydannik, Philipp S.; Cameron, David C.
- Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 30, Issue 1
Highly Conductive and Conformal Poly(3,4-ethylenedioxythiophene) (PEDOT) Thin Films via Oxidative Molecular Layer Deposition
journal, June 2014
- Atanasov, Sarah E.; Losego, Mark D.; Gong, Bo
- Chemistry of Materials, Vol. 26, Issue 11
Organic and inorganic–organic thin film structures by molecular layer deposition: A review
journal, January 2014
- Sundberg, Pia; Karppinen, Maarit
- Beilstein Journal of Nanotechnology, Vol. 5
Macroscopic facilitation of glassy relaxation kinetics: Ultrastable glass films with frontlike thermal response
journal, December 2010
- Léonard, Sébastien; Harrowell, Peter
- The Journal of Chemical Physics, Vol. 133, Issue 24
Tunable molecular orientation and elevated thermal stability of vapor-deposited organic semiconductors
journal, March 2015
- Dalal, Shakeel S.; Walters, Diane M.; Lyubimov, Ivan
- Proceedings of the National Academy of Sciences, Vol. 112, Issue 14
Ultralow Thermal Conductivity of Atomic/Molecular Layer-Deposited Hybrid Organic–Inorganic Zincone Thin Films
journal, October 2013
- Liu, Jun; Yoon, Byunghoon; Kuhlmann, Eli
- Nano Letters, Vol. 13, Issue 11
Pyrolysis of Alucone Molecular Layer Deposition Films Studied Using In Situ Transmission Fourier Transform Infrared Spectroscopy
journal, March 2015
- DuMont, Jaime W.; George, Steven M.
- The Journal of Physical Chemistry C, Vol. 119, Issue 26
Fine-Tunable Absorption of Uniformly Aligned Polyurea Thin Films for Optical Filters Using Sequentially Self-Limited Molecular Layer Deposition
journal, April 2016
- Park, Yi-Seul; Choi, Sung-Eun; Kim, Hyein
- ACS Applied Materials & Interfaces, Vol. 8, Issue 18
Intramolecular and Intermolecular Interactions in Hybrid Organic–Inorganic Alucone Films Grown by Molecular Layer Deposition
journal, June 2016
- Park, Yi-Seul; Kim, Hyein; Cho, Boram
- ACS Applied Materials & Interfaces, Vol. 8, Issue 27
Guidance of growth mode and structural character in organic–inorganic hybrid materials – a comparative study
journal, January 2014
- Klepper, K. B.; Nilsen, O.; Francis, S.
- Dalton Trans., Vol. 43, Issue 9
Deposition of Organic- Inorganic Hybrid Materials by Atomic Layer Deposition
conference, January 2008
- Nilsen, Ola; Klepper, Karina; Nielsen, Heidi
- 214th ECS Meeting, ECS Transactions
Atomic layer deposition of organic–inorganic hybrid materials based on saturated linear carboxylic acids
journal, January 2011
- Klepper, Karina Barnholt; Nilsen, Ola; Hansen, Per-Anders
- Dalton Transactions, Vol. 40, Issue 17
Highly oriented polyamide thin films prepared by vapor deposition polymerization
journal, April 1991
- Kubono, Atsushi; Okui, Norimasa; Tanaka, Katsufumi
- Thin Solid Films, Vol. 199, Issue 2
Quantification of Thin Film Crystallographic Orientation Using X-ray Diffraction with an Area Detector
journal, June 2010
- Baker, Jessy L.; Jimison, Leslie H.; Mannsfeld, Stefan
- Langmuir, Vol. 26, Issue 11
Analysis of polyurethanes using core excitation spectroscopy. Part II: Inner shell spectra of ether, urea and carbamate model compounds
journal, August 1995
- Urquhart, S. G.; Hitchcock, A. P.; Priester, R. D.
- Journal of Polymer Science Part B: Polymer Physics, Vol. 33, Issue 11
Growth and Properties of Hybrid Organic-Inorganic Metalcone Films Using Molecular Layer Deposition Techniques
journal, September 2012
- Lee, Byoung H.; Yoon, Byunghoon; Abdulagatov, Aziz I.
- Advanced Functional Materials, Vol. 23, Issue 5
PM-IRRAS Investigation of Self-Assembled Monolayers Grafted onto SiO 2 /Au Substrates
journal, May 2011
- Ramin, Michaël A.; Le Bourdon, Gwénaëlle; Daugey, Nicolas
- Langmuir, Vol. 27, Issue 10
Epoxy-Terminated Self-Assembled Monolayers Containing Internal Urea or Amide Groups
journal, February 2015
- Ramin, Michaël A.; Le Bourdon, Gwénaëlle; Heuzé, Karine
- Langmuir, Vol. 31, Issue 9
Infrared temperature studies of a simple polyurea
journal, January 1997
- Coleman, Michael M.; Sobkowiak, Maria; Pehlert, George J.
- Macromolecular Chemistry and Physics, Vol. 198, Issue 1
Vertical confinement and interface effects on the microstructure and charge transport of P3HT thin films
journal, February 2013
- Jimison, Leslie H.; Himmelberger, Scott; Duong, Duc T.
- Journal of Polymer Science Part B: Polymer Physics, Vol. 51, Issue 7
X-Ray Diffraction by Macromolecules
book, January 2005
- Kasai, Nobutami; Kakudo, Masao
- Springer Series in Chemical Physics
Two-dimensional charge transport in self-organized, high-mobility conjugated polymers
journal, October 1999
- Sirringhaus, H.; Brown, P. J.; Friend, R. H.
- Nature, Vol. 401, Issue 6754, p. 685-688
Piezoelectric and ferroelectric properties of aliphatic polyurea films synthesized by vapor deposition polymerization
conference, January 1996
- Hattori, T.; Takahashi, Y.; Iijima, M.
- 9th International Symposium on Electrets (ISE 9) Proceedings
Studies on segmented polyurethane—urea elastomers: Structure of segmented polyurethane—urea based on poly(tetramethylene glycol), 4,4'-diphenylmethane diisocyanate, and 4,4'-diaminodiphenylmethane
journal, October 1983
- Ishihara, Hideaki; Kimura, Itsuro; Yoshihara, Nori
- Journal of Macromolecular Science, Part B, Vol. 22, Issue 5-6
On the physical crosslinking of amine-extended polyurethane urea elastomers: A crystallographic analysis of bis-urea from diphenyl methane-4-isocyanate and 1,4-butane diamine
journal, April 1985
- Born, L.; Hespe, H.
- Colloid & Polymer Science, Vol. 263, Issue 4
Synthesis of Aliphatic Polyurea Films by Vapor Deposition Polymerization and Their Piezoelectric Properties
journal, August 1994
- Hattori, Takeshi; Iijima, Masayuki; Takahashi, Yoshikazu
- Japanese Journal of Applied Physics, Vol. 33, Issue Part 1, No. 8
Piezoelectric properties of thin films of aliphatic polyurea 79 synthesized by vapor deposition polymerization
journal, September 1995
- Hattori, Takeshi; Iijima, Masayuki; Takahashi, Yoshikazu
- Ferroelectrics, Vol. 171, Issue 1
Three-dimensional supramolecular assembly having infinite two-dimensional interlocking networks built up only from simple and non-rigid organic molecules via hydrogen bonds. Crystal structures of α,ω-diureidoalkanes H2N(CO)NH–(CH2)n–NH(CO)NH2 with n=4 and 5
journal, October 2005
- Eda, Kazuo; Okazaki, Tadashi; Yamamura, Kimiaki
- Journal of Molecular Structure, Vol. 752, Issue 1-3
Oligomer Orientation in Vapor-Molecular-Layer-Deposited Alkyl-Aromatic Polyamide Films
journal, July 2012
- Peng, Qing; Efimenko, Kirill; Genzer, Jan
- Langmuir, Vol. 28, Issue 28
Molecular Layer Deposition of Alucone Polymer Films Using Trimethylaluminum and Ethylene Glycol
journal, May 2008
- Dameron, A. A.; Seghete, D.; Burton, B. B.
- Chemistry of Materials, Vol. 20, Issue 10
Importance of Trimethylaluminum Diffusion in Three-Step ABC Molecular Layer Deposition Using Trimethylaluminum, Ethanolamine, and Maleic Anhydride
journal, December 2010
- Seghete, Dragos; Hall, Robert A.; Yoon, Byunghoon
- Langmuir, Vol. 26, Issue 24
Cross-Linked Ultrathin Polyurea Films via Molecular Layer Deposition
journal, July 2013
- Zhou, Han; Toney, Michael F.; Bent, Stacey F.
- Macromolecules, Vol. 46, Issue 14
Molecular Recognition and Polymers
book, February 2008
- Rotello, Vincent M.; Thayumanavan, S.
- John Wiley and Sons, INC
Ethylenediamine at Air/Liquid and Air/Silica Interfaces: Protonation Versus Hydrogen Bonding Investigated by Sum Frequency Generation Spectroscopy
journal, March 2006
- Xu, Man; Liu, Dingfang; Allen, Heather C.
- Environmental Science & Technology, Vol. 40, Issue 5
Works referencing / citing this record:
Aromatic versus Aliphatic: Hydrogen Bonding Pattern in Chain-Extended High-Performance Polyurea
journal, February 2018
- Iqbal, Nahid; Tripathi, Manorama; Parthasarathy, Surekha
- ChemistrySelect, Vol. 3, Issue 7
Molecular interaction-dependent surface potentials of sequentially polymerized alucone films
journal, January 2018
- Choi, Ui-Jin; Kim, Hyein; Park, Yi-Seul
- Chemical Communications, Vol. 54, Issue 26
Emergence of time-dependent material properties in chain extended polyureas
journal, August 2018
- Iqbal, N.; Kumar, D.; Roy, P. K.
- Journal of Applied Polymer Science, Vol. 135, Issue 40
Structurally Stable Manganese Alkoxide Films Grown by Hybrid Molecular Layer Deposition for Electrochemical Applications
journal, August 2019
- Bergsman, David S.; Baker, Jon G.; Closser, Richard G.
- Advanced Functional Materials, Vol. 29, Issue 43
On the role of micro-porosity in affecting the environmental stability of atomic/molecular layer deposited (ZnO) a (Zn–O–C 6 H 4 –O) b films
journal, January 2019
- Aghaee, Morteza; Niemelä, Janne-Petteri; Kessels, Wilhelmus M. M.
- Dalton Transactions, Vol. 48, Issue 10