Atomic layer deposition of nanofilms on porous polymer substrates: Strategies for success

Welch, Brian C.; Casetta, Jeanne; Pathak, Rajesh; Elam, Jeffrey W.; Pochat-Bohatier, Céline; Miele, Philippe; Segal-Peretz, Tamar

doi:10.1116/6.0004187

Title: Atomic layer deposition of nanofilms on porous polymer substrates: Strategies for success

Journal Article · 21 January 2025 · Journal of Vacuum Science and Technology A

DOI: https://doi.org/10.1116/6.0004187 · OSTI ID:2561418

^[1];

^[2];

^[3];

^[2];

^[4]

Technion-Israel Institute of Technology, Haifa (Israel); Argonne National Laboratory (ANL), Argonne, IL (United States)
Univ. Montpellier (France). Institut Européen des Membranes
Argonne National Laboratory (ANL), Argonne, IL (United States)
Technion-Israel Institute of Technology, Haifa (Israel)

Atomic layer deposition (ALD) is a versatile technique for engineering the surfaces of porous polymers, imbuing the flexible, high-surface-area substrates with inorganic and hybrid material properties. Previously reported enhancements include fouling resistance, electrical conductance, thermal stability, photocatalytic activity, hydrophilicity, and oleophilicity. However, there are many poorly understood phenomena that introduce challenges in applying ALD to porous polymers. In this paper, we address five common challenges and ways to overcome them: (1) entrapped precursor, (2) embrittlement, (3) film fracture, (4) deformation, and (5) pore collapse. These challenges are often interrelated and can exacerbate one another. To investigate these phenomena, we applied various ALD chemistries to porous polymers including polyethersulfone, polysulfone, polyvinylidene fluoride, and polycarbonate track-etched membranes. Reaction-diffusion modeling revealed why certain precursors and processing conditions result in embrittling subsurface material growth, entrapment of unreacted precursors, and nongrowth. We quantify the limits of ALD processing temperatures that are dictated by thermal expansion mismatch and can lead to fractured ALD films. The results herein allow us to make recommendations to avoid, mitigate, or overcome the difficulties encountered when performing ALD and plasma-enhanced ALD on porous polymers. We intend this article to serve as a “lessons learned” guide informed by previous experience to provide a better understanding of the difficulties and limitations of ALD on porous polymers and knowledge-based guidelines for successful depositions. This knowledge can accelerate future research and help experimentalists navigate and troubleshoot as they expose porous polymers to reactive precursor vapors.

View Journal Article

Cite

Export

Save

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: Horizon 2020 Framework Programme; Israel Ministry of Energy and Water; Israel-United States Binational Industrial Research and Development Foundation (BIRD); USDOE; USDOE Laboratory Directed Research and Development (LDRD) Program

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 2561418

Journal Information:: Journal of Vacuum Science and Technology A, Journal Name: Journal of Vacuum Science and Technology A Journal Issue: 2 Vol. 43; ISSN 1520-8559; ISSN 0734-2101

Publisher:: American Vacuum Society / AIPCopyright Statement

Country of Publication:: United States

Language:: English

References (67)

Polyphenol‐Sensitized Atomic Layer Deposition for Membrane Interface Hydrophilization Yang, Xiaobin; Sun, Pan; Zhang, Huiru Advanced Functional Materials, Vol. 30, Issue 15 https://doi.org/10.1002/adfm.201910062	journal	February 2020
Hybrid Organic–Inorganic–Organic Isoporous Membranes with Tunable Pore Sizes and Functionalities for Molecular Separation Zhang, Zhenzhen; Simon, Assaf; Abetz, Clarissa Advanced Materials, Vol. 33, Issue 48 https://doi.org/10.1002/adma.202105251	journal	September 2021
Molecular layer-by-layer deposition of highly crosslinked polyamide films Johnson, Peter M.; Yoon, Joonsung; Kelly, Jennifer Y. Journal of Polymer Science Part B: Polymer Physics, Vol. 50, Issue 3 https://doi.org/10.1002/polb.23002	journal	November 2011
Review of Recent Advances in Applications of Vapor-Phase Material Infiltration Based on Atomic Layer Deposition Subramanian, Ashwanth; Tiwale, Nikhil; Nam, Chang-Yong JOM, Vol. 71, Issue 1 https://doi.org/10.1007/s11837-018-3141-4	journal	September 2018
Sequential Infiltration Synthesis of Al2O3 in Polyethersulfone Membranes Waldman, Ruben Z.; Choudhury, Devika; Mandia, David J. JOM, Vol. 71, Issue 1 https://doi.org/10.1007/s11837-018-3142-3	journal	September 2018
Stress and strain in the vacuum deposited thin films Tamulevičius, S. Vacuum, Vol. 51, Issue 2 https://doi.org/10.1016/S0042-207X(98)00145-6	journal	October 1998
Outgassing effect in polymeric composites exposed to space environment thermal-vacuum conditions Pastore, R.; Delfini, A.; Albano, M. Acta Astronautica, Vol. 170 https://doi.org/10.1016/j.actaastro.2020.02.019	journal	May 2020
Is atomic layer deposition of silver possible on N95 masks? Hashemi Astaneh, Sarah; Bhatia, Harshdeep; Nagay, Bruna Egumi Applied Surface Science, Vol. 591 https://doi.org/10.1016/j.apsusc.2022.153195	journal	July 2022
Nanoengineering membrane surfaces: A new paradigm for efficient CO2 capture Hu, Leiqing; Bui, Vinh T.; Esmaeili, Narjes Carbon Capture Science & Technology, Vol. 10 https://doi.org/10.1016/j.ccst.2023.100150	journal	March 2024
Plasma activation of porous polytetrafluoroethylene membranes for superior hydrophilicity and separation performances via atomic layer deposition of TiO2 Xu, Qiang; Yang, Yang; Yang, Jie Journal of Membrane Science, Vol. 443 https://doi.org/10.1016/j.memsci.2013.04.061	journal	September 2013
Hydrophilization of porous polypropylene membranes by atomic layer deposition of TiO2 for simultaneously improved permeability and selectivity Xu, Qiang; Yang, Jun; Dai, Jiawei Journal of Membrane Science, Vol. 448 https://doi.org/10.1016/j.memsci.2013.08.018	journal	December 2013
Plasma activation and atomic layer deposition of TiO2 on polypropylene membranes for improved performances of lithium-ion batteries Chen, He; Lin, Qian; Xu, Qiang Journal of Membrane Science, Vol. 458 https://doi.org/10.1016/j.memsci.2014.02.004	journal	May 2014
Enhancing the hydrophilicity and water permeability of polypropylene membranes by nitric acid activation and metal oxide deposition Chen, He; Kong, Liang; Wang, Yong Journal of Membrane Science, Vol. 487 https://doi.org/10.1016/j.memsci.2015.03.044	journal	August 2015
Composite membranes with ultrathin and conformal passivation for universal microfiltration compatible with organic solvents Ahn, Junyong; Ryu, Taehyun; Park, Junyong Journal of Membrane Science, Vol. 651 https://doi.org/10.1016/j.memsci.2022.120455	journal	June 2022
Atomic layer deposition for membrane modification, functionalization and preparation: A review Xiong, Sen; Qian, Xiaofeng; Zhong, Zhaoxiang Journal of Membrane Science, Vol. 658 https://doi.org/10.1016/j.memsci.2022.120740	journal	September 2022
Hybrid nanomaterials through molecular and atomic layer deposition: Top down, bottom up, and in-between approaches to new materials Gregorczyk, Keith; Knez, Mato Progress in Materials Science, Vol. 75 https://doi.org/10.1016/j.pmatsci.2015.06.004	journal	January 2016
Core-shell structured, mixed cellulose ester-alumina composite membranes for air filters with improved environmental resistance Ahn, Junyong; Park, Hyunsol; Ryu, Taehyun Separation and Purification Technology, Vol. 309 https://doi.org/10.1016/j.seppur.2022.123012	journal	March 2023
Atomic layer deposition of TiO2 on porous polysulfone hollow fibers membranes for water treatment Casetta, Jeanne; Ortiz, Danae Gonzalez; Pochat-Bohatier, Céline Separation and Purification Technology, Vol. 312 https://doi.org/10.1016/j.seppur.2023.123377	journal	May 2023
Effect of Al 2 O 3 ALD coating and vapor infusion on the bulk mechanical response of elastic and viscoelastic polymers McClure, Christina D.; Oldham, Christopher J.; Parsons, Gregory N. Surface and Coatings Technology, Vol. 261 https://doi.org/10.1016/j.surfcoat.2014.10.029	journal	January 2015
AgTi nanoparticle hybrid PVDF membrane with stable and high efficiency antibacterial performance by atomic layer deposition Zhang, Lei; He, Dan; Jiang, Yancong Surfaces and Interfaces, Vol. 30 https://doi.org/10.1016/j.surfin.2022.101826	journal	June 2022
Reaction–Diffusion Transport Model to Predict Precursor Uptake and Spatial Distribution in Vapor-Phase Infiltration Processes Ren, Yi; McGuinness, Emily K.; Huang, Chaofan Chemistry of Materials, Vol. 33, Issue 13 https://doi.org/10.1021/acs.chemmater.1c01283	journal	June 2021
Origin of Instability of Titanicone Grown by Molecular Layer Deposition Using TiCl₄ and Ethylene Glycol Kim, Hyeongjin; Hyun, Jieun; Kim, Gaeun Chemistry of Materials, Vol. 36, Issue 1 https://doi.org/10.1021/acs.chemmater.3c02018	journal	December 2023
Tailoring the Interfacial Interactions of Porous Polymer Membranes to Accelerate Atomic Layer Deposition: The Latent Path to Antifouling Membranes Shevate, Rahul; Rozyyev, Vepa; Pathak, Rajesh Chemistry of Materials, Vol. 36, Issue 8 https://doi.org/10.1021/acs.chemmater.3c03090	journal	April 2024
Atomic Layer Deposition for Membranes: Basics, Challenges, and Opportunities Weber, Matthieu; Julbe, Anne; Ayral, André Chemistry of Materials, Vol. 30, Issue 21 https://doi.org/10.1021/acs.chemmater.8b02687	journal	October 2018
Vapor Phase Infiltration of Metal Oxides into Nanoporous Polymers for Organic Solvent Separation Membranes McGuinness, Emily K.; Zhang, Fengyi; Ma, Yao Chemistry of Materials, Vol. 31, Issue 15 https://doi.org/10.1021/acs.chemmater.9b01141	journal	July 2019
Atomic Layer Deposition from Dissolved Precursors Wu, Yanlin; Döhler, Dirk; Barr, Maïssa Nano Letters, Vol. 15, Issue 10 https://doi.org/10.1021/acs.nanolett.5b01424	journal	September 2015
Ultrahigh Elastic Strain Energy Storage in Metal-Oxide-Infiltrated Patterned Hybrid Polymer Nanocomposites Dusoe, Keith J.; Ye, Xinyi; Kisslinger, Kim Nano Letters, Vol. 17, Issue 12 https://doi.org/10.1021/acs.nanolett.7b03238	journal	November 2017
Precisely Engineered Photoreactive Titanium Nanoarray Coating to Mitigate Biofouling in Ultrafiltration Zhang, Lei; Shi, Xingxing; Sun, Meng ACS Applied Materials & Interfaces, Vol. 13, Issue 8 https://doi.org/10.1021/acsami.0c21221	journal	February 2021
Atomic Layer Deposition for Gradient Surface Modification and Controlled Hydrophilization of Ultrafiltration Polymer Membranes Itzhak, Tamar; Segev-Mark, Naama; Simon, Assaf ACS Applied Materials & Interfaces, Vol. 13, Issue 13 https://doi.org/10.1021/acsami.0c23084	journal	March 2021
Mechanical Behavior of Hybrid Thin Films Fabricated by Sequential Infiltration Synthesis in Water-Rich Environment Keren, Shachar; Bukowski, Cynthia; Barzilay, Maya ACS Applied Materials & Interfaces, Vol. 15, Issue 40 https://doi.org/10.1021/acsami.3c09609	journal	September 2023
Electrospinning Combined with Atomic Layer Deposition to Generate Applied Nanomaterials: A Review Vempati, Sesha; Ranjith, Kugalur Shanmugam; Topuz, Fuat ACS Applied Nano Materials, Vol. 3, Issue 7 https://doi.org/10.1021/acsanm.0c01120	journal	May 2020
Controlling Nanoscale Pore Size and Wall Composition in Polycarbonate Membranes via Atomic Layer Deposition and Sequential Infiltration Synthesis: Implications for High Water Permeance Pathak, Rajesh; Rozyyev, Vepa; Shevate, Rahul ACS Applied Nano Materials, Vol. 6, Issue 19 https://doi.org/10.1021/acsanm.3c03161	journal	September 2023
Sequential Infiltration Synthesis of Al₂O₃ in Biodegradable Polybutylene Succinate: Characterization of the Infiltration Mechanism Motta, Alessia; Seguini, Gabriele; Perego, Michele ACS Applied Polymer Materials, Vol. 4, Issue 10 https://doi.org/10.1021/acsapm.2c01073	journal	October 2022
Modeling Water Transport in Interlayered Thin-Film Nanocomposite Membranes: Gutter Effect vs Funnel Effect Wang, Fei; Yang, Zhe; Tang, Chuyang Y. ACS ES&T Engineering, Vol. 2, Issue 11 https://doi.org/10.1021/acsestengg.2c00133	journal	August 2022
The Development and Atomic Structure of Zinc Oxide Crystals Grown within Polymers from Vapor Phase Precursors Weisbord, Inbal; Barzilay, Maya; Cai, Ruoke ACS Nano, Vol. 18, Issue 28 https://doi.org/10.1021/acsnano.4c02846	journal	July 2024
Ultrathin ALD Aluminum Oxide Thin Films Suppress the Thermal Shrinkage of Battery Separator Membranes da Veiga, Leonardo Pires; Jeanguenat, Colin; Lisco, Fabiana ACS Omega, Vol. 7, Issue 49 https://doi.org/10.1021/acsomega.2c06318	journal	November 2022
Elucidation of Titanium Dioxide Nucleation and Growth on a Polydopamine-Modified Nanoporous Polyvinylidene Fluoride Substrate via Low-Temperature Atomic Layer Deposition DeStefano, Audra; Yin, Jiashi; Kraus, Theodore J. ACS Omega, Vol. 3, Issue 9 https://doi.org/10.1021/acsomega.8b00864	journal	September 2018
Improved Mechanical Stability of Dried Collagen Membrane after Metal Infiltration Lee, Seung-Mo; Pippel, Eckhard; Moutanabbir, Oussama ACS Applied Materials & Interfaces, Vol. 2, Issue 8 https://doi.org/10.1021/am100438b	journal	July 2010
Alucone Interlayers to Minimize Stress Caused by Thermal Expansion Mismatch between Al ₂ O ₃ Films and Teflon Substrates Jen, Shih-Hui; George, Steven M.; McLean, Robert S. ACS Applied Materials & Interfaces, Vol. 5, Issue 3 https://doi.org/10.1021/am303077x	journal	January 2013
Conformal Coating on Ultrahigh-Aspect-Ratio Nanopores of Anodic Alumina by Atomic Layer Deposition Elam, J. W.; Routkevitch, D.; Mardilovich, P. P. Chemistry of Materials, Vol. 15, Issue 18, p. 3507-3517 https://doi.org/10.1021/cm0303080	journal	September 2003
Atomic Layer Deposition of Al ₂ O ₃ Films on Polyethylene Particles Ferguson, J. D.; Weimer, A. W.; George, S. M. Chemistry of Materials, Vol. 16, Issue 26 https://doi.org/10.1021/cm040008y	journal	December 2004
Nucleation and Growth during Al ₂ O ₃ Atomic Layer Deposition on Polymers Wilson, C. A.; Grubbs, R. K.; George, S. M. Chemistry of Materials, Vol. 17, Issue 23 https://doi.org/10.1021/cm050704d	journal	November 2005
Molecular Layer Deposition of Titanicone Films using TiCl ₄ and Ethylene Glycol or Glycerol: Growth and Properties Abdulagatov, Aziz I.; Hall, Robert A.; Sutherland, Jackson L. Chemistry of Materials, Vol. 24, Issue 15 https://doi.org/10.1021/cm300162v	journal	July 2012
New Insight into the Mechanism of Sequential Infiltration Synthesis from Infrared Spectroscopy Biswas, Mahua; Libera, Joseph A.; Darling, Seth B. Chemistry of Materials, Vol. 26, Issue 21 https://doi.org/10.1021/cm502427q	journal	October 2014
Atomic Layer Deposition: An Overview George, Steven M. Chemical Reviews, Vol. 110, Issue 1, p. 111-131 https://doi.org/10.1021/cr900056b	journal	January 2010
Molecular Layer Deposition on Carbon Nanotubes Brown, Joseph J.; Hall, Robert A.; Kladitis, Paul E. ACS Nano, Vol. 7, Issue 9 https://doi.org/10.1021/nn402733g	journal	August 2013
Degradation of polymer films Cheneler, David; Bowen, James Soft Matter, Vol. 9, Issue 2 https://doi.org/10.1039/C2SM26502H	journal	January 2013
Vapor phase infiltration (VPI) for transforming polymers into organic–inorganic hybrid materials: a critical review of current progress and future challenges Leng, Collen Z.; Losego, Mark D. Materials Horizons, Vol. 4, Issue 5 https://doi.org/10.1039/C7MH00196G	journal	January 2017
Molecular layer deposited alucone thin films from long-chain organic precursors: from brittle to ductile mechanical characteristics Niemelä, Janne-Petteri; Rohbeck, Nadia; Michler, Johann Dalton Transactions, Vol. 49, Issue 31 https://doi.org/10.1039/D0DT02210A	journal	January 2020
About the importance of purge time in molecular layer deposition of alucone films Jain, Hardik; Poodt, Paul Dalton Transactions, Vol. 50, Issue 17 https://doi.org/10.1039/D1DT00623A	journal	January 2021
Atomic layer deposition enables multi-modal three-dimensional electron microscopy of isoporous membranes Simon, Assaf; Zhang, Zhenzhen; Abetz, Clarissa Nanoscale, Vol. 15, Issue 7 https://doi.org/10.1039/D2NR05477A	journal	January 2023
Interpreting inorganic compositional depth profiles to understand the rate-limiting step in vapor phase infiltration processes Balogun, Shuaib A.; Ren, Yi; Lively, Ryan P. Physical Chemistry Chemical Physics, Vol. 25, Issue 20 https://doi.org/10.1039/D3CP01517C	journal	January 2023
Critical tensile and compressive strains for cracking of Al₂O₃ films grown by atomic layer deposition Jen, Shih-Hui; Bertrand, Jacob A.; George, Steven M. Journal of Applied Physics, Vol. 109, Issue 8 https://doi.org/10.1063/1.3567912	journal	April 2011
Conformality in atomic layer deposition: Current status overview of analysis and modelling Cremers, Véronique; Puurunen, Riikka L.; Dendooven, Jolien Applied Physics Reviews, Vol. 6, Issue 2 https://doi.org/10.1063/1.5060967	journal	June 2019
Thermal Expansion of HfO ₂ and ZrO ₂ : Thermal Expansion Haggerty, Ryan P.; Sarin, Pankaj; Apostolov, Zlatomir D. Journal of the American Ceramic Society, Vol. 97, Issue 7 https://doi.org/10.1111/jace.12975	journal	May 2014
Systematic study of trimethyl aluminum infiltration in polyethylene terephthalate and its effect on the mechanical properties of polyethylene terephthalate fibers Padbury, Richard P.; Jur, Jesse S. Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 33, Issue 1 https://doi.org/10.1116/1.4898435	journal	January 2015
Continuous polymer films deposited on top of porous substrates using plasma-enhanced atomic layer deposition and molecular layer deposition Welch, Brian C.; McIntee, Olivia M.; Ode, Anand B. Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 38, Issue 5 https://doi.org/10.1116/6.0000271	journal	August 2020
Thermomechanical properties of aluminum oxide thin films made by atomic layer deposition Ylivaara, Oili M. E.; Langner, Andreas; Ek, Satu Journal of Vacuum Science & Technology A, Vol. 40, Issue 6 https://doi.org/10.1116/6.0002095	journal	November 2022
Molecular layer deposition of alucone in high aspect ratio trenches: The effect of TMA outgassing on step-coverage Jain, Hardik; Creatore, Mariadriana; Poodt, Paul Journal of Vacuum Science & Technology A, Vol. 41, Issue 1 https://doi.org/10.1116/6.0002249	journal	December 2022
Greatly Increased Toughness of Infiltrated Spider Silk Lee, S. -M.; Pippel, E.; Gosele, U. Science, Vol. 324, Issue 5926 https://doi.org/10.1126/science.1168162	journal	April 2009
Carbon-doped metal oxide interfacial nanofilms for ultrafast and precise separation of molecules Sengupta, Bratin; Dong, Qiaobei; Khadka, Rajan Science, Vol. 381, Issue 6662 https://doi.org/10.1126/science.adh2404	journal	September 2023
Tailoring the Interfacial Interactions of Porous Polymer Membranes to Accelerate Atomic Layer Deposition: The Latent Path to Antifouling Membranes Shevate, Rahul; Rozyyev, Vepa; Pathak, Rajesh ECS Meeting Abstracts, Vol. MA2022-02, Issue 31 https://doi.org/10.1149/MA2022-02311160mtgabs	journal	October 2022
Thermal expansion of anatase and rutile between 300 and 575 K using synchrotron powder X-ray diffraction Hummer, D. R.; Heaney, P. J.; Post, J. E. Powder Diffraction, Vol. 22, Issue 4 https://doi.org/10.1154/1.2790965	journal	December 2007
Young's Modulus and Coefficient of Linear Thermal Expansion of ZnO Conductive and Transparent Ultra-Thin Films Yamamoto, Naoki; Makino, Hisao; Yamamoto, Tetsuya Advances in Materials Science and Engineering, Vol. 2011 https://doi.org/10.1155/2011/136127	journal	January 2011
Metalcones: Hybrid Organic–Inorganic Films Fabricated Using Atomic and Molecular Layer Deposition Techniques George, Steven M.; Lee, Byoung H.; Yoon, Byunghoon Journal of Nanoscience and Nanotechnology, Vol. 11, Issue 9 https://doi.org/10.1166/jnn.2011.5034	journal	September 2011
Recommendations for the characterization of porous solids (Technical Report) Rouquerol, J.; Avnir, D.; Fairbridge, C. W. Pure and Applied Chemistry, Vol. 66, Issue 8, p. 1739-1758 https://doi.org/10.1351/pac199466081739	journal	January 1994
Comparison of the Growth and Thermal Properties of Nonwoven Polymers after Atomic Layer Deposition and Vapor Phase Infiltration Keskiväli, Laura; Heikkilä, Pirjo; Kenttä, Eija Coatings, Vol. 11, Issue 9 https://doi.org/10.3390/coatings11091028	journal	August 2021

Similar Records

Continuous polymer films deposited on top of porous substrates using plasma-enhanced atomic layer deposition and molecular layer deposition

Journal Article · 2020 · Journal of Vacuum Science and Technology A · OSTI ID:1650213

Welch, Brian C.; McIntee, Olivia M.; Ode, Anand B.; +4 more

Crystalline 1D Coordination Polymer Inhibitor Layer Leads to Vertical Sidewalls in Selectively Deposited ZnO on Nanoscale Patterns

Journal Article · 2025 · ACS Nano · OSTI ID:2587685

Shearer, Alexander; Cho, Yukio; Kim, Miso; +5 more

Modeling precursor diffusion and reaction of atomic layer deposition in porous structures

Journal Article · 2014 · Journal of Vacuum Science and Technology. A, Vacuum, Surfaces and Films · OSTI ID:22318047

Keuter, Thomas; Menzler, Norbert Heribert; Mauer, Georg; +3 more

Related Subjects

36 MATERIALS SCIENCE
atomic layer deposition
chemical compounds
materials properties
nanofilms
plasma processing
polymers
reaction-diffusion system
scanning electron microscopy
thermal effects
thin films

Title: Atomic layer deposition of nanofilms on porous polymer substrates: Strategies for success

Citation Formats

References (67)

Similar Records

Related Subjects