@article{zhao_gong_nunn_lemaire_stevens_sidi_williams_oldham_walls_shepherd_et al._2015, title={Conformal and highly adsorptive metal-organic framework thin films via layer-by-layer growth on ALD-coated fiber mats}, volume={3}, ISSN={["2050-7496"]}, url={http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=ORCID&SrcApp=OrcidOrg&DestLinkType=FullRecord&DestApp=WOS_CPL&KeyUT=WOS:000346906100014&KeyUID=WOS:000346906100014}, DOI={10.1039/c4ta05501b}, abstractNote={Fiber@ALD@MOF structures fabricated via ALD and layer-by-layer MOF synthesis show good conformality and high adsorption capacity.}, number={4}, journal={JOURNAL OF MATERIALS CHEMISTRY A}, author={Zhao, Junjie and Gong, Bo and Nunn, William T. and Lemaire, Paul C. and Stevens, Eric C. and Sidi, Fahim I. and Williams, Philip S. and Oldham, Christopher J. and Walls, Howard J. and Shepherd, Sarah D. and et al.}, year={2015}, pages={1458–1464} } @article{atanasov_losego_gong_sachet_maria_williams_parsons_2014, title={Highly Conductive and Conformal Poly(3,4-ethylenedioxythiophene) (PEDOT) Thin Films via Oxidative Molecular Layer Deposition}, volume={26}, ISSN={["1520-5002"]}, url={http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=ORCID&SrcApp=OrcidOrg&DestLinkType=FullRecord&DestApp=WOS_CPL&KeyUT=WOS:000337199400019&KeyUID=WOS:000337199400019}, DOI={10.1021/cm500825b}, abstractNote={This work introduces oxidative molecular layer deposition (oMLD) as a chemical route to synthesize highly conductive and conformal poly(3,4-ethylenedioxythiophene) (PEDOT) thin films via sequential vapor exposures of molybdenum(V) chloride (MoCl5, oxidant) and ethylene dioxythiophene (EDOT, monomer) precursors. The growth temperature strongly affects PEDOT’s crystalline structure and electronic conductivity. Films deposited at ∼150 °C exhibit a highly textured crystalline structure, with {010} planes aligned parallel with the substrate. Electrical conductivity of these textured films is routinely above 1000 S cm–1, with the most conductive films exceeding 3000 S cm–1. At lower temperatures (∼100 °C) the films exhibit a random polycrystalline structure and display smaller conductivities. Compared with typical electrochemical, solution-based, and chemical vapor deposition techniques, oMLD PEDOT films achieve high conductivity without the need for additives or postdeposition treatments. Moreover, the sequent...}, number={11}, journal={CHEMISTRY OF MATERIALS}, author={Atanasov, Sarah E. and Losego, Mark D. and Gong, Bo and Sachet, Edward and Maria, Jon-Paul and Williams, Philip S. and Parsons, Gregory N.}, year={2014}, month={Jun}, pages={3471–3478} } @article{zhao_losego_lemaire_williams_gong_atanasov_blevins_oldham_walls_shepherd_et al._2014, title={Highly adsorptive, MOF-functionalized nonwoven fiber mats for hazardous gas capture enabled by atomic layer deposition}, volume={1}, number={4}, journal={Advanced Materials Interfaces}, author={Zhao, J. J. and Losego, M. D. and Lemaire, P. C. and Williams, P. S. and Gong, B. and Atanasov, S. E. and Blevins, T. M. and Oldham, C. J. and Walls, H. J. and Shepherd, S. D. and et al.}, year={2014} } @misc{parsons_atanasov_dandley_devine_gong_jur_lee_oldham_peng_spagnola_et al._2013, title={Mechanisms and reactions during atomic layer deposition on polymers}, volume={257}, ISSN={["1873-3840"]}, url={http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=ORCID&SrcApp=OrcidOrg&DestLinkType=FullRecord&DestApp=WOS_CPL&KeyUT=WOS:000327915000012&KeyUID=WOS:000327915000012}, DOI={10.1016/j.ccr.2013.07.001}, abstractNote={There is significant growing interest in atomic layer deposition onto polymers for barrier coatings, nanoscale templates, surface modification layers and other applications. The ability to control the reaction between ALD precursors and polymers opens new opportunities in ALD materials processing. It is well recognized that ALD on many polymers involves subsurface precursor diffusion and reaction which are not encountered during ALD on solid surfaces. This article reviews recent insights into chemical reactions that proceed during ALD on polymers, with particular focus on the common Al2O3 reaction sequence using trimethyl aluminum (TMA) and water. We highlight the role of different polymer reactive groups in film growth, and how the balance between precursor diffusion and reaction can change as deposition proceeds. As a strong Lewis acid, TMA forms adducts with Lewis base sites within the polymer, and the reactions that proceed are determined by the neighboring bond structure. Moreover, the Lewis base sites can be saturated by TMA, producing a self-limiting half-reaction within a three-dimensional polymer, analogous to a self-limiting half-reaction commonly observed during ALD on a solid planar surface.}, number={23-24}, journal={COORDINATION CHEMISTRY REVIEWS}, author={Parsons, Gregory N. and Atanasov, Sarah E. and Dandley, Erinn C. and Devine, Christina K. and Gong, Bo and Jur, Jesse S. and Lee, Kyoungmi and Oldham, Christopher J. and Peng, Qing and Spagnola, Joseph C. and et al.}, year={2013}, month={Dec}, pages={3323–3331} } @article{loebl_oldham_devine_gong_atanasov_parsons_fedkiw_2013, title={Solid Electrolyte Interphase on Lithium-Ion Carbon Nanofiber Electrodes by Atomic and Molecular Layer Deposition}, volume={160}, ISSN={["1945-7111"]}, url={http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=ORCID&SrcApp=OrcidOrg&DestLinkType=FullRecord&DestApp=WOS_CPL&KeyUT=WOS:000326905000006&KeyUID=WOS:000326905000006}, DOI={10.1149/2.020311jes}, abstractNote={Carbon nanofibers were coated with Al2O3 by atomic layer deposition (ALD) or with an alumina-organic hybrid thin film layer by molecular layer deposition (MLD) to produce an artificial solid electrolyte interphase (SEI) prior to use as a lithium-ion battery electrode. The elemental composition of the materials was investigated using energy dispersive X-ray spectroscopy (EDX) and inductively coupled plasma mass spectrometry (ICP-MS). A coating of ten Al2O3 layers reduced the lithium lost to the SEI formation from 359 to 291 mAh/g (24%) during the first charge. These same cells possessed 370 mAh/g of stable reversible capacity when tested at low current density (25 mA/g), similar to uncoated material. At increased currents, Al2O3 films of either ten or twenty layers lowered the capacity retention when compared with uncoated materials. When compared to the ALD material, films deposited by MLD resulted in less improvement to reversible capacity and a greater loss of reversible capacity. These results indicate the use of ALD to create a new electrode surface and mitigate the Li losses to SEI formation may be a viable method of addressing the challenges associated with high-surface area electrode materials.}, number={11}, journal={JOURNAL OF THE ELECTROCHEMICAL SOCIETY}, author={Loebl, Andrew J. and Oldham, Christopher J. and Devine, Christina K. and Gong, Bo and Atanasov, Sarah E. and Parsons, Gregory N. and Fedkiw, Peter S.}, year={2013}, pages={A1971–A1978} } @article{gong_parsons_2012, title={Caprolactone Ring-Opening Molecular Layer Deposition of Organic-Aluminum Oxide Polymer Films}, volume={1}, ISSN={["2162-8769"]}, url={http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=ORCID&SrcApp=OrcidOrg&DestLinkType=FullRecord&DestApp=WOS_CPL&KeyUT=WOS:000319446800014&KeyUID=WOS:000319446800014}, DOI={10.1149/2.023204jss}, abstractNote={New hybrid organic-inorganic thin films are finding use in electronics, biomedical, chemical protection, and energy storage systems applications. In a unique vapor-source molecular layer deposition film formation reaction, we find that cyclic ɛ-caprolactone reacts with surface-adsorbed methyl-aluminum species to build a metal-organic hybrid coordination polymer thin film at substrate temperatures between 60 and 120°C. Infrared and X-ray photoelectron spectroscopy analysis confirms (–Al–O–(C8H16)–O–)n bonding, expected from the a Lewis acid catalyzed surface ring-opening reaction. In-situ IR analysis confirms the surface reaction sequence. The materials show good stability and maintain their physical structure in ambient. This surface acid-catalyzed vapor process could extend to other metal organics and vapor/surface ring opening reactions to yield new organic-inorganic film materials for use in gas diffusion barriers, separation membranes and chemical resistance coatings.}, number={4}, journal={ECS JOURNAL OF SOLID STATE SCIENCE AND TECHNOLOGY}, author={Gong, Bo and Parsons, Gregory N.}, year={2012}, pages={P210–P215} } @article{gong_spagnola_arvidson_khan_parsons_2012, title={Directed inorganic modification of bi-component polymer fibers by selective vapor reaction and atomic layer deposition}, volume={53}, ISSN={["1873-2291"]}, url={http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=ORCID&SrcApp=OrcidOrg&DestLinkType=FullRecord&DestApp=WOS_CPL&KeyUT=WOS:000309377400009&KeyUID=WOS:000309377400009}, DOI={10.1016/j.polymer.2012.08.018}, abstractNote={Abstract Nanocomposite organic/inorganic materials with spatially-controlled composition can be formed using vapor-phase atomic layer deposition (ALD) on bi-component polymer fibers. The ALD process promotes selective precursor infusion into the inner core of a core/shell polymer fiber, yielding nanoparticles encapsulated within the core. Likewise, choosing alternate precursors or reaction conditions yield particles or films on the outer polymer shell. In-situ infrared spectroscopy and transmission electron microscopy show that infusion yields selective dispersion of aluminum oxide in different polymer regions, forming fine nanoparticle dispersions or films. Selective inclusion of metal oxide materials during atomic layer deposition on polymers can create unique organic/inorganic composite structures for many advanced uses.}, number={21}, journal={POLYMER}, author={Gong, Bo and Spagnola, Joseph C. and Arvidson, Sara A. and Khan, Saad A. and Parsons, Gregory N.}, year={2012}, month={Sep}, pages={4631–4636} } @article{gong_kim_parsons_2012, title={Mesoporous Metal Oxides by Vapor Infiltration and Atomic Layer Deposition on Ordered Surfactant Polymer Films}, volume={28}, ISSN={["0743-7463"]}, url={http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=ORCID&SrcApp=OrcidOrg&DestLinkType=FullRecord&DestApp=WOS_CPL&KeyUT=WOS:000307479000029&KeyUID=WOS:000307479000029}, DOI={10.1021/la302027b}, abstractNote={Catalysis, chemical separations, and energy conversion devices often depend on well-defined mesoporous materials as supports or active component elements. Herein, we show that ordered assembled organic surfactant films can directly template porous inorganic solids with surface area exceeding 1000 m(2)/g by infusing the polymers with reactive inorganic vapors, followed by anneal. The specific surface area, pore size, chemical composition, and overall shape of the product material are tuned by choice of the polymer and precursor materials as well as the influsion and postinfusion treatment conditions. X-ray diffraction, infrared spectroscopy, and electron microscopy show that vapor infusion changes both the physical and chemical structure of the starting ordered polymer films, consistent with quantified trends in specific surface area and pore size distribution measured by nitrogen adsorption after film annealing. This method yields porous TiO(2) films, for example, that function as an anode layer in a dye-sensitized solar cell.}, number={32}, journal={LANGMUIR}, author={Gong, Bo and Kim, Do Han and Parsons, Gregory N.}, year={2012}, month={Aug}, pages={11915–11922} } @article{gong_parsons_2012, title={Quantitative in situ infrared analysis of reactions between trimethylaluminum and polymers during Al2O3 atomic layer deposition}, volume={22}, ISSN={["1364-5501"]}, url={http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=ORCID&SrcApp=OrcidOrg&DestLinkType=FullRecord&DestApp=WOS_CPL&KeyUT=WOS:000306479600031&KeyUID=WOS:000306479600031}, DOI={10.1039/c2jm32343e}, abstractNote={The reactions of trimethylaluminum (TMA) toward substrates during the Al2O3 atomic layer deposition (ALD) on a variety of polymers were studied by in situ Fourier transform infrared spectroscopy (FTIR). The experiments demonstrate that TMA reacts with certain nucleophilic functional groups on the polymer surface during the first several ALD cycles. For some polymer substrates, TMA vapor penetrates into the polymer and reacts in the polymer bulk. In both cases, the initial reaction plays an important role in the nucleation and growth of Al2O3. For chemically inert polymers, such as polypropylene, nucleation of Al2O3 ALD is relative slow at the initial stage due to the lack of reactive groups on the substrate. However, polyester, polyamide and polyether are more reactive, and in situ FTIR spectra showed a larger extent of reaction with TMA, facilitating the nucleation of ALD film on these polymers. By comparing FTIR spectra, we quantitatively estimate the extent of TMA reaction towards different polymers, and confirmed the results using X-ray photoelectron spectroscopy and scanning electron microscopy. Results give insight into the importance of the polymer structure in determining the nature and extent of the reaction during ALD film processing on polymer substrates.}, number={31}, journal={JOURNAL OF MATERIALS CHEMISTRY}, author={Gong, Bo and Parsons, Gregory N.}, year={2012}, pages={15672–15682} } @article{wang_krommenhoek_bradford_gong_tracy_parsons_luo_zhu_2011, title={Coating Alumina on Catalytic Iron Oxide Nanoparticles for Synthesizing Vertically Aligned Carbon Nanotube Arrays}, volume={3}, ISSN={1944-8244 1944-8252}, url={http://dx.doi.org/10.1021/am201082m}, DOI={10.1021/am201082m}, abstractNote={To synthesize long and uniform vertically aligned carbon nanotube (VACNT) arrays, it is essential to use catalytic nanoparticles (NPs) with monodisperse sizes and to avoid NP agglomeration at the growth temperature. In this work, VACNT arrays were grown on chemically synthesized Fe(3)O(4) NPs of diameter 6 nm by chemical vapor deposition. Coating the NPs with a thin layer of Al(2)O(3) prior to CNT growth preserves the monodisperse sizes, resulting in uniform, thick and dense VACNT arrays. Comparison with uncoated NPs shows that the Al(2)O(3) coating effectively prevents the catalyst NPs from sintering and coalescing, resulting in improved control over VACNT growth.}, number={11}, journal={ACS Applied Materials & Interfaces}, publisher={American Chemical Society (ACS)}, author={Wang, Xin and Krommenhoek, Peter J. and Bradford, Philip D. and Gong, Bo and Tracy, Joseph B. and Parsons, Gregory N. and Luo, Tzy-Jiun M. and Zhu, Yuntian T.}, year={2011}, month={Oct}, pages={4180–4184} } @article{gong_peng_parsons_2011, title={Conformal Organic - Inorganic Hybrid Network Polymer Thin Films by Molecular Layer Deposition using Trimethylaluminum and Glycidol}, volume={115}, ISSN={["1520-6106"]}, url={http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=ORCID&SrcApp=OrcidOrg&DestLinkType=FullRecord&DestApp=WOS_CPL&KeyUT=WOS:000290427100026&KeyUID=WOS:000290427100026}, DOI={10.1021/jp201186k}, abstractNote={Growing interest in nanoscale organic-inorganic hybrid network polymer materials is driving exploration of new bulk and thin film synthesis reaction mechanisms. Molecular layer deposition (MLD) is a vapor-phase deposition process, based on atomic layer deposition (ALD) which proceeds by exposing a surface to an alternating sequence of two or more reactant species, where each surface half-reaction goes to completion before the next reactant exposure. This work describes film growth using trimethyl aluminum and heterobifunctional glycidol at moderate temperatures (90-150 °C), producing a relatively stable organic-inorganic network polymer of the form (-Al-O-(C(4)H(8))-O-)(n). Film growth rate and in situ reaction analysis indicate that film growth does not initially follow a steady-state rate, but increases rapidly during early film growth. The mechanism is consistent with subsurface species transport and trapping, previously documented during MLD and ALD on polymers. A water exposure step after the TMA produces a more linear growth rate, likely by blocking TMA subsurface diffusion. Uniform and conformal films are formed on complex nonplanar substrates. Upon postdeposition annealing, films transform into microporous metal oxides with ∼5 Å pore size and surface area as high as ∼327 m(2)/g, and the resulting structures duplicate the shape of the original substrate. These hybrid films and porous materials could find uses in several research fields including gas separations and diffusion barriers, biomedical scaffolds, high surface area coatings, and others.}, number={19}, journal={JOURNAL OF PHYSICAL CHEMISTRY B}, author={Gong, Bo and Peng, Qing and Parsons, Gregory N.}, year={2011}, month={May}, pages={5930–5938} } @article{oldham_gong_spagnola_jur_senecal_godfrey_parsons_2011, title={Encapsulation and Chemical Resistance of Electrospun Nylon Nanofibers Coated Using Integrated Atomic and Molecular Layer Deposition}, volume={158}, ISSN={["1945-7111"]}, url={http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=ORCID&SrcApp=OrcidOrg&DestLinkType=FullRecord&DestApp=WOS_CPL&KeyUT=WOS:000293175600039&KeyUID=WOS:000293175600039}, DOI={10.1149/1.3609046}, abstractNote={Nanofibers formed by electrospinning provide very large surface areas which can enhance material performance in filtration and product separation. In this work, we explore atomic layer deposition (ALD) as a means to coat and protect electrospun nylon-6 nanofibers. Exposing nylon to trimethyl aluminum (TMA) during ALD of aluminum oxide results in significant fiber degradation. Protecting fibers with a bilayer of ALD ZnO and an organic-inorganic hybrid polymer by molecular layer deposition maintains the shape of the original nanofibers, but chemical modification is still detected. These coating processes may help enable nanofibers with stable physical properties under chemical exposure.}, number={9}, journal={JOURNAL OF THE ELECTROCHEMICAL SOCIETY}, author={Oldham, Christopher J. and Gong, Bo and Spagnola, Joseph C. and Jur, Jesse S. and Senecal, Kris J. and Godfrey, Thomas A. and Parsons, Gregory N.}, year={2011}, pages={D549–D556} } @article{gong_peng_na_parsons_2011, title={Highly active photocatalytic ZnO nanocrystalline rods supported on polymer fiber mats: Synthesis using atomic layer deposition and hydrothermal crystal growth}, volume={407}, ISSN={["0926-860X"]}, url={http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=ORCID&SrcApp=OrcidOrg&DestLinkType=FullRecord&DestApp=WOS_CPL&KeyUT=WOS:000297234400025&KeyUID=WOS:000297234400025}, DOI={10.1016/j.apcata.2011.08.041}, abstractNote={Photocatalytically active zinc oxide nanocrystalline rods are grown on high surface area polybutylene terephthalate (PBT) polymer fiber mats using low temperature solution based methods, where the oxide crystal nucleation is facilitated using conformal thin films formed by low temperature vapor phase atomic layer deposition (ALD). Scanning electron microscopy (SEM) confirms that highly oriented single crystal ZnO nanorod crystals are directed normal to the starting fiber substrate surface, and the extent of nanocrystal growth within the fiber mat bulk is affected by the overall thickness of the ZnO nucleation layer. The high surface area of the nanocrystal-coated fibers is confirmed by nitrogen adsorption/desorption analysis. An organic dye in aqueous solution in contact with the coated fiber degraded rapidly upon ultraviolet light exposure, allowing quantitative analysis of the photocatalytic properties of fibers with and without nanorod crystals present. The dye degrades nearly twice as fast in contact with the ZnO nanorod crystals compared with samples with only an ALD ZnO layer. Additionally, the catalyst on the polymer fiber mat could be reused without need for a particle recovery step. This combination of ALD and hydrothermal processes could produce high surface area finishes on complex polymer substrates for reusable photocatalytic and other surface-reaction applications.}, number={1-2}, journal={APPLIED CATALYSIS A-GENERAL}, author={Gong, Bo and Peng, Qing and Na, Jeong-Seok and Parsons, Gregory N.}, year={2011}, month={Nov}, pages={211–216} } @article{gong_spagnola_parsons_2012, title={Hydrophilic mechanical buffer layers and stable hydrophilic finishes on polydimethylsiloxane using combined sequential vapor infiltration and atomic/molecular layer deposition}, volume={30}, ISSN={["0734-2101"]}, url={http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=ORCID&SrcApp=OrcidOrg&DestLinkType=FullRecord&DestApp=WOS_CPL&KeyUT=WOS:000298992800056&KeyUID=WOS:000298992800056}, DOI={10.1116/1.3670963}, abstractNote={Polydimethylsiloxane (PDMS) is an important polymer material widely used for microfluidic device fabrication, microcontact lithography, and surface morphology molding. However, the hydrophobic surface limits its functionality. Low temperature atomic layer deposition (ALD) has recently been used to functionalize a wide range of polymer surfaces. In previous research, the authors were able to produce a uniform hydrophilic alumina film coating on PDMS using trimethyl aluminum/water ALD. However, the surface recovered its hydrophobicity after 24–48 h in ambient air or under inert gas storage, which was ascribed to organic species outdiffusion through the ALD layer. This paper reports a stable hydrophilic ALD surface modification on the PDMS. The PDMS substrate was first sequentially exposed to trimethylaluminum and water vapor, allowing the vapors to infiltrate and react to create a mechanical and diffusion buffer layer in the PDMS surface region. This buffer layer helps to nucleate a cohesive hydrophilic ALD or molecular layer deposition (MLD) coating and also helps prevent organic outdiffusion that typically leads to PDMS hydrophobic recovery. The results provide valuable insight into reliable surface energy and mechanical modification of PDMS using vapor-phase precursor/polymer reactions. In addition, molecular layer deposition of “alucone” coatings was also investigated to modify the PDMS surface. The experiment result showed the vapor infiltration and MLD coatings produce a viable and stable hydrophilic surface on PDMS.}, number={1}, journal={JOURNAL OF VACUUM SCIENCE & TECHNOLOGY A}, author={Gong, Bo and Spagnola, Joseph C. and Parsons, Gregory N.}, year={2012}, month={Jan} } @article{peng_gong_parsons_2011, title={Making inert polypropylene fibers chemically responsive by combining atomic layer deposition and vapor phase chemical grafting}, volume={22}, ISSN={["1361-6528"]}, url={http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=ORCID&SrcApp=OrcidOrg&DestLinkType=FullRecord&DestApp=WOS_CPL&KeyUT=WOS:000288209700007&KeyUID=WOS:000288209700007}, DOI={10.1088/0957-4484/22/15/155601}, abstractNote={Uniformly grafting organic reactive molecular species, e.g. –NH2, onto substrates that have three-dimensional complex structures and are chemically inert is challenging. The vapor phase chemical grafting of organic molecules enabled by low temperature metal oxide atomic layer deposition (ALD) is presented as a general and promising solution to functionalize inert matrices with complex morphology, such as nonwoven polypropylene mats, through the controllable self-limited molecular assembly mechanism in a combined ALD and vapor phase chemical grafting process.}, number={15}, journal={NANOTECHNOLOGY}, author={Peng, Qing and Gong, Bo and Parsons, Gregory N.}, year={2011}, month={Apr} } @article{gong_peng_jur_devine_lee_parsons_2011, title={Sequential Vapor Infiltration of Metal Oxides into Sacrificial Polyester Fibers: Shape Replication and Controlled Porosity of Microporous/Mesoporous Oxide Monoliths}, volume={23}, ISSN={0897-4756 1520-5002}, url={http://dx.doi.org/10.1021/cm200694w}, DOI={10.1021/cm200694w}, abstractNote={The preparation of microporous and mesoporous metal oxide materials continues to attract considerable attention, because of their possible use in chemical separations, catalyst support, chemical sensors, optical and electronic devices, energy storage, and solar cells. While many methods are known for the synthesis of porous materials, researchers continue to seek new methods to control pore size distribution and macroscale morphology. In this work, we show that sequential vapor infiltration (SVI) can yield shape-controlled micro/mesoporous materials with tunable pore size, using polyesters as a sacrificial template. The reaction proceeds by exposing polymer fiber templates to a controlled sequence of metal organic and co-reactant vapor exposure cycles in an atomic layer deposition (ALD) reactor. The precursors infuse sequentially and thereby distribute and react uniformly within the polymer, to yield an organic–inorganic hybrid material that retains the physical dimensions of the original polymer template...}, number={15}, journal={Chemistry of Materials}, publisher={American Chemical Society (ACS)}, author={Gong, Bo and Peng, Qing and Jur, Jesse S. and Devine, Christina K. and Lee, Kyoungmi and Parsons, Gregory N.}, year={2011}, month={Aug}, pages={3476–3485} } @article{scarel_na_gong_parsons_2010, title={Phonon Response in the Infrared Region to Thickness of Oxide Films Formed by Atomic Layer Deposition}, volume={64}, ISSN={["1943-3530"]}, DOI={10.1366/000370210790571954}, abstractNote={ Experimental transmission infrared spectra of γ-Al2O3 and ZnO films are collected from heat-treated thin oxide films deposited with uniform thickness on Si(100) using atomic layer deposition. We show that the Berreman thickness, i.e. the upper limit for a linear relationship between oxide film thickness and phonon absorbance in the infrared region in transmission configuration, is a concept that applies to both transverse and longitudinal optical phonons. We find that for aluminum oxide films the Berreman thickness is 125 nm, and we estimate that it is around approximately 435 nm for zinc oxide films. Combining experiment and simulation, we also show that the Berreman thickness is the maximum distance allowed between interfaces for Snell's law and Fresnel's formulas to determine the optical properties in the infrared region and in transmission configuration for a layer system including an oxide film. Below the Berreman thickness, a Taylor series expansion of the absorbance coefficient determines the linear relationship between phonon absorbance and oxide film thickness t, so that as t → 0 absorption Ap ∝ 4πωph t, where ωph indicates optical phonon frequency. Above the Berreman thickness, field boundary conditions at the air/oxide film interface effectively contribute with a single interface in explaining optical phonon absorbance. Preliminary infrared spectra in reflection configuration for γ-Al2O3/Si(100) are discussed, and the obtained data support the conclusions reported for the transmission configuration. }, number={1}, journal={APPLIED SPECTROSCOPY}, author={Scarel, Giovanna and Na, Jeong-Seok and Gong, Bo and Parsons, Gregory N.}, year={2010}, month={Jan}, pages={120–126} } @article{spagnola_gong_arvidson_jur_khan_parsons_2010, title={Surface and sub-surface reactions during low temperature aluminium oxide atomic layer deposition on fiber-forming polymers}, volume={20}, ISSN={["0959-9428"]}, url={http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=ORCID&SrcApp=OrcidOrg&DestLinkType=FullRecord&DestApp=WOS_CPL&KeyUT=WOS:000277563800026&KeyUID=WOS:000277563800026}, DOI={10.1039/c0jm00355g}, abstractNote={Fundamental reaction processes between vapor-phase chemical precursors and high molecular weight polymers are important for polymer coating, encapsulation and surface modification. Using trimethylaluminium and water in an atomic layer deposition (ALD) exposure sequence, reactions between vapor-phase trimethylaluminium and common polymers with different substituents are quantified using in situ infrared transmission analysis. Exposing polypropylene to trimethylaluminium results in reactant uptake with minimal precursor/polymer reaction, but the precursor/water ALD sequence leads to subsurface alumina nucleation. A similar treatment to polyvinyl alcohol and polyamide-6 results in rapid precursor diffusion and significant reaction observed by IR, and the extent of reaction is consistent with results from in situ quartz crystal microgravimetry and transmission electron microscopy. Reacting trimethylaluminium with polyamide-6 leads to methyl group insertion into the amide carbonyl group and interaction with the hydrogen-bonded amine units. Multiple ALD reaction cycles produce film coatings on all polymers studied, but the coating structure depends strongly on the starting polymer composition. For the weakly interacting polypropylene, cross-sectional transmission electron microscopy demonstrates enhanced sub-surface growth at 90 °C as compared to that at 60 °C, while images of coated polyamide-6 fibers showed that growth is not strongly temperature dependent in that range. Micrograph images of polyamide-6 samples exposed to extended TMA doses revealed significant modification of the fiber surface region, demonstrating that the precursor could diffuse and react to depths in excess of 100 nm into the surface of the polymer at 90 °C. Improved understanding of specific precursor/polymer reaction pathways can be important to optimize the performance of conformal inorganic thin film coatings on polymers.}, number={20}, journal={JOURNAL OF MATERIALS CHEMISTRY}, author={Spagnola, Joseph C. and Gong, Bo and Arvidson, Sara A. and Jur, Jesse S. and Khan, Saad A. and Parsons, Gregory N.}, year={2010}, pages={4213–4222} } @article{spagnola_gong_parsons_2010, title={Surface texture and wetting stability of polydimethylsiloxane coated with aluminum oxide at low temperature by atomic layer deposition}, volume={28}, url={http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=ORCID&SrcApp=OrcidOrg&DestLinkType=FullRecord&DestApp=WOS_CPL&KeyUT=WOS:000283745300011&KeyUID=WOS:000283745300011}, DOI={10.1116/1.3488604}, abstractNote={The performance of polydimethylsiloxane (PDMS) elastomer in many of its applications, including surface molding and replication, microcontact lithography, and microfluidic device structures, is strongly influenced by its surface properties. While PDMS polymer is simple to use, the surface hydrophobicity and adsorptive properties of PDMS limit its functionality, for example, in aqueous microfluidic applications. Atomic layer deposition (ALD) is a low temperature vapor phase thin film coating technique that has recently been used to modify and encapsulate a wide range of polymer materials. In this work, the authors investigate reactions that proceed when PDMS polymer films are treated with cyclic gas exposure sequences commonly used to perform aluminum oxide ALD. Film growth is characterized by electron and infrared spectroscopy and by contact angle goniometry for a range of surface treatments and postdeposition air exposure times. The authors find that trimethylaluminum/water ALD can produce a smooth and uniform film coating on PDMS at 25–50 °C and that cracks become visible under optical microscopy for films >100 Å thick. At moderate temperatures, unique buckled surface textures appear in the deposited coating, which are ascribed to substrate thermal expansion effects. Aluminum oxide coatings on native PDMS, as well as on PDMS pretreated with UV ozone or oxygen plasma, show a hydrophilic surface condition immediately after deposition, but the surface becomes more hydrophobic after 24–48 h in ambient air or under inert gas storage, likely due to organic species out-diffusion through defects in the ALD coating. Infrared analysis is also used to identify consistent mechanisms associated with subsurface ALD nucleation on cast PDMS layers. These results provide valuable insight into a means to reliably modify the surface of PDMS using vapor phase precursor/surface reactions.}, number={6}, journal={Journal of Vacuum Science & Technology a}, author={Spagnola, Joseph C. and Gong, Bo and Parsons, Gregory}, year={2010}, pages={1330–1337} } @article{jur_spagnola_lee_gong_peng_parsons_2010, title={Temperature-Dependent Subsurface Growth during Atomic Layer Deposition on Polypropylene and Cellulose Fibers}, volume={26}, ISSN={["0743-7463"]}, url={http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=ORCID&SrcApp=OrcidOrg&DestLinkType=FullRecord&DestApp=WOS_CPL&KeyUT=WOS:000277928100078&KeyUID=WOS:000277928100078}, DOI={10.1021/la904604z}, abstractNote={Nucleation and subsequent growth of aluminum oxide by atomic layer deposition (ALD) on polypropylene fiber substrates is strongly dependent on processing temperature and polymer backbone structure. Deposition on cellulose cotton, which contains ample hydroxyl sites for ALD nucleation and growth on the polymer backbone, readily produces a uniform and conformal coating. However, similar ALD processing on polypropylene, which contains no readily available active sites for growth initiation, results in a graded and intermixed polymer/inorganic interface layer. The structure of the polymer/inorganic layer depends strongly on the process temperature, where lower temperature (60 degrees C) produced a more abrupt transition. Cross-sectional transmission electron microscopy images of polypropylene fibers coated at higher temperature (90 degrees C) show that non-coalesced particles form in the near-surface region of the polymer, and the particles grow in size and coalesce into a film as the number of ALD cycles increases. Quartz crystal microbalance analysis on polypropylene films confirms enhanced mass uptake at higher processing temperatures, and X-ray photoelectron spectroscopy data also confirm heterogeneous mixing between the aluminum oxide and the polypropylene during deposition at higher temperatures. The strong temperature dependence of film nucleation and subsurface growth is ascribed to a relatively large increase in bulk species diffusivity that occurs upon the temperature-driven free volume expansion of the polypropylene. These results provide helpful insight into mechanisms for controlled organic/inorganic thin film and fiber materials integration.}, number={11}, journal={LANGMUIR}, author={Jur, Jesse S. and Spagnola, Joseph C. and Lee, Kyoungmi and Gong, Bo and Peng, Qing and Parsons, Gregory N.}, year={2010}, month={Jun}, pages={8239–8244} } @article{peng_gong_vangundy_parsons_2009, title={"Zincone" Zinc Oxide-Organic Hybrid Polymer Thin Films Formed by Molecular Layer Deposition}, volume={21}, ISSN={["1520-5002"]}, url={http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=ORCID&SrcApp=OrcidOrg&DestLinkType=FullRecord&DestApp=WOS_CPL&KeyUT=WOS:000263891700009&KeyUID=WOS:000263891700009}, DOI={10.1021/cm8020403}, abstractNote={Hybrid organic−inorganic polymer thin films of the form (−O−Zn−O−C2H4−)n have been deposited from diethyl zinc and ethylene glycol using molecular layer deposition (MLD) over a range of substrate temperatures between 100 and 170 °C. Infrared transmission confirms that the films consist of Zn−O and ethylene-oxide units. In analogy with known alucone polymers of the form (−O−Al−O−R−)n, the zinc-based hybrid material is an example of a “zincone” polymer. In situ quartz crystal microbalance analysis indicated that the sequential surface reactions of diethyl zinc and ethylene glycol are sufficiently self-limiting and saturating to enable well-controlled MLD growth. Quantitative analysis of in situ quartz crystal microbalance and film thickness results indicate that ethylene glycol molecules can undergo a “double reaction” where the OH groups on both ends of the diol react with available Zn−C2H5 surface sites to produce a relatively inert bridging alkane. The mass uptake per MLD cycle during Zn−hybrid film depo...}, number={5}, journal={CHEMISTRY OF MATERIALS}, author={Peng, Qing and Gong, Bo and VanGundy, Ryan M. and Parsons, Gregory N.}, year={2009}, month={Mar}, pages={820–830} } @article{hyde_scarel_spagnola_peng_lee_gong_roberts_roth_hanson_devine_et al._2010, title={Atomic Layer Deposition and Abrupt Wetting Transitions on Nonwoven Polypropylene and Woven Cotton Fabrics}, volume={26}, ISSN={["0743-7463"]}, url={http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=ORCID&SrcApp=OrcidOrg&DestLinkType=FullRecord&DestApp=WOS_CPL&KeyUT=WOS:000274342200056&KeyUID=WOS:000274342200056}, DOI={10.1021/la902830d}, abstractNote={Atomic layer deposition (ALD) of aluminum oxide on nonwoven polypropylene and woven cotton fabric materials can be used to transform and control fiber surface wetting properties. Infrared analysis shows that ALD can produce a uniform coating throughout the nonwoven polypropylene fiber matrix, and the amount of coating can be controlled by the number of ALD cycles. Upon coating by ALD aluminum oxide, nonwetting hydrophobic polypropylene fibers transition to either a metastable hydrophobic or a fully wetting hydrophilic state, consistent with well-known Cassie-Baxter and Wenzel models of surface wetting of roughened surfaces. The observed nonwetting/wetting transition depends on ALD process variables such as the number of ALD coating cycles and deposition temperature. Cotton fabrics coated with ALD aluminum oxide at moderate temperatures were also observed to transition from a natural wetting state to a metastable hydrophobic state and back to wetting depending on the number of ALD cycles. The transitions on cotton appear to be less sensitive to deposition temperature. The results provide insight into the effect of ALD film growth mechanisms on hydrophobic and hydrophilic polymers and fibrous structures. The ability to adjust and control surface energy, surface reactivity, and wettability of polymer and natural fiber systems using atomic layer deposition may enable a wide range of new applications for functional fiber-based systems.}, number={4}, journal={LANGMUIR}, author={Hyde, G. Kevin and Scarel, Giovanna and Spagnola, Joseph C. and Peng, Qing and Lee, Kyoungmi and Gong, Bo and Roberts, Kim G. and Roth, Kelly M. and Hanson, Christopher A. and Devine, Christina K. and et al.}, year={2010}, month={Feb}, pages={2550–2558} } @article{na_gong_scarel_parsons_2009, title={Surface Polarity Shielding and Hierarchical ZnO Nano-Architectures Produced Using Sequential Hydrothermal Crystal Synthesis and Thin Film Atomic Layer Deposition}, volume={3}, ISSN={["1936-086X"]}, url={http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=ORCID&SrcApp=OrcidOrg&DestLinkType=FullRecord&DestApp=WOS_CPL&KeyUT=WOS:000271106100043&KeyUID=WOS:000271106100043}, DOI={10.1021/nn900702e}, abstractNote={Three-dimensional nanoscale constructs are finding applications in many emerging fields, including energy generation and storage, advanced water and air purification, and filtration strategies, as well as photocatalytic and biochemical separation systems. Progress in these important technologies will benefit from improved understanding of fundamental principles underlying nanostructure integration and bottom-up growth processes. While previous work has identified hydrothermal synthesis conditions to produce nanoscale ZnO rods, sheets, and plates, strategies to systematically integrate these elements into more complex nano-architectures are not previously described. This article illustrates that amorphous nanoscale coatings formed by atomic layer deposition (ALD) are a viable means to modulate and screen the surface polarity of ZnO crystal faces and thereby regulate the growth morphology during successive hydrothermal nanocrystal synthesis. Using this new strategy, this work demonstrates direct integration and sequential assembly of nanocrystalline rods and sheets to produce complex three-dimensional geometric forms, where structure evolution is achieved by modifying the surface growth condition, keeping the hydrothermal growth chemistry unchanged. Therefore, rational planning of seed layer and feature spacing geometries may allow researchers to engineer, at the nanoscale, complex three-dimensional crystalline and semicrystalline constructs for a wide range of future applications.}, number={10}, journal={ACS NANO}, author={Na, Jeong-Seok and Gong, Bo and Scarel, Giovanna and Parsons, Gregory N.}, year={2009}, month={Oct}, pages={3191–3199} }