Vapor Phase Infiltration Research Articles

Atomic Layer Processing (ALP): Ubi es et Quo Vadis?

AbstractAtomic Layer Processing (ALP) techniques have transformed materials engineering by enabling atomic/molecular‐level control over composition, fidelity in structure replication, and properties. Tracing its origins to pioneering molecular layering and atomic layer deposition work in the mid‐20th century, this multifaceted field has remarkably diversified to include molecular layer deposition (MLD), atomic layer etching (ALE), area‐selective deposition (ASD), and vapor‐phase infiltration (VPI) processes. ALP is making great impacts across diverse disciplines – facilitating semiconductor miniaturization through ultrathin dielectric films, improving battery materials and engineering catalysts for energy applications, creating bioactive surfaces for advanced biomaterials, and promoting sustainable membranes for environmental remediation. As ALP techniques continue evolving through integration with additive manufacturing, machine learning, and in situ diagnostics, new frontiers in materials design are emerging, driven by the growing focus on environmental considerations like renewable precursors, energy‐efficient processes, and waste minimization. This perspective article examines ALP's historical development, highlights current state‐of‐the‐art applications across selected fields, and provides insights into the anticipated future trajectory, emerging application domains, and the pivotal role of academic‐industry‐research laboratory collaborations in catalyzing ALP innovations and facilitating its widespread adoption as a transformative manufacturing platform.

(Invited) Advance in Single-Wall Carbon Nanotubes Filling

Single-wall carbon nanotubes (SWCNTs) are renowned for their outstanding charge carrier mobility, optical, thermal, and mechanical properties. Combining these characteristics with their nanometer-scale diameter renders them highly promising for developing (opto)-electronic devices, where the challenge lies in achieving miniaturization without compromising performance. In addition to their intrinsic characteristics, SWCNTs feature a hollow core that can be filled with various molecules1, resulting in unique one-dimensional hybrids that integrate the properties of the nanotube with those of the encapsulated molecule. This study emphasizes recent advancements, particularly the extensive chirality-sorting2 of these hybrids and a novel methodology utilizing vapor phase infiltration and tailored synthesis strategies to create new fillers. These approaches aim to enhance control over the filling process for finer tuning of the SWCNT doping level or their photosensitization/reactivity capabilities under visible light.

Numerical simulation and experimental validation of ICVI-C/C reaction process by methane/propane gas mixture source

This study aimed to optimize the preparation of carbon/carbon (C/C) composites by developing and validating a computational model for three-dimensional (3D) transient densification through an isothermal chemical vapor-phase infiltration (ICVI) process using a methane/propane mixture. Simplified multistep parallel reaction kinetics were employed to simulate the pore evolution using a two-dimensional representative volume element model and a 3D stochastic fiber model. The permeability, flow modeling, and material transfer behaviors were calculated using the Ergun, Brinkman, and mixing diffusion equations. The density was calculated to be 1.294 g/cm3 after 50 h of deposition with specific flow rates and temperatures. The experimental densities were lower than those predicted with an increased propane flow, highlighting the complex reaction kinetics. The numerical simulation results exhibited strong agreement with the experimental results at 1328 K, achieving a correlation of up to 5.918. This study provides a robust theoretical and experimental basis for optimizing the structure and process control of C/C composites.

The Development and Atomic Structure of Zinc Oxide Crystals Grown within Polymers from Vapor Phase Precursors.

Sequential infiltration synthesis (SIS), also known as vapor phase infiltration (VPI), is a quickly expanding technique that allows growth of inorganic materials within polymers from vapor phase precursors. With an increasing materials library, which encompasses numerous organometallic precursors and polymer chemistries, and an expanding application space, the importance of understanding the mechanisms that govern SIS growth is ever increasing. In this work, we studied the growth of polycrystalline ZnO clusters and particles in three representative polymers: poly(methyl methacrylate), SU-8, and polymethacrolein using vapor phase diethyl zinc and water. Utilizing two atomic resolution methods, high-resolution scanning transmission electron microscopy and synchrotron X-ray absorption spectroscopy, we probed the evolution of ZnO nanocrystals size and crystallinity level inside the polymers with advancing cycles─from early nucleation and growth after a single cycle, through the formation of nanometric particles within the films, and to the coalescence of the particles upon polymer removal and thermal treatment. Through in situ Fourier transform infrared spectroscopy and microgravimetry, we highlight the important role of water molecules throughout the process and the polymers' hygroscopic level that leads to the observed differences in growth patterns between the polymers, in terms of particle size, dispersity, and the evolution of crystalline order. These insights expand our understanding of crystalline materials growth within polymers and enable rational design of hybrid materials and polymer-templated inorganic nanostructures.

Vapor Phase Infiltration of Titanium Oxide into P3HT to Create Organic-Inorganic Hybrid Photocatalysts.

Herein, we report for the first time the use of vapor phase infiltration (VPI) to infuse conducting polymers with inorganic metal oxide clusters that together form a photocatalytic material. While vapor infiltration has previously been used to electrically dope conjugated polymers, this is the first time, to our knowledge, that the resultant hybrid material has been demonstrated to have photocatalytic properties. The system studied is poly(3-hexylthiophene-2,5-diyl) (P3HT) vapor infiltrated with TiCl4 and H2O to create P3HT-TiOx organic-inorganic hybrid photocatalytic materials. X-ray photoelectron spectroscopy analysis shows that P3HT-TiOx VPI films consist of a partially oxidized P3HT matrix, and the infiltrated titanium inorganic is in a 4+ oxidation state with mostly oxide coordination. Upon visible light illumination, these P3HT-TiOx hybrids degrade methylene blue dye molecules. The P3HT-TiOx hybrids are 4.6× more photocatalytically active than either the P3HT or TiO2 individually or when sequentially deposited (e.g., P3HT on TiO2). On a per surface area basis, these hybrid photocatalysts are comparable or better than other best in class polymer semiconductor photocatalysts. VPI of TiCl4 + H2O into P3HT makes a unique hybrid structure and idealized photocatalyst architecture by creating nanoscale TiOx clusters concentrated toward the surface achieving extremely high catalytic rates. The mechanism for this enhanced photocatalytic rate is understood using photoluminescence spectroscopy, which shows significant quenching of excitons in P3HT-TiOx as compared to neat P3HT, indicating that P3HT acts as a photosensitizer for the TiOx catalyst sites in the hybrid material. This work introduces a new approach to designing and synthesizing organic-inorganic hybrid photocatalytic materials, with expansive opportunities for further exploration and optimization.

Efficiently tuning the electrical performance of PBTTT-C14 thin film via in situ controllable multiple precursors (Al2O3:ZnO) vapor phase infiltration

Conjugated polymer-based organic/inorganic hybrid materials become the current research frontier and show great potential to integrate flexible polymers and rigid solid materials, which have been widely used in the field of various flexible electronics and optical devices. In this study, based on the multiple vapor phase infiltration (VPI) process, various precursor molecules (diethylzinc DEZ, trimethylaluminum TMA, H2O) are applied for the in situ modification of PBTTT-C14 films. The conductivity of the PBTTT-C14/Al2O3:ZnO (AZO) film is significantly enhanced, and the maximum value of conductivity is 1.16 S cm−1, which is eight orders of magnitude higher than the undoped PBTTT-C14 thin film. Here, the change of morphologies and crystalline states are analyzed via SEM, AFM, and XRD. And the chemical changes during the VPI process of PBTTT-C14 are characterized through Raman, XPS, and UV–vis. During the AZO VPI process, the formation of new ZnS matrix in the polymer subsurface can generate new additional electron conduction pathways through the crosslinking of polymer chains with inorganic materials, and the addition of Al2O3 can bring about the increase of average grain size of ZnO crystals, which is also benefit to the conductivity increase of PBTTT-C14 thin film. Generally, the synergistic effect between the inorganic and polymer constituents results in the significantly enhancement of the conductivity of PBTTT-C14/AZO thin films.

Preparation of stable multilayer PDMS composite pervaporation membrane incorporated with in-situ transformed metal organic frameworks for enhanced butanol recovery

In this study, stable and non-defective multilayer polydimethylsiloxane (PDMS) composite pervaporation mixed matrix membranes incorporated with in-situ transformed metal organic frameworks was successfully synthesized via ligand vapor phase infiltration and spin-coating. Metal zinc sources were uniformly distributed in PDMS which were in-situ transformed into homogeneous zeolitic imidazolate framework-8 (ZIF-8) nanoparticles, effectively alleviating the aggregation of ZIF-8. Thermal cross-linking of PDMS and the formation of MOFs occurred simultaneously, omitting the complicated preparation and re-dispersion steps of MOF nanoparticles. MOF nanoparticles and PDMS formed a more stabilized composite structure by in-situ transformation, in which PDMS and metal of MOFs can interact with the -Si-O- of silane coupling groups on membrane surface to construct solid multilayer composite membrane, ensuring long-term stability. Moreover, with the aid of hydrophobic interlayer, polymer infiltration into channels of substrate was restricted and casting solution spread out smoothly, facilitating the formation of defect-free PDMS selective layer. Various techniques including Attenuated Total Reflection-Fourier Transform Infrared Spectrometer, Field Emission Scanning Electron Microscopy, Atomic Force Microscope and X-ray Diffraction were applied to explore the morphology, composition and structure of nanoparticles and membranes, and pervaporation tests were taken to investigate the behavior of hydrophobic polymer-based multilayer membranes. For the recovery of low concentration n-butanol, the prepared non-defective multilayer TAO/ZIF-8/K-PDMS composite membrane displayed excellently total permeate flux of 2890 g m−2 h−1 with competitive separation factor of 40.3.

Volume compensating materials after vapor phase infiltration: effect of different butyl isomers of polymer side-chains on high process temperature durability

Vapor phase infiltration is a facile process that adds metallic features to organic polymer patterns. Generally, volume expansion in typical polymers such as poly(methyl methacrylate) (PMMA) is observed after metal infiltration, which limits the application of this technique in nanofabrication processes. In this study, poly(sec-butyl methacrylate) P(sBuMA) and poly(iso-butyl methacrylate) P(iBuMA) with leaving groups were selected as alternatives for PMMA and poly(tert-butyl methacrylate) P(tBuMA), and their aluminum (Al) infiltration behaviors were investigated. Notably, Al species infiltrated into P(sBuMA) and P(iBuMA) at 200 °C, whereas no Al infiltration was observed at 100 °C. Volume shrinkage was observed for both polymers after infiltration. This shows that the volume change in the base material after metal infiltration can be minimized by combining a conventional volume-expanding polymer, such as PMMA, with volume-shrinking polymers with high process temperature durability.

A triple-crosslinking strategy for high-performance regenerated cellulose fibers derived from waste cotton textiles

Regenerated cellulose fibers has attracted increasing attention for high-grade textile raw materials and industrial textiles, but the low mechanical property caused by differences in regenerated raw materials and production levels limits its commercial application in the product diversity. Herein, we proposed a novel triple-crosslinking strategy by coupling with hydrogen bonds, chemical crosslinking, and internal mineralization from multiple pulsed vapor phase infiltration (MPI) to improve the mechanical performance of regenerated cellulose fibers. A binary solvent composed of ionic liquid (IL) and dimethyl sulfoxide (DMSO) is used to dissolve waste cotton textile and then wet spinning. Dual-crosslinking is firstly achieved by coupling glutaraldehyde (GA) and cellulose reaction. Subsequently, a metal oxide is intentionally infiltrated into inner cellulosic through MPI technology to form a third form of crosslinking, accompanied by the ultra-thin metal oxide nano-layer onto the surface of regenerated cellulose fibers. Results showed that the triple-crosslinking strategy has increased the tensile stress of the fiber by 43.57 % to 287.03 MPa. In all, triple-crosslinking strategy provides a theoretical basis and technical approach for the reinforcement of weak fibers in waste cotton recycling, which is expected to accelerate the development of the waste textile recycling industry and promote of the added-value of regenerated products.

Understanding Organic Photovoltaic Materials Using Simple Thermal Analysis Methodologies.

Large strides have been made in designing an ever-increasing set of modern organic materials of high functionality and thus, often, of high complexity, including semiconducting polymers, organic ferroelectrics, light-emitting small molecules, and beyond. Here, we review how broadly applied thermal analysis methodologies, especially differential scanning calorimetry, can be utilized to provide unique information on the assembly and solid-state structure of this extensive class of materials, as well as the phase behavior of intrinsically intricate multicomponent systems. Indeed, highly relevant insights can be gained that are useful, e.g., for further materials-discovery activities and the establishment of reliable processing protocols, in particular if combined with X-ray diffraction techniques, spectroscopic tools, and scanning electron microscopy enabled by vapor-phase infiltration staining. We, hence, illustrate that insights far richer than simple melting point- and glass-transition identification can be obtained with differential scanning calorimetry, rendering it a critical methodology to understand complex matter, including functional macromolecules and blends.

Dealkylation of Poly(methyl methacrylate) by TiCl4 Vapor Phase Infiltration (VPI) and the Resulting Chemical and Thermophysical Properties of the Hybrid Material.

This study examines the chemical reaction pathways for vapor phase infiltration (VPI) of TiCl4 into poly(methyl methacrylate) (PMMA). VPI is a processing method that transforms organic polymers into organic-inorganic hybrid materials with new properties of interest for microelectronic patterning, technical textiles, and chemical separations. Understanding the fundamental chemical mechanisms of the VPI process is essential for establishing approaches to design the chemical structure and properties of these hybrid materials. While prior work has suggested that TiCl4 infiltration into PMMA does not disrupt the polymer's carbonyl bond, a clear reaction mechanism has yet to be proposed. Here, we present a detailed X-ray photoelectron spectroscopy study that presents evidence for a concerted reaction mechanism that involves TiCl4 coordinating with the PMMA's ester group to dealkylate the methyl side group, creating a chloromethane byproduct and primary chemical bonds between the organic and inorganic components of the hybrid material. Additional spectroscopy, quartz crystal microbalance gravimetry, and thermophysical and chemical property measurements of this material, including solubility studies and thermal expansion measurements, provide further evidence for this chemical reaction pathway and the subsequent creation of inorganic cross-links that network these TiOx-PMMA hybrid materials.

Effects of alumina priming on the electrical properties of ZnO nanostructures derived from vapor-phase infiltration into self-assembled block copolymer thin films

Alumina priming, typically used for vapor-phase infiltration (VPI) of weakly reactive precursors, increases both ZnO VPI fidelity and its electrical conductivity, as demonstrated in the ZnO nanostructures derived from self-assembled block copolymers.

ZnO vapor phase infiltration into photo-patternable polyacrylate networks for the microfabrication of hybrid organic–inorganic structures

The incorporation of inorganics into a patterned polymer can generate many new interesting properties in microfabricated structures.

Synthesis of Lewis Acid Sites in SBA-15 and Amorphous Silica Using Vapor Phase Infiltration of Zr and Sn

Synthesis of Lewis Acid Sites in SBA-15 and Amorphous Silica Using Vapor Phase Infiltration of Zr and Sn

Engineering organic solvent reverse osmosis in hybrid AlOxHy / polymer of intrinsic microporosity 1 (PIM-1) membranes using vapor phase infiltration

A solvent-free post-treatment process known as vapor phase infiltration (VPI) is used to engineer the organic solvent reverse osmosis (OSRO) performance of polymer of intrinsic microporosity 1 (PIM-1) membranes via infiltration of trimethylaluminum (TMA) metal-organic vapor. The infiltration of inorganic aluminum constituents hybridizes the pure polymer PIM-1 into an organic-inorganic material (AlOxHy/PIM-1) with enhanced chemical stability. A homogenous distribution of inorganic loading in PIM-1 is achieved due to the reaction-limited infiltration mechanism, and the OSRO performance is enhanced as a result. OSRO separations of ethanol/isooctane mixtures using these membranes are shown to be capable of breaking the azeotropic composition with a separation factor for ethanol over isooctane greater than 5 and an ethanol permeance of 0.1 Lm–2h–1bar–1. Thus, these organic-inorganic hybrid membranes created via VPI show promise as an alternative method for separating azeotropic liquid mixtures.

Limiting reagent conditions to control inorganic loading in AlOx–PET hybrid fabrics created through vapor-phase infiltration

In this work, the vapor-phase infiltration (VPI) of polyethylene terephthalate (PET) fabrics with trimethylaluminum (TMA) and coreaction with water vapor is explored as a function of limiting TMA reagent conditions versus excess TMA reagent conditions at two infiltration temperatures. TMA is found to sorb rapidly into PET fibers, with a significant pressure drop occurring within seconds of TMA exposure. When large quantities of polymer are placed within the chamber, minimal residual precursor remains at the end of the pressure drop. This rapid and complete sorption facilitates the control of inorganic loading by purposely delivering a limited quantity of the TMA reagent. The inorganic loading for this system scales linearly with a Precursor:C=O molar ratio of up to 0.35 at 140 °C and 0.5 at 80 °C. After this point, inorganic loading is constant irrespective of the amount of additional TMA reagent supplied. The SEM analysis of pyrolyzed hybrids indicates that this is likely due to the formation of an impermeable layer to subsequent infiltration as the core of the fibers remains uninfiltrated. The Precursor:C=O molar ratio in the subsaturation regime is found to tune the hybrid fabric morphology and material properties such as the optical properties of the fabric. Overall, this work demonstrates how a reagent-limited processing route can control the inorganic loading in VPI synthesized hybrid materials in a simpler manner than trying to control kinetics-driven methods.

Understanding the multilevel phenomena that enables inorganic atomic layer deposition to provide barrier coatings for highly-porous 3-D printed plastic in vacuums

The potential of 3-D printing polymers to achieve low-weight space flight hardware has seen increasing interest. Additionally, robust 3-D printed polymer vacuum equipment would provide highly attractive low-cost alternatives to conventional industrial-scale tools for the scientific community. Inorganic barrier coatings of plastic parts can be used to minimize outgassing and damage to polymers from extreme vacuum environments. Among different coating technologies in this area of research, atomic layer deposition (ALD) has shown the most promise. Nevertheless, the exact formation morphology of ALD coatings on 3-D printed polymers under vacuum are not yet well understood, which hinders use of 3-D printed polymers in vacuum environments. In this study, the film formation mechanisms of ALD alumina on porous 3-D printed polymers are investigated via SEM, EDS, XRD, ATR-FTIR, and XPS. ALD alumina is deposited on 3-D printed pigmented and un-pigmented acrylonitrile butadiene styrene, polycarbonate, commercially available polypropylene, and pure polypropylene. The results reveal that the formation of the ALD barrier layer, its thickness, and diffusion of ALD precursor materials into the polymer substrate is a multi-scale phenomenon, and that substrate porosity and polymer functionality both dominate film formation behavior. Additionally, this study demonstrates that during ALD processes on 3-D printed polymers a vapor phase infiltration (VPI) growth mode also occurs, especially where porosity is present.

Unraveling the ultrahigh modulus of resilience of Core-Shell SU-8 nanocomposite nanopillars fabricated by vapor-phase infiltration

Modulus of resilience, the maximum strain energy density that can be stored in an elastically deformed solid, is an important mechanical property for developing artificial muscles in robotics, soft electronics panels, and micro-/nano-electromechanical actuators. In this study, core–shell SU-8 nanocomposites were fabricated via vapor-phase infiltration of nanoscale amorphous aluminum oxides into SU-8 nanopillars and performed transmission electron microscopy, nanomechanical testing, analytical modeling, and atomistic simulations to gain a fundamental insight into the ultrahigh modulus of resilience much higher than that of most high-strength materials. This study shows that the ultrahigh modulus of resilience results from: the low aspect ratio of amorphous aluminum oxide nano-particulates; the particulate size thicker than the free volume size; and the thin aluminum oxide interconnecting links within nano-particulates. These unique microstructural features produce the unusual combination of low specific Young’s modulus (E), 4 MPa/(kg/m3), and high specific yield strength (σy), 0.2 MPa/(kg/m3), leading to the specific modulus of resilience, 5.21 ± 0.39 kJ/kg (σy2/(2E)) about ten times higher than materials with the similar yield strength. This study demonstrates that vapor-phase infiltration is an excellent fabrication method to produce a polymer nanocomposite that can absorb and release a large amount of elastic strain energy.

Incorporating Binary Metal Oxides in Poly(ethylene oxide)-Based Solid Electrolytes by Vapor Phase Infiltration

Vapor phase infiltration (VPI) derived from atomic layer deposition (ALD) enables inorganic materials to nucleate and grow within the free volume of polymers, which has shown promising prospects in the field of composite solid polymer electrolytes (CSPEs). However, there are only a few types of metal oxides that can be incorporated into the polymer matrix by VPI, let alone binary metal oxides, due to the limited knowledge of the VPI synthesis process. To combine the merits of different metal oxides, we investigate the VPI method to prepare ZnO-Al2O3 composites in poly(ethylene oxide) (PEO). When the introducing order is Al2O3/ZnO (AZO), due to the extremely high reactivity of trimethyl aluminum (TMA) with PEO, VPI-Al2O3 will accumulate near the surface of PEO. The surface Al2O3 layer inhibits the further diffusion of the diethyl zinc (DEZ) into the PEO matrix, leading to weak polymer-filler interactions and limited improvement of the Li+ conduction. In the incorporation order of ZnO/Al2O3 (ZAO), the moderate reactivity of DEZ renders the uniform distribution of VPI-ZnO within PEO, and the following TMA can both react with PEO and VPI-ZnO particles near the surface of PEO, which not only preserves the interactions between VPI-ZnO and PEO but also better inhibits the growth of lithium dendrites. The incorporation order plays a crucial role in the morphology and composition of binary metal oxides synthesized by VPI.

Vapor Phase Infiltration Improves Thermal Stability of Organic Layers in Perovskite Solar Cells

Despite the rapid increase in power conversion efficiency (PCE) of perovskite solar cells (PSCs) over the past decade, stability remains a major roadblock to commercialization. This work shows vapor phase infiltration (VPI) as a tool to create hybrid organic–inorganic layers that improve the stability of organic charge transport layers, such as hole-selective spiro-OMeTAD in PSCs and in other organic electronic devices. Using X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), and grazing incident wide-angle X-ray scattering (GIWAXS), we identify that infiltration of TiOx via VPI hinders the crystallization of the spiro-OMeTAD layer by likely preventing the π–π stacking of the molecules. Infiltrated PSCs retained more than 80% of their original efficiency after an operando stability test of 200 h at 75 °C, double the efficiency retained by devices without infiltration, in which the efficiency rapidly decreases in the first 50 h. This work provides a blueprint for using VPI to stabilize organic charge transport layers via prevention of π–π stacking leading to deleterious crystallization that shortens device lifetimes.