Xiaoxue Wang

CVD Polymers for Devices and Device Fabrication

Chemical vapor deposition (CVD) polymerization directly synthesizes organic thin films on a substrate from vapor phase reactants. Dielectric, semiconducting, electrically conducting, and ionically conducting CVD polymers have all been readily integrated into devices. The absence of solvent in the CVD process enables the growth of high‐purity layers and avoids the potential of dewetting phenomena, which lead to pinhole defects. By limiting contaminants and defects, ultrathin (<10 nm) CVD polymeric device layers have been fabricated in multiple laboratories. The CVD method is particularly suitable for synthesizing insoluble conductive polymers, layers with high densities of organic functional groups, and robust crosslinked networks. Additionally, CVD polymers are prized for the ability to conformally cover rough surfaces, like those of paper and textile substrates, as well as the complex geometries of micro‐ and nanostructured devices. By employing low processing temperatures, CVD polymerization avoids damaging substrates and underlying device layers. This report discusses the mechanisms of the major CVD polymerization techniques and the recent progress of their applications in devices and device fabrication, with emphasis on initiated CVD (iCVD) and oxidative CVD (oCVD) polymerization.

Functionalizable and electrically conductive thin films formed by oxidative chemical vapor deposition (oCVD) from mixtures of 3-thiopheneethanol (3TE) and ethylene dioxythiophene (EDOT)

Mixtures of 3-thiopheneethanol (3TE) and 3,4-ethylenedioxythiophene (EDOT) were used as the reactants for oxidative chemical vapor deposition (oCVD). Monomer (3TE : EDOT) feed ratios of (3 : 1), (3 : 2), (3 : 3), (2 : 3), and (1 : 3) were employed to obtain conductive polymer thin films with varying densities of hydroxyl pendant groups. The incorporation of both 3TE and EDOT units into the deposited films was confirmed by a combination of high resolution mass spectrometry, UV-visible-Near Infrared (UV-vis-NIR), and Fourier transform infrared (FTIR) spectroscopy, yielding conductive and –OH functionalized thin films. Theoretical analysis of the initial formation of dimers was studied by using density functional theory (DFT). The calculation predicts that the reaction of 3TE and EDOT is kinetically favored over the combination of two 3TE monomers. The π–π* transition observed at 425 nm in the UV-vis-NIR spectra of the 3TE polymerized film red shifts with increasing EDOT incorporation. This transition is observed at 523 nm in the film prepared using (1 : 3) a monomer feed ratio.

Small-Area, Resistive Volatile Organic Compound (VOC) Sensors Using Metal–Polymer Hybrid Film Based on Oxidative Chemical Vapor Deposition (oCVD)

We report a novel room temperature methanol sensor comprised of gold nanoparticles covalently attached to the surface of conducting copolymer films. The copolymer films are synthesized by oxidative chemical vapor deposition (oCVD), allowing substrate-independent deposition, good polymer conductivity and stability. Two different oCVD copolymers are examined: poly(3,4-ethylenedioxythiophene-co-thiophene-3-aceticacid)[poly(EDOT-co-TAA)] and poly(3,4-ehylenedioxythiophene-co-thiophene-3-ethanol)[poly(EDOT-co-3-TE)]. Covalent attachment of gold nanoparticles to the functional groups of the oCVD films results in a hybrid system with efficient sensing response to methanol. The response of the poly(EDOT-co-TAA)/Au devices is found to be superior to that of the other copolymer, confirming the importance of the linker molecules (4-aminothiophenol) in the sensing behavior. Selectivity of the sensor to methanol over n-pentane, acetone, and toluene is demonstrated. Direct fabrication on a printed circuit board (PCB) is achieved, resulting in an improved electrical contact of the organic resistor to the metal circuitry and thus enhanced sensing properties. The simplicity and low fabrication cost of the resistive element, mild working temperature, together with its compatibility with PCB substrates pave the way for its straightforward integration into electronic devices, such as wireless sensor networks.

Recent progress on submicron gas-selective polymeric membranes

Polymeric membranes have been applied in industrial gas separations for decades. Competing technologies, such as cryogenic distillation and sorption processes, require the gases to be either condensed or thermally regenerated from the sorbents. In contrast, membrane gas separation does not involve phase transition, representing the potential for a more energy efficient and eco-friendly separation process. However, the overall energy consumption by membrane gas separation is highly dependent on the quality of the membrane employed for the separation process. With the goal of reducing the energy input needed for creating the transmembrane pressure difference, numerous bulk polymers have been investigated. However, less effort has been devoted to processing polymers into ultrathin membranes and investigating their gas permeation properties, which can be quite different from their bulk counterparts. This review summarizes recent advances in fabricating ultrathin gas-selective polymeric membranes. Several classes of ultrathin polymeric membranes are highlighted: microporous polymers, facilitated transport polymeric membranes, Langmuir–Blodgett (LB) films and Layer-by-Layer (LbL) deposited polyelectrolyte multilayers (PEMs), polyamides and other commercial polymers. The application of gas-selective polymeric membranes beyond gas separation is also included as a meaningful extension to this review.

Water‐Assisted Vapor Deposition of PEDOT Thin Film

The synthesis and characterization of poly(3,4-ethylenedioxythiophene) (PEDOT) using water-assisted vapor phase polymerization (VPP) and oxidative chemical vapor deposition (oCVD) are reported. For the VPP PEDOT, the oxidant, FeCl3 , is sublimated onto the substrate from a heated crucible in the reactor chamber and subsequently exposed to 3,4-ethylenedioxythiophene (EDOT) monomer and water vapor in the same reactor. The oCVD PEDOT was produced by introducing the oxidant, EDOT monomer, and water vapor simultaneously to the reactor. The enhancement of doping and crystallinity is observed in the water-assisted oCVD thin films. The high doping level observed at UV-vis-NIR spectra for the oCVD PEDOT, suggests that water acts as a solubilizing agent for oxidant and its byproducts. Although the VPP produced PEDOT thin films are fully amorphous, their conductivities are comparable with that of the oCVD produced ones.

Molecular engineered conjugated polymer with high thermal conductivity

Molecular engineering of intra- and interchain interactions transforms polymers into good heat conductors. Traditional polymers are both electrically and thermally insulating. The development of electrically conductive polymers has led to novel applications such as flexible displays, solar cells, and wearable biosensors. As in the case of electrically conductive polymers, the development of polymers with high thermal conductivity would open up a range of applications in next-generation electronic, optoelectronic, and energy devices. Current research has so far been limited to engineering polymers either by strong intramolecular interactions, which enable efficient phonon transport along the polymer chains, or by strong intermolecular interactions, which enable efficient phonon transport between the polymer chains. However, it has not been possible until now to engineer both interactions simultaneously. We report the first realization of high thermal conductivity in the thin film of a conjugated polymer, poly(3-hexylthiophene), via bottom-up oxidative chemical vapor deposition (oCVD), taking advantage of both strong C=C covalent bonding along the extended polymer chain and strong π-π stacking noncovalent interactions between chains. We confirm the presence of both types of interactions by systematic structural characterization, achieving a near–room temperature thermal conductivity of 2.2 W/m·K, which is 10 times higher than that of conventional polymers. With the solvent-free oCVD technique, it is now possible to grow polymer films conformally on a variety of substrates as lightweight, flexible heat conductors that are also electrically insulating and resistant to corrosion.

High electrical conductivity and carrier mobility in oCVD PEDOT thin films by engineered crystallization and acid treatment

We present a structural engineered air-stable conducting polymer with high electrical conductivity and carrier mobility. Air-stable, lightweight, and electrically conductive polymers are highly desired as the electrodes for next-generation electronic devices. However, the low electrical conductivity and low carrier mobility of polymers are the key bottlenecks that limit their adoption. We demonstrate that the key to addressing these limitations is to molecularly engineer the crystallization and morphology of polymers. We use oxidative chemical vapor deposition (oCVD) and hydrobromic acid treatment as an effective tool to achieve such engineering for conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT). We demonstrate PEDOT thin films with a record-high electrical conductivity of 6259 S/cm and a remarkably high carrier mobility of 18.45 cm2 V−1 s−1 by inducing a crystallite-configuration transition using oCVD. Subsequent theoretical modeling reveals a metallic nature and an effective reduction of the carrier transport energy barrier between crystallized domains in these thin films. To validate this metallic nature, we successfully fabricate PEDOT-Si Schottky diode arrays operating at 13.56 MHz for radio frequency identification (RFID) readers, demonstrating wafer-scale fabrication compatible with conventional complementary metal-oxide semiconductor (CMOS) technology. The oCVD PEDOT thin films with ultrahigh electrical conductivity and high carrier mobility show great promise for novel high-speed organic electronics with low energy consumption and better charge carrier transport.

Room Temperature Sensing Achieved by GaAs Nanowires and oCVD Polymer Coating

Novel structures comprised of GaAs nanowire arrays conformally coated with conducting polymers (poly(3,4-ethylenedioxythiophene) (PEDOT) or poly(3,4-ethylenedioxythiophene-co-3-thiophene acetic acid) display both sensitivity and selectivity to a variety of volatile organic chemicals. A key feature is room temperature operation, so that neither a heater nor the power it would consume, is required. It is a distinct difference from traditional metal oxide sensors, which typically require elevated operational temperature. The GaAs nanowires are prepared directly via self-seeded metal-organic chemical deposition, and conducting polymers are deposited on GaAs nanowires using oxidative chemical vapor deposition (oCVD). The range of thickness for the oCVD layer is between 100 and 200 nm, which is controlled by changing the deposition time. X-ray diffraction analysis indicates an edge-on alignment of the crystalline structure of the PEDOT coating layer on GaAs nanowires. In addition, the positive correlation between the improvement of sensitivity and the increasing nanowire density is demonstrated. Furthermore, the effect of different oCVD coating materials is studied. The sensing mechanism is also discussed with studies considering both nanowire density and polymer types. Overall, the novel structure exhibits good sensitivity and selectivity in gas sensing, and provides a promising platform for future sensor design.