Gradient Polymer Nanofoams for Encrypted Recording of Chemical Events.

We have fabricated gradient-grafted nanofoam films that are able to record the presence of volatile chemical compounds in an offline regime. In essence, the nanofoam film (100-300 nm thick) is anchored to a surface cross-linked polymer network in a metastable extended configuration that can relax back to a certain degree upon exposure to a chemical vapor. The level of the chain relaxation is associated with thermodynamic affinity between the polymer chains and the volatile compounds. In our design, the chemical composition of the nanofoam film is not uniform; therefore, the film possesses a gradually changing local affinity to a vapor along the surface. Upon vapor exposure, the nonuniform changes in local film morphology provide a permanent record or "fingerprint" for the chemical event of interest. This permanent modification in the film structure can be directly detected via changes not only in the film surface profile but also in the film optical characteristics. To this end, we demonstrated that sensing/recording nanofoam films can be prepared and interrogated on the surfaces of optical waveguides, microring optical resonators. It is important that the initial surface profile and structure of the nanofoam film are encrypted by the distinctive conditions that were used to fabricate the film and practically impossible to replicate without prior knowledge.

Temperature controlled shape change of grafted nanofoams.

We demonstrated that nanoscale-level actuation can be, in principle, achieved with grafted polymer nanofoams by forces associated with conformational changes of stretched macromolecular chains. The nanofoams are fabricated via a two-step procedure. First, the "grafting to" technique is used to obtain a 20-200 nm anchored and cross-linked poly(glycidyl methacrylate) film. Second, the film is swollen in solvent and freeze dried until the solvent is sublimated. The grafted nanofoam possesses the behavior of a shape-memory material, exhibiting gradual mechanical contraction at the nanometer scale as temperature is increased. Both the thickness and shape-recovery ratio of the nanofoam have a close to linear dependency on temperature. We also demonstrated that by modification of the poly(glycidyl methacrylate) nanofoam with grafting low molecular weight polymers, one can tune an absolute nanoscale mechanical response of the porous polymer film.

Mid-infrared materials and devices on a Si platform for optical sensing.

In this article, we review our recent work on mid-infrared (mid-IR) photonic materials and devices fabricated on silicon for on-chip sensing applications. Pedestal waveguides based on silicon are demonstrated as broadband mid-IR sensors. Our low-loss mid-IR directional couplers demonstrated in SiN x waveguides are useful in differential sensing applications. Photonic crystal cavities and microdisk resonators based on chalcogenide glasses for high sensitivity are also demonstrated as effective mid-IR sensors. Polymer-based functionalization layers, to enhance the sensitivity and selectivity of our sensor devices, are also presented. We discuss the design of mid-IR chalcogenide waveguides integrated with polycrystalline PbTe detectors on a monolithic silicon platform for optical sensing, wherein the use of a low-index spacer layer enables the evanescent coupling of mid-IR light from the waveguides to the detector. Finally, we show the successful fabrication processing of our first prototype mid-IR waveguide-integrated detectors.