Thermo-responsive polymers reversibly react to changes in temperature and water content of their environment (i.e., relative humidity, RH). In the present contribution, the thermo-responsiveness of poly(N-vinylcaprolactam) thin films cross-linked by di(ethylene glycol) divinyl ether deposited by initiated chemical vapor deposition are investigated to assess their applicability to sensor and actuator setups. A lower critical solution temperature (LCST) is observed at around 16°C in aqueous environment, associated with a dramatic change in film thickness (e.g., 200% increase at low temperatures) and refractive index, while only thermal expansion of the polymeric system is found, when ramping the temperature in dry atmosphere. In humid environment, we observed a significant response occurring in low RH (already below 5% RH), with the moisture swelling the thin film (up to 4%), but mainly replacing air in the polymeric structure up to ~40% RH. Non-temperature-dependent swelling is observed up to 80% RH. Above that, thermo-responsive behavior is also demonstrated to be present in humid environment for the first time, whereas towards 100% RH, film thickness and index appear to approach the values obtained in water at the respective temperatures. The response times are similar in a large range of RH and are faster than the ones of the reference humidity sensor used (i.e., seconds). A sensor/actuator hygromorphic device was built by coating a thin flower-shaped poly-(dimethylsiloxane) (PDMS) substrate with the thermo-responsive polymer. The large swelling due to water uptake upon exposure to humid environment at temperatures below the LCST caused the petals to bend, mimicking the capability of plants to respond to environmental stimuli via reversible mechanical motion.

In this study, a novel, fully polymeric setup for piezoresistive sensing is prepared and tested. Monolayers of polystyrene (PS) nanospheres are assembled on flexible polyethylene naphthalate substrates. Subsequently, thin layers (≈50–100 nm) of poly(3,4‐ethylenedioxythiophene) (PEDOT) are deposited conformally around the spheres by oxidative chemical vapor deposition (oCVD). Voltage−current characteristics and direct resistance measurements are performed to test the electrical properties of the samples in their unstrained state and their piezoresistive response during bending. Substrate deposition temperature (T_sub) and film thickness (t_PEDOT) are used as parameters to alter properties of the PEDOT thin films; increased T_sub and t_PEDOT lead to samples exhibiting lower intrinsic resistance. The electrical conductivity of the samples is estimated to range as high as tens of S cm⁻¹. Dopant exchange of the oCVD‐PEDOT layer (intrinsically, chlorine‐doped) is performed by putting the samples in 0.5 m sulfuric acid, which decreases their resistance by ≈1/3. Regarding the piezoresistive properties of the devices, acid treatment, higher T_sub and t_PEDOT (thus, lower intrinsic resistance) yield samples with increased response. As a result, gauge factors as high as 11.4 are achieved. Due to their flexibility and low‐cost, the proposed structures can be readily employed as skin‐inspired or wearable electronic devices.

In this contribution, the temperature-dependent swelling behavior of vapor-deposited smart polymer thin films is shown to depend on cross-linking and deposited film thickness. Smart polymers find application in sensor and actuator setups and are mostly fabricated on delicate substrates with complex nanostructures that need to be conformally coated. As initiated chemical vapor deposition (iCVD) meets these specific requirements, the present work concentrates on temperature-dependent swelling behavior of iCVD poly(N-isopropylacrylamide) thin films. The transition between swollen and shrunken state and the corresponding lower critical solution temperature (LCST) was investigated by spectroscopic ellipsometry in water. The films’ density in the dry state evaluated from X-ray reflectivity could be successfully correlated to the position of the LCST in water and was found to vary between 1.1 and 1.3 g/cm³ in the thickness range 30–330 nm. This work emphasizes the importance of insights in both the deposition process and mechanisms during swelling of smart polymeric structures.

In this contribution, we report on the thin-film synthesis of a novel thermoresponsive polymer, namely, poly(N-vinylcaprolactam) cross-linked by di(ethylene glycol)divinyl ether [p(NVCL-co-DEGDVE)] by initiated chemical vapor deposition (iCVD). Its transition between swollen and shrunken states in film thickness and the corresponding lower critical solution temperature (LCST) was investigated by spectroscopic ellipsometry in water. Water contact angle measurements and nano-indentation experiments reveal that the transition is accompanied by a change in wettability and elastic modulus. The amount of cross-linking was used to tune the thermoresponsive behavior of the thin films, resulting in higher swelling and LCST, increased surface rearrangement, and lower stiffness for less cross-linked polymers. For the first time, the filament temperature during iCVD synthesis was used to vary the chain length of the resulting polymeric systems and, thus, the position of their thermoresponsive transition. With that, swelling of up to 250% compared to the dry thickness and transition temperatures ranging from 16 to 40 °C could be achieved.

In this contribution, we report on the thin film synthesis of a thermo-responsive polymer onto another polymer used as an enteric coating in drug applications. In particular, we deposit cross-linked poly(N-vinylcaprolactam) (pNVCL) thin films by initiated chemical vapor deposition (iCVD) onto spin-coated Eudragit® (EUD) layers. Already upon iCVD-synthesis, the layered structure starts to form wrinkles at a minimum iCVD-thickness of 30 nm. By changing the EUD layer thickness and the amount of cross-linking used during iCVD, the morphology of the wrinkles is demonstrated to be readily tunable. Laterally, the double-layer structures vary in morphology from being ultrasmooth to exhibiting up to 3.5 µm wrinkle wavelength. The surface roughness and, thus, the wrinkles’ height can be tailored from below 1 up to 100 nm. From the resulting wavelength of wrinkles, an estimation of the elastic modulus of pNVCL proves its tunability over a wide range of values facilitating the iCVD process. This study elucidates an uncomplicated way to tune the wrinkles’ morphology and, thus, the surface area of a system that can be employed in drug delivery applications. Hence, an enteric coating of EUD together with an iCVD-synthesized thermo-responsive thin film is proposed as a promising composite encapsulation layer to outperform established systems in terms of tunability of the response to multiple external stimuli.

The synthesis of MLD-derived mesoporous ZnO with 20% of porosity is demonstrated and studied by advanced in situ characterization techniques.