Zinc oxide (ZnO) nanowires (NWs) are excellent candidates for the fabrication of energy harvesters, mechanical sensors, and piezotronic and piezophototronic devices. In order to integrate ZnO NWs into flexible devices, low-temperature fabrication methods are required that do not damage the plastic substrate. To date, the deposition of patterned ceramic thin films on flexible substrates is a difficult task to perform under vacuum-free conditions. Printing methods to deposit functional thin films offer many advantages, such as a low cost, low temperature, high throughput, and patterning at the same stage of deposition. Among printing techniques, gravure-based techniques are among the most attractive due to their ability to produce high quality results at high speeds and perform deposition over a large area. In this paper, we explore gravure printing as a cost-effective high-quality method to deposit thin ZnO seed layers on flexible polymer substrates. For the first time, we show that by following a chemical bath deposition (CBD) process, ZnO nanowires may be grown over gravure-printed ZnO nanoparticle seed layers. Piezo-response force microscopy (PFM) reveals the presence of a homogeneous distribution of Zn-polar domains in the NWs, and, by use of the data, the piezoelectric coefficient is estimated to be close to 4 pm/V. The overall results demonstrate that gravure printing is an appropriate method to deposit seed layers at a low temperature and to undertake the direct fabrication of flexible piezoelectric transducers that are based on ZnO nanowires. This work opens the possibility of manufacturing completely vacuum-free solution-based flexible piezoelectric devices.

Pyroelectric energy harvesting is one of the more recent and promising solid-state approaches for directly converting time-dependent temperature fluctuations into electric energy. Conventional printing technologies can offer many advantages for the production of pyroelectric thin-film-based devices, such as low cost, low temperature, the use of flexible substrates and shaping at the same time as deposition. Nevertheless, some issues related to low printed thickness and film-forming microstructure control need to be addressed. In this exploratory study, the possibility of exploiting the highly attractive gravure printing process for the potential industrial manufacture of flexible polyvinylidene fluoride (PVDF) thin-film pyroelectric devices was investigated. By the use of corona pre-treatment of the printing substrate and low-temperature polar solvent evaporation, multilayer gravure-printed PVDF pyroelectric devices were successfully manufactured for the first time, achieving a maximum generated current of 0.1 nA at 2.5 K/s from a device with an active area of 1 cm². Considering the very low thermal inertia and performance scaling by the area expected for pyroelectric thin-film-based devices, combined with the upscaling potential of roll-to-roll gravure printing, our results provide new opportunities for on-demand, low-cost pyroelectric device manufacture and their integration in hybrid harvesters.

Zinc oxide (ZnO) nanogenerators have attracted increasing interest in the scientific community for use in energy harvesting and mechanical sensing applications. Understanding the interplay between piezoelectricity and semiconductor physics is fundamental to enhancing these devices’ performances, although direct characterization at the nanoscale is challenging. With this work, we present a new strategy to improve piezoresponse force microscopy (PFM) measurements and analysis. This strategy was applied to study the piezoelectric performances of ZnO nanowires grown on seed layers deposited by gravure printing onto flexible substrates. We demonstrate the influence of nanowire diameter and atomic force microscope (AFM) tip position on the piezoresponse amplitude. We also explain our results with simulations showing the importance of considering semiconducting properties in the analysis.

Thermal camouflage is a highly coveted technology aimed at enhancing the survivability of military equipment against infrared (IR) detectors. Recently, two-dimensional (2D) nanomaterials have shown low IR emissivity, widely tunable opto-electronic properties, and compatibility with stealth applications. Among these, graphene and graphene-like materials are the most appealing 2D materials for thermal camouflage applications. In multilayer graphene (MLG), charge density can be effectively tuned through sufficiently intense electric fields or through electrolytic gating. Therefore, MLG’s optical properties, like infrared emissivity and absorbance, can be controlled in a wide range by voltage bias. The large emissivity modulation achievable with this material makes it suitable in the design of thermal dynamic camouflage devices. Generally, the emissivity modulation in the multilayered graphene medium is governed by an intercalation process of non-volatile ionic liquids under a voltage bias. The electrically driven reduction of emissivity lowers the apparent temperature of a surface, aligning it with the background temperature to achieve thermal camouflage. This characteristic is shared by other graphene-based materials. In this review, we focus on recent advancements in the thermal camouflage properties of graphene in composite films and aerogel structures. We provide a summary of the current understanding of how thermal camouflage materials work, their present limitations, and future opportunities for development.