No abstract

Over the past years, the layer-by-layer (LbL) assembly has been widely developed as one of the most powerful techniques to prepare multifunctional films with desired functions, structures and morphologies because of its versatility in the process steps in both material and substrate choices. Among various functional nanoscale objects, carbon-based nanomaterials, such as carbon nanotubes and graphene sheets, are promising candidates for emerging science and technology with their unique physical, chemical, and mechanical properties. In particular, carbon-based functional multilayer coatings based on the LbL assembly are currently being actively pursued as conducting electrodes, batteries, solar cells, supercapacitors, fuel cells and sensor applications. In this article, we give an overview on the use of carbon materials in nanostructured films and capsules prepared by the LbL assembly with the aim of unraveling the unique features and their applications of carbon multilayers prepared by the LbL assembly.

We demonstrate a controlled, systematic method to tune the charge transport in graphene field-effect transistors based on alternating layer-by-layer assembly of positively and negatively charged graphene oxide followed by thermal reduction. Surprisingly, tuning the number of bilayers of thermally reduced graphene oxide multilayer films allowed achieving either ambipolar or unipolar (both n- and p-type) transport in graphene transistors. On the basis of X-ray photoemission spectroscopy, Raman spectroscopy, time-of-flight secondary ion mass spectrometry, and temperature-dependent charge transport measurements, we found that nitrogen atoms from the functional groups of positively charged graphene oxide are incorporated into the reduced graphene oxide films and substitute carbon atoms during the thermal reduction. This nitrogen-doping process occurs in different degrees for graphene multilayers with varying numbers of bilayers and thereby results in the interesting transition in the electrical behavior in graphene multilayer transistors. We believe that such a versatile method to control the charge transport in graphene multilayers will further promote their applications in solution-processable electronic devices based on graphene.

Molybdenum disulfide (MoS2) multilayers with functional polyelectrolyte nanospacing layers are presented. Taking advantage of the facile method of layer-by-layer (LbL) assembly, individual chemically exfoliated MoS2 layers are not only effectively isolated from interlayer coupling but also doped by functional polymeric layers. It is clearly demonstrated that MoS2 nanosheets separated by polymeric trilayers exhibit a much larger increase in photoluminescence (PL) as the number of layers is increased. The enhanced PL has been correlated to the ratio of excitons to trions with the type of polymeric spacers. Because uniform heterogeneous interfaces can be formed between various transition metal dichalcogenides and other soft materials, LbL assembly offers possibilities for further development in the solution-processable assemblies of two-dimensional materials.

Polyolefins dominate the market for commodity plastics due to their low cost and suitable properties, but polyolefins are rarely used in 3D printing due to issues with deformation of the printed structure during crystallization from the large volume change. Here, we demonstrate that filaments containing approximately 50% of either high density or low density polyethylene (HDPE/LDPE) as a shell with a polycarbonate (PC)/acrylonitrile-butadiene-styrene (ABS) blend core can be printed using standard fused filament fabrication methods with adequate to good dimensional accuracy, improved impact resistance, and enhanced elongation at break relative to samples printed with PC/ABS alone. The combination of lower crystallinity (28%) of LDPE in comparison to HDPE (62%) and lower crystallization temperature of LDPE (89 °C) than HDPE (117 °C) leads to improved dimensional accuracy of the printed part. However, the elastic modulus of the composite containing LDPE is only 48% of the part printed with only PC/ABS for flat ( XY ) orientations, whereas the reduction in modulus with the HDPE shell is significantly less. The mechanical behavior can be rationalized in terms of aligned fiber composite theory where anisotropic modulus is expected to be dependent on the angle between stretching direction and fiber axis. The low cost of LDPE and HDPE along with the ability to increase impact strength and extensibility of printed parts further demonstrate the promise of composite core–shell filaments for additive manufacturing.