Giovanni Ligorio

Harnessing the Liquid‐Phase Exfoliation of Graphene Using Aliphatic Compounds: A Supramolecular Approach

The technological exploitation of the extraordinary properties of graphene relies on the ability to achieve full control over the production of a high-quality material and its processing by up-scalable approaches in order to fabricate large-area films with single-layer or a few atomic-layer thickness, which might be integrated in working devices. A simple method is reported for producing homogenous dispersions of unfunctionalized and non-oxidized graphene nanosheets in N-methyl-2-pyrrolidone (NMP) by using simple molecular modules, which act as dispersion-stabilizing compounds during the liquid-phase exfoliation (LPE) process, leading to an increase in the concentration of graphene in dispersions. The LPE-processed graphene dispersion was shown to be a conductive ink. This approach opens up new avenues for the technological applications of this graphene ink as low-cost electrodes and conducting nanocomposite for electronics.

Energy-Level Engineering at ZnO/Oligophenylene Interfaces with Phosphonate-Based Self-Assembled Monolayers.

We used aromatic phosphonates with substituted phenyl rings with different molecular dipole moments to form self-assembled monolayers (SAMs) on the Zn-terminated ZnO(0001) surface in order to engineer the energy-level alignment at hybrid inorganic/organic semiconductor interfaces, with an oligophenylene as organic component. The work function of ZnO was tuned over a wide range of more than 1.7 eV by different SAMs. The difference in the morphology and polarity of the SAM-modified ZnO surfaces led to different oligophenylene orientation, which resulted in an orientation-dependent ionization energy that varied by 0.7 eV. The interplay of SAM-induced work function modification and oligophenylene orientation changes allowed tuning of the offsets between the molecular frontier energy levels and the semiconductor band edges over a wide range. Our results demonstrate the versatile use of appropriate SAMs to tune the energy levels of ZnO-based hybrid semiconductor heterojunctions, which is important to optimize its function, e.g., targeting either interfacial energy- or charge-transfer.

Tuning the Electronic Structure of Graphene by Molecular Dopants: Impact of the Substrate

A combination of ultraviolet and X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, and first principle calculations was used to study the electronic structure at the interface between the strong molecular acceptor 1,3,4,5,7,8-hexafluorotetracyano-naphthoquinodimethane (F6TCNNQ) and a graphene layer supported on either a quartz or a copper substrate. We find evidence for fundamentally different charge redistribution mechanisms in the two ternary systems, as a consequence of the insulating versus metallic character of the substrates. While electron transfer occurs exclusively from graphene to F6TCNNQ on the quartz support (p-doping of graphene), the Cu substrate electron reservoir induces an additional electron density flow to graphene decorated with the acceptor monolayer. Remarkably, graphene on Cu is n-doped and remains n-doped upon F6TCNNQ deposition. On both substrates, the work function of graphene increases substantially with a F6TCNNQ monolayer atop, the effect being more pronounced (∼1.3 eV) on Cu compared to quartz (∼1.0 eV) because of the larger electrostatic potential drop associated with the long-distance graphene-mediated Cu-F6TCNNQ electron transfer. We thus provide a means to realize high work function surfaces for both p- and n-type doped graphene.

Charging and exciton-mediated decharging of metal nanoparticles in organic semiconductor matrices

Gold nanoparticles (Au-NPs) were deposited on the surface of n- and p-type organic semiconductors to form defined model systems for charge storage based electrically addressable memory elements. We used ultraviolet photoelectron spectroscopy to study the electronic properties and found that the Au-NPs become positively charged because of photoelectron emission, evidenced by spectral shifts to higher binding energy. Upon illumination with light that can be absorbed by the organic semiconductors, dynamic charge neutrality of the Au-NPs could be re-established through electron transfer from excitons. The light-controlled charge state of the Au-NPs could add optical addressability to memory elements.

Lithography-Free Miniaturization of Resistive Nonvolatile Memory Devices to the 100 nm Scale by Glancing Angle Deposition

The scaling of nonvolatile memory (NVM) devices based on resistive filament switching to below a 100 nm2 footprint area without employing cumbersome lithography is demonstrated. Nanocolumns of the organic semiconductor 4,4-bis[N-(1-naphthyl)-N-phenyl-amino]diphenyl (α-NPD) were grown by glancing angle deposition on a silver electrode. Individual NVM devices were electrically characterized by conductive atomic force microscopy with the tip of a conductive cantilever serving as second electrode. The resistive switching mechanism is unambiguously attributed to Ag filament formation between the electrodes. This sets the upper limit for the filament diameter to well below 100 nm. Full functionality of these NVM nanodevices is evidenced, revealing a potential memory density of >1 GB/cm2 in appropriate architectures.

Metal nanoparticle mediated space charge and its optical control in an organic hole-only device

We reveal the role of localized space charges in hole-only devices based on an organic semiconductor with embedded metal nanoparticles (MNPs). MNPs act as deep traps for holes and reduce the current density compared to a device without MNPs by a factor of 104 due to the build-up of localized space charge. Dynamic MNPs charged neutrality can be realized during operation by electron transfer from excitons created in the organic matrix, enabling light sensing independent of device bias. In contrast to the previous speculations, electrical bistability in such devices was not observed.

Nanocrystalline Ga2O3 films deposited by spray pyrolysis from water-based solutions on glass and TCO substrates

A low-cost and up-scalable fabrication method for high-quality gallium oxide films using spray pyrolysis from water-based solutions and moderate temperatures is presented. The solution chemistry and spraying process parameters were optimized to obtain homogeneous films on glass and three different transparent conducting oxide substrates. Structural and optical film properties of the deposited nanocrystalline Ga2O3 were evaluated by scanning electron microscopy, grazing-incidence X-ray diffraction, atomic force microscopy and optical spectroscopy. The elemental composition of the surface and the bulk film was analyzed by X-ray photoemission spectroscopy depth profiling. To show the applicability of the deposited Ga2O3 in electronic devices, the electronic valence region of the material was studied by ultraviolet photoemission spectroscopy, resulting in an energy level diagram of the material.

Versatile and Scalable Strategy To Grow Sol–Gel Derived 2H-MoS2 Thin Films with Superior Electronic Properties: A Memristive Case

Transition metal dichalcogenides, such as molybdenum disulfide (MoS2), show peculiar chemical/physical properties that enable their use in applications ranging from micro- and nano-optoelectronics to surface catalysis, gas and light detection, and energy harvesting/production. One main limitation to fully harness the potential of MoS2 is given by the lack of scalable and low environmental impact synthesis of MoS2 films with high uniformity, hence setting a significant challenge for industrial applications. In this work, we develop a versatile and scalable sol-gel-derived MoS2 film fabrication by spin coating deposition of an aqueous sol on different technologically relevant, flexible substrates with annealing at low temperatures (300 °C) and without the need of sulfurization and/or supply of hydrogen as compared to cutting-edge techniques. The electronic and physical properties of the MoS2 thin films were extensively investigated by means of surface spectroscopy and structural characterization techniques. Spatially homogenous nanocrystalline 2H-MoS2 thin films were obtained exhibiting high chemical purity and excellent electronic properties such as an energy band gap of 1.35 eV in agreement with the 2H phase of the MoS2, and a density of states that corresponds to the n-type character expected for high-quality 2H-MoS2. The potential use of sol-gel-grown MoS2 as the candidate material for electronic applications was tested via electrical characterization and demonstrated via the reversible switching in resistivity typical for memristors with a measured ON-OFF ratio ≥102. The obtained results highlight that the novel low-cost fabrication method has a great potential to promote the use of high-quality MoS2 in technological and industrial-relevant scalable applications.

Organic Semiconductor/Gold Interface Interactions: From Physisorption on Planar Surfaces to Chemical Reactions with Metal Nanoparticles

The interaction of gold nanoparticles (AuNPs) with prototypical organic semiconductors used in optoelectronics, namely, tris(8-hydroxyquinoline)aluminium (Alq3 ) and 4,4-bis[N-(1-naphthyl)-N-phenylamino]diphenyl (α-NPD), is investigated in situ by X-ray photoelectron spectroscopy (XPS). These AuNPs-on-molecule experiments are compared with the reversed molecule-on-Au cases. The molecules-on-Au systems show only weak interactions, and the evolution of the XP spectra is dominated by final-state effects. In contrast, in the AuNPs-on-molecules cases, both initial-state effects and final-state effects occur. Spectral features arising for both molecules and metal indicate charge transfer and the formation of organometallic complexes (initial-state effects). The energy shift in the metal emission underlines the size-induced nanometric nature of the molecule/Au interaction (final-state effects). Consequently, the chemical interaction between metals and organic semiconductors likely depends strongly on the deposition sequence in general.

All solution processed blue multi-layer light emitting diodes realized by thermal layer stabilization and orthogonal solvent processing

Herein we report on the fabrication and the properties of two highly efficient blue light emitting multilayer polymer light emitting diodes (PLEDs). The first device structure combines a thermally stabilized polymer with a material processed from an orthogonal solvent, allowing for the fabrication of a triple layer structure from solution. The well known poly(9,9-dioctyl-fluorene-co-N-(4-butylphenyl)-diphenylamine) (TFB), which can be stabilized in a bake-out procedure, was used as a hole transporting layer. A novel pyrene – triphenylamine (PPyrTPA) copolymer was used as emissive layer. The stack was finalized by a poly(fluorene) - derivative with polar side-chains, therefore being soluble in a polar solvent which allows for the deposition onto PPyrTPA without redissolving. The resulting PLED showed bright-blue electroluminescence (CIE1931 coordinates x=0.163; y=0.216) with a high efficiency of 1.42 cd/A and a peak luminescence of 16500 cd/m². The second presented device configuration comprises a thermally stabilized indenofluorene – triphenylamine copolymer acting as hole transporter, and an emissive copolymer with building blocks specifically designed for blue light emission, effective charge carrier injection and transport as well as for exciton generation. This multilayer PLED led to deep-blue emission (CIE1931 x=0.144; y=0.129) with a remarkably high device efficiency of 9.7 cd/A. Additionally, atomic force microscopy was carried out to investigate the film morphology of the components of the stack and x-ray photoemission spectroscopy was performed to ensure a full coverage of the materials on top of each other. Ultraviolet photoemission spectroscopy confirmed the desired type-II band level offsets on the individual interfaces.