Revealing the Correlation of the Electrochemical Properties and the Hydration of Inkjet-Printed CdSe/CdS Semiconductor Gels.

The mobility of charge carriers across a semiconductor-nanoparticle-based 3D network (i.e., a gel) and the interfacial transfer of the charge carriers across the nanoparticle network/electrolyte boundary are elementary processes for applications in the fields of sensing and energy harvesting. The automated manufacturing of electrodes coated with porous networks can be realized by inkjet printing. By simultaneous printing of CdSe/CdS dot-in-rod-shaped nanorods (NRs) and the destabilization reagent, CdSe/CdS gel-network-coated electrodes can be obtained. In this work, the charge carrier mobility of the electrons and the holes within the porous CdSe/CdS nanorod gel network is investigated via photoelectrochemistry. Using linear sweep voltammograms (LSVs) and intensity-modulated photocurrent spectroscopy (IMPS), it is shown that the electron is moving within the tip-to-tip-connected CdSe/CdS NR gel structure, while the holes are trapped in the CdSe seed of the semiconductor heterostructures. Furthermore, the preparation process of gel structures is related to the elementary mechanism of hydration, which can be shown via photoelectrochemical long-term studies.

Photoluminescence Lifetime Based Investigations of Linker Mediated Electronic Connectivity Between Substrate and Nanoparticle.

The evolution of systems based on nanoparticles as the main component seems to be a self-accelerating process during the last five decades. Hence, an overview across this field gets more and more challenging. It is sometimes rewarding to focus on the fundamental physical phenomenon of the electronic interconnection between the different building blocks of the obtained devices. Therefore, the investigation of charge transport among the utilized particles and their substrate is one of the mandatory steps in the development of semiconductor nanoparticle based devices like e.g., sensors and LEDs. The investigation of the influence of tunneling barriers on the properties of nanoparticle-functionalized surfaces is a challenging task. The different basic influences on the charge transport dynamics are often difficult to separate from each other. Non-invasive and easily viable experiments are still required to resolve the charge distributing mechanisms in the systems. In the presented work, we want to focus on thin and transparent indium tin oxide (ITO) layers covered glass slides since this substrate is frequently utilized in nanoelectronics. CdSe/CdS nanorods (NRs) are applied as an optically addressable probe for the electronic surface states of the conductive glass. The presented experimental design provides the proof of electronic interconnections in ITO coated glass/linker/NR electrodes via easy reproducible functionalization and polishing experiments. UV/Vis absorption and photoluminescence (PL) lifetime measurements revealed changes in the optical properties caused by differences in the charge carrier dynamics between the system. Our work is focused on the modification of charge carrier dynamics due to the application of linker molecules with different functional groups like (3-mercaptopropyl)methoxysilane (MPTMS) and (3-aminopropyl)trimethoxysilane (APTMS). The presented observations are explained with a simple kinetic model.

Nanoplatelet cryoaerogels with potential application in photoelectrochemical sensing.

Semiconductor nanoparticle based porous 3D assemblies are interesting materials for various applications in the fields of photovoltaics, catalysis, or optical sensing. For use as photoelectrodes in photoelectrochemical sensors they need to be characterised by a high porosity, a good photostability, and a high charge carrier mobility. Our work reports on the preparation of cryoaerogel photoelectrodes based on CdSe nanoplatelets and their photoelectrochemical characterisation by means of linear sweep voltammetry (LSV) and intensity modulated photocurrent spectroscopy (IMPS). The obtained open-pored cryoaerogel films were observed to produce much higher photocurrents than comparable drop-cast films. By means of IMPS, the performance differences could be linked to the occurrence of charge carrier movement, which could solely be proven for the cryoaerogels. In a proof-of-principle experiment, the potential of the prepared photoelectrodes for application in photoelectrochemical sensing was moreover demonstrated.

Electronic transport in CdSe nanoplatelet based polymer fibres.

One of the most significant objectives in the field of nanotechnology is the transfer of specific properties of smaller nanoparticle building blocks into larger units. In this way, nanoscopic properties can be linked to the macroscopic addressability of larger systems. Such systems might find applications in fields like photoelectrochemical sensing or solar energy harvesting. Our work reports on the novel synthesis of hybrid semiconductor/polymer fibres, which are based on stacks of 4 monolayer (ML) thick CdSe nanoplatelets (NPLs) encapsulated into a polymer shell. The polymer encapsulation not only enables the water transfer of the NPL stacks but also allows the preparation of photoelectrodes by linking the fibres to surface modified indium tin oxide (ITO) glass slides. By applying electrochemical techniques like intensity modulated photocurrent spectroscopy (IMPS), it was possible to prove the motion of charge carriers inside the nanoplatelet stacks and by this the electronic addressibility of them.