Thomas Blaudeck

Formation Principles and Ligand Dynamics of Nanoassemblies of CdSe Quantum Dots and Functionalised Dye Molecules

Functional dye molecules, such as porphyrins, attached to CdSe quantum dots (QDs) through anchoring meso-pyridyl substituents, form quasi-stable nanoassemblies. This fact results in photoluminescence (PL) quenching of the QDs both due to Förster resonance energy transfer (FRET) and the formation of non-radiative surface states under conditions of quantum confinement (non-FRET). The formation process is in competition with the ligand dynamics. At least two timescales are found for the formation of the assemblies: 1) one faster than 60 s attributed to saturation of empty attachment sites and 2) one slower than 600 s, which is attributed to a reorganisation of the tri-n-octylphosphine oxide (TOPO) ligand shell. Finally, this process results in almost complete exchange of the TOPO shell by porphyrin dye molecules. Following a Stern-Volmer analysis, we established a microscopic description of PL quenching and assembly formation. Based on this formalism, we determined the equilibrium constant for assembly formation between QDs and the pyridyl-functionalised dye molecules to be K ≈ 10(5) - 10(7)  M(-1), which is several orders of magnitude larger than that of the TOPO ligands. Our results give additional insights into the non-FRET PL quenching processes involved and show that the QD surface is inhomogeneous with respect to the involved attachment and detachment processes. In comparison with other methods, such as NMR spectroscopy, the advantage of our approach is that ligand dynamics can be investigated at extremely low ratios of dye molecules to QDs.

Chemical post-treatment and thermoelectric properties of poly(3,4-ethylenedioxylthiophene):poly(styrenesulfonate) thin films

We report on the modification of the thermoelectric properties of poly(3,4-ethylenedioxylthiophene):poly(styrenesulfonate) (PEDOT:PSS) thin films by means of a simple post treatment of the solid thin films realized by drop-coating. We show that the organic polar solvents, dimethyl sulfoxide and ethylene glycol as secondary dopants for PEDOT:PSS, only affect the film morphology for which a high electrical conductivity is observed. In contrast, ethanolamine (MEA) and ammonia solutions are reduction agents that improve the density of PEDOT chains in the reduced forms (polaron and neutral states), resulting in the trade-off between Seebeck coefficient and electrical conductivity. Furthermore, we show that the nature of amines determines the reduction degree: the nitrogen lone pair electrons in MEA are easier to be donated than those in ammonia solution and will therefore neutralize the PEDOT chains.

Inkjet printing as a tool for the patterned deposition of octadecylsiloxane monolayers on silicon oxide surfaces

We present a case study about inkjet printing as a tool for molecular patterning of silicon oxide surfaces with hydrophobic functionality, mediated by n-octadecyltrichlorosilane (OTS) molecules. In contrast to state-of-the-art techniques such as micro contact printing or chemical immersion with subsequent lithography processes, piezo drop-on-demand inkjet printing does not depend on physical masters, which allows an effective direct-write patterning of rigid or flexible substrates and enables short run-lengths of the individual pattern. In this paper, we used mesithylene-based OTS inks, jetted them in droplets of 10 pL on a silicon oxide surface, evaluated the water contact angle of the patterned areas and fitted the results with Cassies law. For inks of 2.0 mM OTS concentration, we found that effective area coverages of 38% can be obtained. Our results hence show that contact times of the order of hundred milliseconds are sufficient to form a pattern of regions with OTS molecules adsorbed to the surface, representing at least a fragmented, inhomogeneous self-assembled OTS monolayer (OTS-SAM).

Size-Dependent Non-FRET Photoluminescence Quenching in Nanocomposites Based on Semiconductor Quantum Dots CdSe/ZnS and Functionalized Porphyrin Ligands

We review recent experimental work to utilize the size dependence of the luminescence quenching of colloidal semiconductor quantum dots induced by functionalized porphyrin molecules attached to the surface to describe a photoluminescence (PL) quenching process which is different from usual models of charge transfer (CT) or Foerster resonant energy transfer (FRET). Steady-state and picosecond time-resolved measurements were carried out for nanocomposites based on colloidal CdSe/ZnS and CdSe quantum dots (QDs) of various sizes and surfacely attached tetra-mesopyridyl-substituted porphyrin molecules (“Quantum Dot-Porphyrin” nanocomposites), in toluene at 295 K. It was found that the major part of the observed strong quenching of QD PL in “QD-Porphyrin” nanocomposites can neither be assigned to FRET nor to photoinduced charge transfer between the QD and the chromophore. This PL quenching depends on QD size and shell and is stronger for smaller quantum dots: QD PL quenching rate constants 𝑘𝑞 scale inversely with the QD diameter. Based on the comparison of experimental data and quantum mechanical calculations, it has been concluded that QD PL quenching in “QD-Porphyrin” nanocomposites can be understood in terms of a tunneling of the electron (of the excited electron-hole pair) followed by a (self-) localization of the electron or formation of trap states. The major contribution to PL quenching is found to be proportional to the calculated quantum-confined exciton wave function at the QD surface. Our findings highlight that single functionalized molecules can be considered as one of the probes for the complex interface physics and dynamics of colloidal semiconductor QD.

Photophysical properties of self-aggregated porphyrin: semiconductor nanoassemblies

Colloidal semiconductor nanocrystals from CdSe show photoluminescence quenching via titration with porphyrin derivatives. This quenching is an indication of the formation of nanoassemblies via surface attachment of pyridyl linker groups. As a consequence of the complex formation, dynamic and/or static interactions between QD and porphyrins are induced. Quenching efficiencies depend critically on sample stability, temperature, solvent, and electronic properties of the porphyrins. In order to optimize photoinduced dynamic processes these parameters have to be under control.

Inkjet Printing of Colloidal Nanospheres: Engineering the Evaporation-Driven Self-Assembly Process to Form Defined Layer Morphologies

We report on inkjet printing of aqueous colloidal suspensions containing monodisperse silica and/or polystyrene nanosphere particles and a systematic study of the morphology of the deposits as a function of different parameters during inkjet printing and solvent evaporation. The colloidal suspensions act as a model ink for an understanding of layer formation processes and resulting morphologies in inkjet printing in general. We investigated the influence of the surface energy and the temperature of the substrate, the formulation of the suspensions, and the multi-pass printing aiming for layer stacks on the morphology of the deposits. We explain our findings with models of evaporation-driven self-assembly of the nanosphere particles in a liquid droplet and derive methods to direct the self-assembly processes into distinct one- and two-dimensional deposit morphologies.

Quantitative in-situ scanning electron microscope pull-out experiments and molecular dynamics simulations of carbon nanotubes embedded in palladium

In this paper, we present our results of experimental and numerical pull-out tests on carbon nanotubes (CNTs) embedded in palladium. We prepared simple specimens by employing standard silicon wafers, physical vapor deposition of palladium and deposition of CNTs with a simple drop coating technique. An AFM cantilever with known stiffness connected to a nanomanipulation system was utilized inside a scanning electron microscope (SEM) as a force sensor to determine forces acting on a CNT during the pull-out process. SEM-images of the cantilever attached to a CNT have been evaluated for subsequent displacement steps with greyscale correlation to determine the cantilever deflection. We compare the experimentally obtained pull-out forces with values of numerical investigations by means of molecular dynamics and give interpretations for deviations according to material impurities or defects and their influence on the pull-out data. We find a very good agreement of force data from simulation and experiment, which ...

Experimental and computational studies on the role of surface functional groups in the mechanical behavior of interfaces between single-walled carbon nanotubes and metals

To study the mechanical interface behavior of single-walled carbon nanotubes (CNTs) embedded in a noble metal, we performed CNT–metal pull-out tests with in situ scanning electron microscope experiments. Molecular dynamics (MD) simulations were conducted to predict force–displacement data during pull-out, providing critical forces for failure of the system. In MD simulations, we focused on the influence of carboxylic surface functional groups (SFGs) covalently linked to the CNT. Experimentally obtained maximum forces between 10 and 102 nN in palladium and gold matrices and simulated achievable pulling forces agree very well. The dominant failure mode in the experiment is CNT rupture, although several pull-out failures were also observed. We explain the huge scatter of experimental values with varying embedding length and SFG surface density. From simulation, we found that SFGs act as small anchors in the metal matrix and significantly enhance the maximum forces. This interface reinforcement can lead to tensile stresses sufficiently high to initiate CNT rupture. To qualify the existence of carboxylic SFGs on our CNT material, we performed analytical investigation by means of fluorescence labeling of surface species and discuss the results. With this contribution, we focus on a synergy between computational and experimental approaches involving MD simulations, nano scale testing, and analytics (1) to predict to a good degree of accuracy maximum pull-out forces of single-walled CNTs embedded in a noble metal matrix and (2) to provide valuable input to understand the underlying mechanisms of failure with focus on SFGs. This is of fundamental interest for the design of future mechanical sensors incorporating piezoresistive single-walled CNTs as the sensing element.

Metal nanoparticles reveal the organization of single-walled carbon nanotubes in bundles†

Single-walled carbon nanotubes (SWCNTs) were decorated with metal nanoparticles. Using a complementary analysis with spatially resolved micro-Raman spectroscopy, high resolution transmission electron microscopy, electron diffraction, and tip-enhanced Raman spectroscopy, we show that the SWCNTs form bundles in which smaller diameter SWCNTs are the ones preferentially affected by the presence of Au and Ag nanoparticles. This result is exploited to evaluate the structural organization of SWCNTs with mixed chiralities in bundles, leading us to postulate that smaller diameter SWCNTs surround larger ones. We found that this effect occurs for very distinct scenarios including SWCNTs both in nanometer thin films and in field effect transistor configurations at the wafer-level, suggesting a universal phenomenon for SWCNTs deposited from dispersions.

Investigation of RFID passive strain sensors based on carbon nanotubes using inkjet printing technology

Because of their remarkable properties, carbon nanotubes (CNTs) have been used in many applications [1-5]. Stain sensors based on CNTs can overcome several limitations of the existing conventional sensors, including limited monitoring locations and separation from the structure that is being monitored. Many deposition methods were applied to deposit CNTs on substrate; inkjet technology among others will possibly turn out as a fast and flexible manufacturing method for CNT-based sensors. We report about a wireless passive strain sensor made by inkjet-printing of CNT dispersions on flexible substrates. According to the radio frequency identification (RFID) principles, a square planar coil was patterned using inkjet orienting technology on a flexible substrate (Polyethylene terephthalate - PET) in order to measure strain wirelessly [6, 7]. Several settings of printing were investigated and optimized. Coils of different design parameters including variation of the number of windings, inner diameter, outer diameter and number of printed layers were manufactured using inkjet printing. The investigation of the readout mechanism of the sensor was done by applying the electrical impedance spectroscopy (EIS) analysis. By measuring the change in the complex impedance of the coupled coil, the changes in the resonance frequencies of the sensors were detected wirelessly. The change in the bandwidth is considered to be the main effect of the sensor under strain.