Enhancing the Dispersibility of TiO₂ Nanorods and Gaining Control over Region-Selective Layer Formation

We demonstrate that the dispersibility and reactivity of core–shell TiO₂ nanorods (NRs) can be controlled significantly through functionalization with a combination of ligands based on phosphonic acid derivatives (PAs). Specifically, a glycol based PA allows dispersion of the NRs in methanol (MeOH). On the other hand, incorporating an alkyne terminated PA in the ligand shell of the NRs allows for a copper-catalyzed alkyne–azide cycloaddition (CuAAC) reaction with an azide-patterned aluminum oxide (AlO_<i>x</i>) substrate and forms a region-selectively deposited film of NRs. We clearly demonstrate that the quality of the NR films correlates strongly with the stability of the NR dispersions in the reaction medium. In particular, tuning the concentration of alkyne PA in the ligand shell inhibits aggregation of the NRs on the substrate, while reactivity for the CuAAC reaction is maintained. The surface coverage with NRs fits the Langmuir model. This study illustrates that surface functionalization of AlO_<i>x</i> substrates can be effectively and conveniently controlled through enhancing the dispersibility of the NRs using mixed ligand shells

Self-Assembled Monolayer Exchange Reactions as a Tool for Channel Interface Engineering in Low-Voltage Organic Thin-Film Transistors

In this work, we compared the kinetics of monolayer self-assembly long-chained carboxylic acids and phosphonic acids on thin aluminum oxide surfaces and investigated their dielectric properties in capacitors and low-voltage organic thin-film transistors. Phosphonic acid anchor groups tend to substitute carboxylic acid molecules on aluminum oxide surfaces and thus allow the formation of mixed or fully exchanged monolayers. With different alkyl chain substituents (<i>n</i>-alkyl or fluorinated alkyl chains), the exchange reaction can be monitored as a function of time by static contact angle measurements. The threshold voltage in α,α′-dihexyl-sexithiophene thin-film transistors composed of such mixed layer dielectrics correlates with the exchange progress and can be tuned from negative to positive values or vice versa depending on the dipole moment of the alkyl chain substituents. The change in the dipole moment with increasing exchange time also shifts the capacitance of these devices. The rate constants for exchange reactions determined by the time-dependent shift of static contact angle, threshold voltage, and capacitance exhibit virtually the same value thus proving the exchange kinetics to be highly controllable. In general, the exchange approach is a powerful tool in interface engineering, displaying a great potential for tailoring of device characteristics

Structural Investigations of Self-Assembled Monolayers for Organic Electronics: Results from X‑ray Reflectivity

ConspectusSelf-assembled monolayers (SAMs) have been established as crucial interlayers and electronically active layers in organic electronic devices, such as organic light emitting diodes (OLEDs), organic photovoltaics (OPVs), organic thin film transistors (OTFTs), and nonvolatile memories (NVMs). The use of self-assembling functionalized organic molecules is beneficial due to mainly three advantages compared with common thin film deposition approaches. (1) Molecular self-assembly occurs with surface selectivity, determined by the interaction between the functional anchor group of the organic molecules and the target surface. (2) The film thickness of the resulting layers is perfectly controllable on the angstrom scale, due to the self-terminating film formation to only a single molecular layer. And finally, (3) the wide variability in the chemical structure of such molecules enables different SAM functionalities for devices, ranging from electrical insulation to charge storage to charge transport. The SAM approach can be further expanded by employing several functionalized molecules to create mixed SAMs with consequently mixed properties.The function of SAMs in devices depends not only on the chemical structure of the molecules but also on their final arrangement and orientation on the surface. A reliable and nondestructive in-depth characterization of SAMs on nonconductive oxide surfaces is still challenging because of the very small thickness and the impracticality of methods such as scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS).In this Account, we illustrate how X-ray reflectivity (XRR) provides analytical access to major questions of SAM composition, morphology, and even formation by means of investigations of pure and mixed SAMs based on phosphonic acids (PAs) of various chain structures on flat alumina (AlO_<i>x</i>) surfaces. XRR is an analytical method that provides access to spatially averaged structural depth profiles over a relatively large area of several square micrometers. The key outcome of XRR, the surface-normal electron density profile of the SAMs, leads to precise information on the SAM thickness with subangstrom resolution and allows for the determination of molecular tilt angles and packing densities.We have systematically increased the chemical complexity of PA molecules and the resulting SAMs, utilizing XRR to provide insight into the SAM structures. In SAMs composed of functionalized molecules or complex chain structures, the distribution of electron rich and electron poor signatures is detected and thus the molecular order within the SAM is determined.In mixed SAMs of two different molecular species, electron density profiles reveal the morphology and how the surface-normal structure changes if one component of the mixed SAM is altered. Furthermore, XRR was applied to investigate in situ the self-assembly of functionalized PA molecules from solution by tracking the monolayer growth over time. Even though the results provided by XRR on in-plane molecular arrangement are limited, it presents excellent information on the molecular scale along the surface normal and in addition allows for drawing conclusions on the intermolecular interactions within the SAM

Low-Voltage Organic Field Effect Transistors with a 2‑Tridecyl[1]benzothieno[3,2‑<i>b</i>][1]benzothiophene Semiconductor Layer

An asymmetric <i>n</i>-alkyl substitution pattern was realized in 2-tridecyl[1]­benzothieno­[3,2-<i>b</i>]­[1]­benzothiophene (C₁₃-BTBT) in order to improve the charge transport properties in organic thin-film transistors. We obtained large hole mobilities up to 17.2 cm²/(V·s) in low-voltage operating devices. The large mobility is related to densely packed layers of the BTBT π-systems at the channel interface dedicated to the substitution motif and confirmed by X-ray reflectivity measurements. The devices exhibit promising stability in continuous operation for several hours in ambient air

Impact of Oxygen Plasma Treatment on the Device Performance of Zinc Oxide Nanoparticle-Based Thin-Film Transistors

Thin-films of zinc oxide nanoparticles were investigated by photoluminescence spectroscopy and a broad defect-related yellow-green emission was observed. Oxygen plasma treatment was applied in order to reduce the number of defects, and the emission intensity was quenched to 4% of the initial value. Thin-film transistors that incorporate the nanoparticles as active semiconducting layers show an improved device performance after oxygen plasma treatment. The maximum drain current and the charge carrier mobility increased more than 1 order of magnitude up to a nominal value of 23 cm² V^–1 s^–1 and the threshold voltage was lowered

Phosphonate- and Carboxylate-Based Self-Assembled Monolayers for Organic Devices: A Theoretical Study of Surface Binding on Aluminum Oxide with Experimental Support

We report a computational study on the chemical bonding of phosphonates and carboxylates to aluminum oxide surfaces and how the binding properties are related to the amount of water in the experimental environment. Two different surface structures were used in the calculations in order to model representative adsorption sites for the phosphonates and carboxylates and to account for the amorphous nature of the hydroxylated AlO_<i>x</i> films in experiment. For the phosphonates, we find that the thermodynamically preferred binding mode changes between mono-, bi-, and tridentate depending on the surface structure and the amount of residual water. For the carboxylates, on the other hand, monodentate adsorption is always lower in energy at all experimental conditions. Phosphonates are more strongly bound to aluminum oxide than carboxylates, so that carboxylates can be replaced easily by phosphonates. The theoretical findings are consistent with those obtained in adsorption, desorption, and exchange reactions of <i>n</i>-alkyl phosphonic and carboxylic acids on AlO_<i>x</i> surfaces. The results provide an atomistic understanding of the adsorption and help to optimize experimental conditions for self-assembly of organic films on aluminum oxide surfaces

High-Mobility ZnO Nanorod Field-Effect Transistors by Self-Alignment and Electrolyte-Gating

High mobility, solution-processed field-effect transistors are important building blocks for flexible electronics. Here we demonstrate the alignment of semiconducting, colloidal ZnO nanorods by a simple solvent evaporation technique and achieve high electron mobilities in field-effect transistors at low operating voltages by electrolyte-gating with ionic liquids. The degree of alignment varies with nanorod length, concentration and solvent evaporation rate. We find a strong dependence of electron mobility on the degree of alignment but less on the length of the nanorods. Maximum field-effect mobilities reach up to 9 cm² V^–1 s^–1 for optimal alignment. Because of the low process temperature (150 °C), ZnO nanorod thin films are suitable for application on flexible polymer substrates

Effect of Structure and Disorder on the Charge Transport in Defined Self-Assembled Monolayers of Organic Semiconductors

Self-assembled monolayer field-effect transistors (SAMFETs) are not only a promising type of organic electronic device but also allow detailed analyses of structure–property correlations. The influence of the morphology on the charge transport is particularly pronounced, due to the confined monolayer of 2D-π-stacked organic semiconductor molecules. The morphology, in turn, is governed by relatively weak van-der-Waals interactions and is thus prone to dynamic structural fluctuations. Accordingly, combining electronic and physical characterization and time-averaged X-ray analyses with the dynamic information available at atomic resolution from simulations allows us to characterize self-assembled monolayer (SAM) based devices in great detail. For this purpose, we have constructed transistors based on SAMs of two molecules that consist of the organic p-type semiconductor benzothieno­[3,2-<i>b</i>]­[1]­benzothiophene (BTBT), linked to a C₁₁ or C₁₂ alkylphosphonic acid. Both molecules form ordered SAMs; however, our experiments show that the size of the crystalline domains and the charge-transport properties vary considerably in the two systems. These findings were confirmed by molecular dynamics (MD) simulations and semiempirical molecular-orbital electronic-structure calculations, performed on snapshots from the MD simulations at different times, revealing, in atomistic detail, how the charge transport in organic semiconductors is influenced and limited by dynamic disorder

The Relationship between Threshold Voltage and Dipolar Character of Self-Assembled Monolayers in Organic Thin-Film Transistors

We report a quantitative study that describes and correlates the threshold voltage of low-voltage organic field-effect transistors with the molecular structure of self-assembled monolayer dielectrics. We have observed that the component of the dipole moment of such self-assembled molecules perpendicular to the surface correlates linearly with the threshold voltage shift in devices. The model was validated using three different organic semiconductors (pentacene, α,α′-dihexylsexithiophene, and fullerene–C₆₀) on six different self-assembled monolayers. The correlation found can help optimize future devices, by tuning the dipole moments of the molecules that constitute the self-assembled monolayer

Evidence of Tailoring the Interfacial Chemical Composition in Normal Structure Hybrid Organohalide Perovskites by a Self-Assembled Monolayer

Current–voltage hysteresis is a major issue for normal architecture organo-halide perovskite solar cells. In this manuscript we reveal a several-angstrom thick methylammonium iodide-rich interface between the perovskite and the metal oxide. Surface functionalization via self-assembled monolayers allowed us to control the composition of the interface monolayer from Pb poor to Pb rich, which, in parallel, suppresses hysteresis in perovskite solar cells. The bulk of the perovskite films is not affected by the interface engineering and remains highly crystalline in the surface-normal direction over the whole film thickness. The subnanometer structural modifications of the buried interface were revealed by X-ray reflectivity, which is most sensitive to monitor changes in the mass density of only several-angstrom thin interfacial layers as a function of substrate functionalization. From Kelvin probe force microscopy study on a solar cell cross section, we further demonstrate local variations of the potential on different electron-transporting layers within a solar cell. On the basis of these findings, we present a unifying model explaining hysteresis in perovskite solar cells, giving an insight into one crucial aspect of hysteresis for the first time and paving way for new strategies in the field of perovskite-based opto-electronic devices