External Control of GaN Band Bending Using Phosphonate Self-Assembled Monolayers.

We report on the optoelectronic properties of GaN(0001) and (11̅00) surfaces after their functionalization with phosphonic acid derivatives. To analyze the possible correlation between the acid's electronegativity and the GaN surface band bending, two types of phosphonic acids, n-octylphosphonic acid (OPA) and 1H,1H,2H,2H-perfluorooctanephosphonic acid (PFOPA), are grafted on oxidized GaN(0001) and GaN(11̅00) layers as well as on GaN nanowires. The resulting hybrid inorganic/organic heterostructures are investigated by X-ray photoemission and photoluminescence spectroscopy. The GaN work function is changed significantly by the grafting of phosphonic acids, evidencing the formation of dense self-assembled monolayers. Regardless of the GaN surface orientation, both types of phosphonic acids significantly impact the GaN surface band bending. A dependence on the acids' electronegativity is, however, only observed for the oxidized GaN(11̅00) surface, indicating a relatively low density of surface states and a favorable band alignment between the surface oxide and acids' electronic states. Regarding the optical properties, the covalent bonding of PFOPA and OPA on oxidized GaN layers and nanowires significantly affects their internal quantum efficiency, especially in the nanowire case due to the large surface-to-volume ratio. The variation in the internal quantum efficiency is related to the modification of both the internal electric fields and surface states. These results demonstrate the potential of phosphonate chemistry for the surface functionalization of GaN, which could be exploited for selective sensing applications.

Structure-Property Relationship of Phenylene-Based Self-Assembled Monolayers for Record Low Work Function of Indium Tin Oxide.

Studying the structure-property relations of tailored dipolar phenyl and biphenylphosphonic acids, we report self-assembled monolayers with a significant decrease in the work function (WF) of indium-tin oxide (ITO) electrodes. Whereas the strengths of the dipoles are varied through the different molecular lengths and the introduction of electron-withdrawing fluorine atoms, the surface energy is kept constant through the electron-donating N, N-dimethylamine head groups. The self-assembled monolayer formation and its modification of the electrodes are investigated via infrared reflection absorption spectroscopy, contact angle measurements, and photoelectron spectroscopy. The WF decrease in ITO correlates with increasing molecular dipoles. The lowest ever recorded WF of 3.7 eV is achieved with the fluorinated biphenylphosphonic acid.

Correlation of Device Performance and Fermi Level Shift in the Emitting Layer of Organic Light-Emitting Diodes with Amine-Based Electron Injection Layers.

We investigate three amine-based polymers, polyethylenimine and two amino-functionalized polyfluorenes, as electron injection layers (EILs) in organic light-emitting diodes (OLEDs) and find correlations between the molecular structure of the polymers, the electronic alignment at the emitter/EIL interface, and the resulting device performance. X-ray photoelectron spectroscopy measurements of the emitter/EIL interface indicate that all three EIL polymers induce an upward shift of the Fermi level in the emitting layer close to the interface similar to n-type doping. The absolute value of this Fermi level shift, which can be explained by an electron transfer from the EIL polymers into the emitting layer, correlates with the number of nitrogen-containing groups in the side chains of the polymers. Whereas polyethylenimine (PEI) and one of the investigated polyfluorenes (PFCON-C) have six such groups per monomer unit, the second investigated polyfluorene (PFN) only possesses two. Consequently, we measure Fermi level shifts of 0.5-0.7 eV for PEI and PFCON-C and only 0.2 eV for PFN. As a result of these Fermi level shifts, the energetic barrier for electron injection is significantly lowered and OLEDs which comprise PEI or PFCON-C as an EIL exhibit a more than twofold higher luminous efficacy than OLEDs with PFN.

Tetraazapentacene constructs: controlling bulk-morphology through molecular dimensionality.

Multi-core TIPSTAP-constructs of different dimensionality were created via "geometrization" of the monomeric, highly crystalline parent using alkyne linkers. Morphological diversity is produced, while the material acceptor strength remains untouched. We establish structure-function relationships as the bulk morphology is predicted from the molecular geometry.

Functionalized Nickel Oxide Hole Contact Layers: Work Function versus Conductivity.

Nickel oxide (NiO) is a widely used material for efficient hole extraction in optoelectronic devices. However, its surface characteristics strongly depend on the processing history and exposure to adsorbates. To achieve controllability of the electronic and chemical properties of solution-processed nickel oxide (sNiO), we functionalize its surface with a self-assembled monolayer (SAM) of 4-cyanophenylphosphonic acid. A detailed analysis of infrared and photoelectron spectroscopy shows the chemisorption of the molecules with a nominal layer thickness of around one monolayer and gives an insight into the chemical composition of the SAM. Density functional theory calculations reveal the possible binding configurations. By the application of the SAM, we increase the sNiO work function by up to 0.8 eV. When incorporated in organic solar cells, the increase in work function and improved energy level alignment to the donor does not lead to a higher fill factor of these cells. Instead, we observe the formation of a transport barrier, which can be reduced by increasing the conductivity of the sNiO through doping with copper oxide. We conclude that the widespread assumption of maximizing the fill factor by only matching the work function of the oxide charge extraction layer with the energy levels in the active material is a too narrow approach. Successful implementation of interface modifiers is only possible with a sufficiently high charge carrier concentration in the oxide interlayer to support efficient charge transfer across the interface.

Electric-Field-Controlled Dopant Distribution in Organic Semiconductors.

Stable electrical doping of organic semiconductors is fundamental for the functionality of high performance devices. It is known that dopants can be subjected to strong diffusion in certain organic semiconductors. This work studies the impact of operating conditions on thin films of the polymer poly(3-hexylthiophene) (P3HT) and the small molecule Spiro-MeOTAD, doped with two differently sized p-type dopants. The negatively charged dopants can drift upon application of an electric field in thin films of doped P3HT over surprisingly large distances. This drift is not observed in the small molecule Spiro-MeOTAD. Upon the dopants' directional movement in P3HT, a dedoped region forms at the negatively biased electrode, increasing the overall resistance of the thin film. In addition to electrical measurements, optical microscopy, spatially resolved infrared spectroscopy, and scanning Kelvin probe microscopy are used to investigate the drift of dopants. Dopant mobilities of 10-9 to 10-8 cm2 V-1 s-1 are estimated. This drift over several micrometers is reversible and can be controlled. Furthermore, this study presents a novel memory device to illustrate the applicability of this effect. The results emphasize the importance of dynamic processes under operating conditions that must be considered even for single doped layers.

Naphthalene Tetracarboxydiimide-Based n-Type Polymers with Removable Solubility via Thermally Cleavable Side Chains.

Multilayer solution-processed devices in organic electronics show the tendency of intermixing of subsequently deposited layers. Here, we synthesize naphthalene tetracarboxydiimide (NDI)-based n-type semiconducting polymers with thermally cleavable side chains which upon removal render the polymer insoluble. Infrared and photoelectron spectroscopy were performed to investigate the pyrolysis process. Characterization of organic field-effect transistors provides insight into charge transport. After the pyrolysis homogeneous films could be produced which are insoluble in the primary solvent. By varying curing temperature and time we show that these process parameters govern the amount of side chains in the film and influence the device performance.

Dipolar SAMs Reduce Charge Carrier Injection Barriers in n-Channel Organic Field Effect Transistors.

In this work we examine small conjugated molecules bearing a thiol headgroup as self assembled monolayers (SAM). Functional groups in the SAM-active molecule shift the work function of gold to n-channel semiconductor regimes and improve the wettability of the surface. We examine the effect of the presence of methylene linkers on the orientation of the molecule within the SAM. 3,4,5-Trimethoxythiophenol (TMP-SH) and 3,4,5-trimethoxybenzylthiol (TMP-CH2-SH) were first subjected to computational analysis, predicting work function shifts of -430 and -310 meV. Contact angle measurements show an increase in the wetting envelope compared to that of pristine gold. Infrared (IR) measurements show tilt angles of 22 and 63°, with the methylene-linked molecule (TMP-CH2-SH) attaining a flatter orientation. The actual work function shift as measured with photoemission spectroscopy (XPS/UPS) is even larger, -600 and -430 meV, respectively. The contact resistance between gold electrodes and poly[N,N'-bis(2-octyldodecyl)-naphthalene-1,4:5,8-bis(dicarboximide)-2,6-diyl]-alt-5,5'-(2,2'-bithiophene) (Polyera Aktive Ink, N2200) in n-type OFETs is demonstrated to decrease by 3 orders of magnitude due to the use of TMP-SH and TMP-CH2-SH. The effective mobility was enhanced by two orders of magnitude, significantly decreasing the contact resistance to match the mobilities reported for N2200 with optimized electrodes.

Processing follows function: pushing the formation of self-assembled monolayers to high-throughput compatible time scales.

Self-assembled monolayers (SAMs) of organic molecules can be used to tune interface energetics and thereby improve charge carrier injection at metal-semiconductor contacts. We investigate the compatibility of SAM formation with high-throughput processing techniques. Therefore, we examine the quality of SAMs, in terms of work function shift and chemical composition as measured with photoelectron and infrared spectroscopy and in dependency on molecular exposure during SAM formation. The functionality of the SAMs is determined by the performance increase of organic field-effect transistors upon SAM treatment of the source/drain contacts. This combined analytical and device-based approach enables us to minimize the necessary formation times via an optimization of the deposition conditions. Our findings demonstrate that SAMs composed of partially fluorinated alkanethiols can be prepared in ambient atmosphere from ethanol solution using immersion times as short as 5 s and still exhibit almost full charge injection functionality if process parameters are chosen carefully. This renders solution-processed SAMs compatible with high-throughput solution-based deposition techniques.

Investigation of solution-processed ultrathin electron injection layers for organic light-emitting diodes.

We study two types of water/alcohol-soluble aliphatic amines, polyethylenimine (PEI) and polyethylenimine-ethoxylated (PEIE), for their suitability as electron injection layers in solution-processed blue fluorescent organic light-emitting diodes (OLEDs). X-ray photoelectron spectroscopy is used to determine the nominal thickness of the polymer layers while ultraviolet photoelectron spectroscopy is carried out to determine the induced work-function change of the silver cathode. The determined work-function shifts are as high as 1.5 eV for PEI and 1.3 eV for PEIE. Furthermore, atomic force microscopy images reveal that homogeneous PEI and PEIE layers are present at nominal thicknesses of about 11 nm. Finally, we solution prepare blue emitting polymer-based OLEDs using PEI/PEIE in combination with Ag as cathode layers. Luminous efficiency reaches 3 and 2.2 cd A(-1), whereas maximum luminance values are as high as 8000 and 3000 cd m(-2) for PEI and PEIE injection layers, respectively. The prepared devices show a comparable performance to Ca/Ag OLEDs and an improved shelf lifetime.

Role of the Selective Contacts in the Performance of Lead Halide Perovskite Solar Cells.

The effect of electron- and hole-selective contacts in the final cell performance of hybrid lead halide perovskite, CH3NH3PbI3, solar cells has been systematically analyzed by impedance spectroscopy. Complete cells with compact TiO2 and spiro-OMeTAD as electron- and hole-selective contacts have been compared with incomplete cells without one or both selective contacts to highlight the specific role of each contact. It has been described how selective contacts contribute to enhance the cell FF and how the hole-selective contact is mainly responsible for the high Voc in this kind of device. We have determined that the recombination rate is mainly governed by the selective contacts. This fact has important implication for the future optimization of perovskite solar cells. Finally, we have developed a method to analyze the results obtained, and it has been applied for three different electron-selecting materials: TiO2, ZnO, and CdS.

Efficient Planar Heterojunction Perovskite Solar Cells Based on Formamidinium Lead Bromide.

The development of medium-bandgap solar cell absorber materials is of interest for the design of devices such as tandem solar cells and building-integrated photovoltaics. The recently developed perovskite solar cells can be suitable candidates for these applications. At present, wide bandgap alkylammonium lead bromide perovskite absorbers require a high-temperature sintered mesoporous TiO2 photoanode in order to function efficiently, which makes them unsuitable for some of the above applications. Here, we present for the first time highly efficient wide bandgap planar heterojunction solar cells based on the structurally related formamidinium lead bromide. We show that this material exhibits much longer diffusion lengths of the photoexcited species than its methylammonium counterpart. This results in planar heterojunction solar cells exhibiting power conversion efficiencies approaching 7%. Hence, formamidinium lead bromide is a strong candidate as a wide bandgap absorber in perovskite solar cells.

Conformal and highly luminescent monolayers of Alq3 prepared by gas-phase molecular layer deposition.

The gas-phase molecular layer deposition (MLD) of conformal and highly luminescent monolayers of tris(8-hydroxyquinolinato)aluminum (Alq3) is reported. The controlled formation of Alq3 monolayers is achieved for the first time by functionalization of the substrate with amino groups, which serve as initial docking sites for trimethyl aluminum (TMA) molecules binding datively to the amine. Thereby, upon exposure to 8-hydroxyquinoline (8-HQ), the self-limiting formation of highly luminescent Alq3 monolayers is afforded. The growth process and monolayer formation were studied and verified by in situ quartz crystal monitoring, optical emission and absorption spectroscopy, and X-ray photoelectron spectroscopy. The nature of the MLD process provides an avenue to coat arbitrarily shaped 3D surfaces and porous structures with high surface areas, as demonstrated in this work for silica aerogels. The concept presented here paves the way to highly sensitive luminescent sensors and dye-sensitized metal oxides for future applications (e.g., in photocatalysis and solar cells).

Synthesis of nanoparticle/ligand composite thin films by sequential ligand self assembly and surface complex reduction.

Nanocomposite thin films consisting of ligand-connected metal nanoparticles were deposited by iteration of ligand assembly, surface complex formation and reduction. This novel and convenient approach combines characteristics of the layer-by-layer (LbL) and the successive ion layer adsorption and reaction (SILAR) techniques. In contrast to classical LbL assembly, the nanoparticle formation is performed in situ, avoiding separate reduction, protection and attachment steps. To demonstrate the versatility of the approach, different metal precursors (Pd, Ag and Au salts) and linkers (1,2-ethanedithiol, 1,4-benzenedithiol and polythiol) were applied. The formation of dithiol-linked nanoparticle films was confirmed by TEM and XPS. By combining the deposition protocol with ion track etched polycarbonate templates, nanotubes and nanowires with high aspect ratios of up to 300 could be fabricated.