Correlation between Chemical and Electronic Properties of Solution-Processed Nickel Oxide

Solution-processed nickel oxide (sNiO) is known to be an excellent charge-selective interlayer in optoelectronic devices. Its beneficial properties can be further enhanced by an oxygen plasma (OP) treatment. In order to elucidate the mechanism behind this improvement, we use infrared transmission and X-ray photoelectron spectroscopy to probe the bulk and surface properties of the sNiO. We find that increasing the annealing temperature of the sNiO not only increases the structural order of the material but also reduces the concentration of nickel hydroxide species present in the bulk and on the surface of the film. This results in a decrease of the work function, while an additional OP treatment raises the work function to between 5.5 and 5.6 eV. For all annealing temperatures investigated, the consequences of the OP treatment are identified as reactions of both NiO and β-Ni­(OH)₂ to form thin β-NiOOH phases in the first atomic layers. Our results emphasize the importance of understanding the correlation between the preparation and resulting properties of sNiO layers and provides further insight into the interpretation of interface properties of NiO

Dopant Diffusion in Sequentially Doped Poly(3-hexylthiophene) Studied by Infrared and Photoelectron Spectroscopy

The diffusivity of dopants in semiconducting polymers is of high interest as it enables methods of sequential doping but also affects device stability. In this study, we investigate the diffusion of a bulky sequentially deposited p-dopant in poly­(3-hexylthiophene) (P3HT) thin films using nondestructive <i>in situ</i> infrared (IR) spectroscopy and photoelectron spectroscopy (PES). We probe dopant diffusion into the polymer film at varying coverage by differentially evaluating electron transfer in the bulk and at the surface. Thereby it is possible to determine dopant coverages at which both electron transfer and incorporation of dopants are saturated. By use of PES, neutral and charged dopants can be distinguished, revealing that charged dopants are less mobile in the diffusion process than neutral molecules. We further compare the diffusivity in semicrystalline and fully amorphous P3HT. We find that at high coverage semicrystalline P3HT seems to yield a higher capacity for dopants than fully amorphous P3HT. A temperature-dependent measurement of sequential doping shows directly that the incorporation of dopants is thermally activated and requires temperatures close to room temperature

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

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

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

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 <i>N</i>,<i>N-</i>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

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)

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[<i>N</i>,<i>N</i>′-bis­(2-octyldodecyl)-naphthalene-1,4:5,8-bis­(dicarboximide)-2,6-diyl]-<i>alt</i>-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