The interface structure of graphene with thermally evaporated metal oxide layers, in particular molybdenum trioxide (MoO3), is studied combining photoemission spectroscopy, sheet resistance measurements and organic light emitting diode (OLED) characterization. Thin (<5 nm) MoO3 layers give rise to an 1.9 eV large interface dipole and a downwards bending of the MoO3 conduction band towards the Fermi level of graphene, leading to a near ideal alignment of the transport levels. The surface charge transfer manifests itself also as strong and stable p-type doping of the graphene layers, with the Fermi level downshifted by 0.25 eV and sheet resistance values consistently below 50 Ω/sq for few-layer graphene films. The combination of stable doping and highly efficient charge extraction/injection allows the demonstration of simplified graphene-based OLED device stacks with efficiencies exceeding those of standard ITO reference devices.

Organic electrochemical transistors (OECTs) show great promise for flexible, low‐cost, and low‐voltage sensors for aqueous solutions. The majority of OECT devices are made using the polymer blend poly(ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS), in which PEDOT is intrinsically doped due to inclusion of PSS. Because of this intrinsic doping, PEDOT:PSS OECTs generally operate in depletion mode, which results in a higher power consumption and limits stability. Here, a straightforward method to de‐dope PEDOT:PSS using commercially available amine‐based molecular de‐dopants to achieve stable enhancement‐mode OECTs is presented. The enhancement‐mode OECTs show mobilities near that of pristine PEDOT:PSS (≈2 cm2 V−1 s−1) with stable operation over 1000 on/off cycles. The electron and proton exchange among PEDOT, PSS, and the molecular de‐dopants are characterized to reveal the underlying chemical mechanism of the threshold voltage shift to negative voltages. Finally, the effect of the de‐doping on the microstructure of the spin‐cast PEDOT:PSS films is investigated.

Minimizing the reverse bias dark current while retaining external quantum efficiency is crucial if the light detection sensitivity of organic photodiodes (OPDs) is to compete with inorganic photodetectors. However, a quantitative relationship between the magnitude of the dark current density under reverse bias (  Jd) and the properties of the bulk heterojunction (BHJ) active layer has so far not been established. Here, a systematic analysis of Jd in state‐of‐the‐art BHJ OPDs using five polymers with a range of energy levels and charge transport characteristics is presented. The magnitude and activation energy of Jd are explained using a model that assumes charge injection from the metal contacts into an energetically disordered semiconductor. By relating Jd to material parameters, insights into the origin of Jd are obtained that enable the future selection of successful OPD materials.

Perovskites with bandgaps between 1.7 and 1.8 eV are optimal for tandem configurations with crystalline silicon (c-Si) because they facilitate efficient harvest of solar energy. In that respect, achieving a high open-circuit voltage (V OC ) in such wide-bandgap perovskite solar cells is crucial for a high overall power conversion efficiency (PCE). Here, we provide key insights into the factors affecting the V OC in wide-bandgap perovskite solar cells. We show that the influence of the hole transport layer (HTL) on V OC is not simply through its ionization potential but mainly through the quality of the perovskite−HTL interface. With effective interface passivation, we demonstrate perovskite solar cells with a bandgap of 1.72 eV that exhibit a V OC of 1.22 V. Furthermore, by combining the high-V OC perovskite solar cell with a c-Si solar cell, we demonstrate a perovskite−Si four-terminal tandem solar cell with a PCE of 27.1%, exceeding the record PCE of single-junction Si solar cells.

Interfaces between the photoactive and charge transport layers are crucial for the performance of perovskite solar cells. Surface passivation of SnO2 as electron transport layer (ETL) by fullerene derivatives is known to improve the performance of n–i–p devices, yet organic passivation layers are susceptible to removal during perovskite deposition. Understanding the nature of the passivation is important for further optimization of SnO2 ETLs. X‐ray photoelectron spectroscopy depth profiling is a convenient tool to monitor the fullerene concentration in passivation layers at a SnO2 interface. Through a comparative study using [6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) and [6,6]‐phenyl‐C61‐butyric acid (PCBA) passivation layers, a direct correlation is established between the formation of interfacial chemical bonds and the retention of passivating fullerene molecules at the SnO2 interface that effectively reduces the number of defects and enhances electron mobility. Devices with only a PCBA‐monolayer‐passivated SnO2 ETL exhibit significantly improved performance and reproducibility, achieving an efficiency of 18.8%. Investigating thick and solvent‐resistant C60 and PCBM‐dimer layers demonstrates that the charge transport in the ETL is only improved by chemisorption of the fullerene at the SnO2 surface.

Poly (3,4-ethylenedioxythiophene) : poly(styrenesulphonic acid) (PEDOT : PSS) is commonly used as an anode in polymer light-emitting diodes (PLED). We have studied the effect of the pH and Na + ion concentration of the aqueous PEDOT : PSS dispersion on the bulk and surface properties of spincoated films by various techniques, including UV-vis-NIR optical absorbance spectrometry, Raman spectroscopy, X-ray Photoelectron Spectroscopy (XPS) and Ultraviolet Photoemission Spectroscopy (UPS). A pH increase by addition of NaOH modifies the PEDOT : PSS properties in a similar way as electrochemical dedoping: the IR absorbance decreases, the Raman peaks shift, sharpen and increase in intensity, and the work function decreases. Consequently, a barrier for hole injection is introduced for several classes of light-emitting polymers. We argue that the mechanism of the pH-effect is different from electrochemical dedoping, and originates from a change in the relative stability of polarons and bipolarons on the doped thiophene. The changes in the electronic properties of PEDOT : PSS point to the determining role of the counter-ion in the stabilisation of oxidised thiophene units. Polymer LEDs comprising Na + -rich, proton poor PEDOT : PSS can show lower lifetime and efficiency than the corresponding Na + -free, proton-rich devices. For light emitting polymers which suffer from the addition of sodium to the hole injecting PEDOT : PSS, the decreased lifetime hints at hole injection as limiting factor in the degradation of these PLEDs.

For 19 diketopyrrolopyrrole polymers, the highest occupied molecular orbital (HOMO) energies are determined from i) the oxidation potential with square-wave voltammetry (SWV), ii) the ionization potential using ultraviolet photoelectron spectroscopy (UPS), and iii) density functional theory (DFT) calculations. The SWV HOMO energies show an excellent linear correlation with the open-circuit voltage (V oc ) of optimized solar cells in which the polymers form blends with a fullerene acceptor ([6,6]-phenyl-C 61 -butyl acid methyl ester or [6,6]-phenyl-C 71 -butyl acid methyl ester).Remarkably, the slope of the best linear fit is 0.75 ± 0.04, i.e., significantly less than unity. A weaker correlation with V oc is found for the HOMO energies obtained from UPS and DFT. Within the experimental error, the SWV and UPS data are correlated with a slope close to unity. The results show that electrochemically determined oxidation potentials provide an excellent method for predicting the V oc of bulk heterojunction solar cells, with absolute deviations less than 0.1 V.

Careful interface design and engineering are “keys” to effectively implement a conformal 10 nm plasma-assisted atomic-layer-deposited NiO film as hole transport layer in a p–i–n perovskite solar cell architecture.