Julian Kalb

Toward High-Efficiency Solution-Processed Planar Heterojunction Sb2S3 Solar Cells

Low‐cost hybrid solar cells have made tremendous steps forward during the past decade owing to the implementation of extremely thin inorganic coatings as absorber layers, typically in combination with organic hole transporters. Using only extremely thin films of these absorbers reduces the requirement of single crystalline high‐quality materials and paves the way for low‐cost solution processing compatible with roll‐to‐roll fabrication processes. To date, the most efficient absorber material, except for the recently introduced organic–inorganic lead halide perovskites, has been Sb2S3, which can be implemented in hybrid photovoltaics using a simple chemical bath deposition. Current high‐efficiency Sb2S3 devices utilize absorber coatings on nanostructured TiO2 electrodes in combination with polymeric hole transporters. This geometry has so far been the state of the art, even though flat junction devices would be conceptually simpler with the additional potential of higher open circuit voltages due to reduced charge carrier recombination. Besides, the role of the hole transporter is not completely clarified yet. In particular, additional photocurrent contribution from the polymers has not been directly shown, which points toward detrimental parasitic light absorption in the polymers. This study presents a fine‐tuned chemical bath deposition method that allows fabricating solution‐processed low‐cost flat junction Sb2S3 solar cells with the highest open circuit voltage reported so far for chemical bath devices and efficiencies exceeding 4%. Characterization of back‐illuminated solar cells in combination with transfer matrix‐based simulations further allows to address the issue of absorption losses in the hole transport material and outline a pathway toward more efficient future devices.

Thiophene-Functionalized Hybrid Perovskite Microrods and their Application in Photodetector Devices for Investigating Charge Transport Through Interfaces in Particle-Based Materials

Particle-based semiconductor materials are promising constituents of future technologies. They are described by unique features resulting from the combination of discrete nanoparticle characteristics and the emergence of cooperative phenomena based on long-range interaction within their superstructure. (Nano)particles of outstanding quality with regards to size and shape can be prepared via colloidal synthesis using appropriate capping agents. The classical capping agents are electrically insulating, which impedes particle-particle electronic communication. Consequently, there exists a high demand for realizing charge transport through interfaces especially for semiconductors of relevance like hybrid perovskites (HYPEs), for example, CH3NH3PbI3 (MAPI) as one of the most prominent representatives. Of particular interest are crystals in the micrometer range, as they possess synergistic advantages of single crystalline bulk properties, shape control as well as the possibility of being functionalized. Here we provide a synthetic strategy toward thiophene-functionalized single crystalline MAPI microrods originating from the single source precursor CH3NH3PbI3TEG2 (TEG = triethylene glycol). In the dark, the microrods show enhanced charge transport characteristics of holes over 2 orders of magnitude compared to microscale cuboids with insulating alkyl surface modifiers and nonfunctionalized random sized particles. In large-area prototype photodetector devices (2.21 cm2), the thiophene functionalization improves the response times because of the interparticle charge transport (tON = 190 ms, tOFF = 430 ms) compared to alkyl-functionalized particles (tON = 1055 ms, tOFF = 60 ms), at similar responsivities of 0.65 and 0.71 mA W-1, respectively. Further, the surface functionalization and crystal grains on the micrometer scale improve the device stability. Therefore, this study provides clear evidence for the interplay and importance of crystal size, shape and surface modification of MAPI crystals, which is of major importance in every optoelectronic device.

Tuning the Electronic Conductivity in Hydrothermally Grown Rutile TiO2 Nanowires: Effect of Heat Treatment in Different Environments

Hydrothermally grown rutile TiO2 nanowires are intrinsically full of lattice defects, especially oxygen vacancies. These vacancies have a significant influence on the structural and electronic properties of the nanowires. In this study, we report a post-growth heat treatment in different environments that allows control of the distribution of these defects inside the nanowire, and thus gives direct access to tuning of the properties of rutile TiO2 nanowires. A detailed transmission electron microscopy study is used to analyze the structural changes inside the nanowires which are correlated to the measured optical and electrical properties. The highly defective as-grown nanowire arrays have a white appearance and show typical semiconducting properties with n-type conductivity, which is related to the high density of oxygen vacancies. Heat treatment in air atmosphere leads to a vacancy condensation and results in nanowires which possess insulating properties, whereas heat treatment in N2 atmosphere leads to nanowire arrays that appear black and show almost metal-like conductivity. We link this high conductivity to a TiO2−x shell which forms during the annealing process due to the slightly reducing N2 environment.

Role of the Metal-Oxide Work Function on Photocurrent Generation in Hybrid Solar Cells

ZnO is a widely used metal-oxide semiconductor for photovoltaic application. In solar cell heterostructures they not only serve as a charge selective contact, but also act as electron acceptor. Although ZnO offers a suitable interface for exciton dissociation, charge separation efficiencies have stayed rather poor and conceptual differences to organic acceptors are rarely investigated. In this work, we employ Sn doping to ZnO nanowires in order to understand the role of defect and surface states in the charge separation process. Upon doping we are able to modify the metal-oxide work function and we show its direct correlation with the charge separation efficiency. For this purpose, we use the polymer poly(3-hexylthiophene) as donor and the squaraine dye SQ2 as interlayer. Interestingly, neither mobilities nor defects are prime performance limiting factor, but rather the density of available states around the conduction band is of crucial importance for hybrid interfaces. This work highlights crucial aspects to improve the charge generation process of metal-oxide based solar cells and reveals new strategies to improve the power conversion efficiency of hybrid solar cells.

Incoherent Pathways of Charge Separation in Organic and Hybrid Solar Cells

In this work, we investigate the exciton dissociation dynamics occurring at the donor:acceptor interface in organic and hybrid blends employed in the realization of photovoltaic cells. Fundamental differences in the charge separation process are studied with the organic semiconductor polymer poly(3-hexylthiophene) (P3HT) and either [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) or titanium dioxide (TiO2) acting as the acceptor. By using ultrafast broad-band transient absorption spectroscopy with few-fs temporal resolution, we observe that in both cases the incoherent formation of free charges dominates the charge generation process. From the optical response of the polymer and by tracking the excited-state absorption, we extract pivotal similarities in the incoherent energy pathways that follow the impulsive excitation. On time scales shorter than 200 fs, we observe that the two acceptors display similar dynamics in the exciton delocalization. Significant differences arise only on longer time scales with only an impact on the overall photocarrier generation efficiency.

Fabrication and characterization of abrupt TiO2–SiOx core-shell nanowires by a simple heat treatment

Three dimensional hierarchical metal oxide nanostructures, like TiO2 nanowire arrays, have attracted great attention for electrochemical energy conversion and storage applications. The functionality of such devices can be further enhanced by adding a nanowire shell with a different stoichiometry or composition compared to the core. Here, we report an approach with a facile heat treatment at 1050 °C, which allows the fabrication of rutile TiO2–SiOx core-shell nanowire arrays on silicon substrates. Our detailed electron microscopic investigation shows that this method is able to cover hydrothermally grown rutile TiO2 nanowires with a uniform shell of several nanometers in thickness. Moreover, the treatment improves the quality of the rutile TiO2 core by removing lattice defects, introduced from the hydrothermal growth. Electron energy loss spectroscopy reveals that the homogeneous shell around the TiO2 core consists of amorphous SiOx and does not form any intermediate phase with TiO2 at the interface. Thus,...