Charge Transfer Dynamics between Carbon Nanotubes and Hybrid Organic Metal Halide Perovskite Films

In spite of the rapid rise of metal organic halide perovskites for next-generation solar cells, little quantitative information on the electronic structure of interfaces of these materials is available. The present study characterizes the electronic structure of interfaces between semiconducting single walled carbon nanotube (SWCNT) contacts and a prototypical methylammonium lead iodide (MAPbI₃) absorber layer. Using photoemission spectroscopy we provide quantitative values for the energy levels at the interface and observe the formation of an interfacial dipole between SWCNTs and perovskite. This process can be ascribed to electron donation from the MAPbI₃ to the adjacent SWCNT making the nanotube film <i>n</i>-type at the interface and inducing band bending throughout the SWCNT layer. We then use transient absorbance spectroscopy to correlate this electronic alignment with rapid and efficient photoexcited charge transfer. The results indicate that SWCNT transport and contact layers facilitate rapid charge extraction and suggest avenues for enhancing device performance

Defect Tolerance in Methylammonium Lead Triiodide Perovskite

Photovoltaic applications of perovskite semiconductor material systems have generated considerable interest in part because of predictions that primary defect energy levels reside outside the bandgap. We present experimental evidence that this enabling material property is present in the halide-lead perovskite, CH₃NH₃PbI₃ (MAPbI₃), consistent with theoretical predictions. By performing X-ray photoemission spectroscopy, we induce and track dynamic chemical and electronic transformations in the perovskite. These data show compositional changes that begin immediately with exposure to X-ray irradiation, whereas the predominant electronic structure of the thin film on compact TiO₂ appears tolerant to the formation of compensating defect pairs of V_I and V_MA and for a large range of I/Pb ratios. Changing film composition is correlated with a shift of the valence-band maximum only as the halide–lead ratio drops below 2.5. This delay is attributed to the invariance of MAPbI₃ electronic structure to distributed defects that can significantly transform the electronic density of states only when in high concentrations

Air-Exposure-Induced Gas-Molecule Incorporation into Spiro-MeOTAD Films

Combined photoemission and charge-transport property studies of the organic hole transport material 2,2′,7,7′-tetrakis­(<i>N</i>,<i>N</i>-di-<i>p</i>-methoxyphenylamine)-9,9′-spirobifluorene (spiro-MeOTAD) under air exposure and controlled environments of O₂, H₂O + N₂, and N₂ (1 atm and under dark conditions) reveal the incorporation of gas molecules causing a decrease in charge mobility. Ultraviolet photoelectron spectroscopy shows the Fermi level shifts toward the highest occupied molecular orbital of spiro-MeOTAD when exposed to air, O₂, and H₂O resembling p-type doping. However, no traces of oxidized spiro-MeOTAD⁺ are observed by X-ray photoelectron spectroscopy (XPS) and UV–visible spectroscopy. The charge-transport properties were investigated by fabricating organic field-effect transistors with the 10 nm active layer at the semiconductor–insulator interface exposed to different gases. The hole mobility decreases substantially upon exposure to air, O₂, and H₂O. In the case of N₂, XPS reveals the incorporation of N₂ molecules into the film, but the decrease in the hole mobility is much smaller

High-Work-Function Molybdenum Oxide Hole Extraction Contacts in Hybrid Organic–Inorganic Perovskite Solar Cells

We investigate the effect of high work function contacts in halide perovskite absorber-based photovoltaic devices. Photoemission spectroscopy measurements reveal that band bending is induced in the absorber by the deposition of the high work function molybdenum trioxide (MoO₃). We find that direct contact between MoO₃ and the perovskite leads to a chemical reaction, which diminishes device functionality. Introducing an ultrathin spiro-MeOTAD buffer layer prevents the reaction, yet the altered evolution of the energy levels in the methylammonium lead iodide (MAPbI₃) layer at the interface still negatively impacts device performance

Disrupted Attosecond Charge Carrier Delocalization at a Hybrid Organic/Inorganic Semiconductor Interface

Despite significant interest in hybrid organic/inorganic semiconductor interfaces, little is known regarding the fate of charge carriers at metal oxide interfaces, particularly on ultrafast time scales. Using core–hole clock spectroscopy, we investigate the ultrafast charge carrier dynamics of conductive ZnO films at a hybrid interface with an organic semiconductor. The adsorption of C₆₀ on the ZnO surface strongly suppresses the ultrafast carrier delocalization and increases the charge carrier residence time from 400 attoseconds to nearly 30 fs. Here, we show that a new hybridized interfacial density of states with substantial molecular character is formed, fundamentally altering the observed carrier dynamics. The remarkable change in the dynamics sheds light on the fate of carriers at hybrid organic/inorganic semiconductor interfaces relevant to organic optoelectronics and provides for the first time an atomistic picture of the electronically perturbed near-interface region of a metal oxide

Dithiocarbamate Self-Assembled Monolayers as Efficient Surface Modifiers for Low Work Function Noble Metals

Tuning the work function of the electrode is one of the crucial steps to improve charge extraction in organic electronic devices. Here, we show that <i>N</i>,<i>N</i>-dialkyl dithiocarbamates (DTC) can be effectively employed to produce low work function noble metal electrodes. Work functions between 3.1 and 3.5 eV are observed for all metals investigated (Cu, Ag, and Au). Ultraviolet photoemission spectroscopy (UPS) reveals a maximum decrease in work function by 2.1 eV as compared to the bare metal surface. Electronic structure calculations elucidate how the complex interplay between intrinsic dipoles and dipoles induced by bond formation generates such large work function shifts. Subsequently, we quantify the improvement in contact resistance of organic thin film transistor devices with DTC coated source and drain electrodes. These findings demonstrate that DTC molecules can be employed as universal surface modifiers to produce stable electrodes for electron injection in high performance hybrid organic optoelectronics

Revisiting the Valence and Conduction Band Size Dependence of PbS Quantum Dot Thin Films

We use a high signal-to-noise X-ray photoelectron spectrum of bulk PbS, GW calculations, and a model assuming parabolic bands to unravel the various X-ray and ultraviolet photoelectron spectral features of bulk PbS as well as determine how to best analyze the valence band region of PbS quantum dot (QD) films. X-ray and ultraviolet photoelectron spectroscopy (XPS and UPS) are commonly used to probe the difference between the Fermi level and valence band maximum (VBM) for crystalline and thin-film semiconductors. However, we find that when the standard XPS/UPS analysis is used for PbS, the results are often unrealistic due to the low density of states at the VBM. Instead, a parabolic band model is used to determine the VBM for the PbS QD films, which is based on the bulk PbS experimental spectrum and bulk GW calculations. Our analysis highlights the breakdown of the Brillioun zone representation of the band diagram for large band gap, highly quantum confined PbS QDs. We have also determined that in 1,2-ethanedithiol-treated PbS QD films the Fermi level position is dependent on the QD size; specifically, the smallest band gap QD films have the Fermi level near the conduction band minimum and the Fermi level moves away from the conduction band for larger band gap PbS QD films. This change in the Fermi level within the QD band gap could be due to changes in the Pb:S ratio. In addition, we use inverse photoelectron spectroscopy to measure the conduction band region, which has similar challenges in the analysis of PbS QD films due to a low density of states near the conduction band minimum

Revisiting the Valence and Conduction Band Size Dependence of PbS Quantum Dot Thin Films

We use a high signal-to-noise X-ray photoelectron spectrum of bulk PbS, GW calculations, and a model assuming parabolic bands to unravel the various X-ray and ultraviolet photoelectron spectral features of bulk PbS as well as determine how to best analyze the valence band region of PbS quantum dot (QD) films. X-ray and ultraviolet photoelectron spectroscopy (XPS and UPS) are commonly used to probe the difference between the Fermi level and valence band maximum (VBM) for crystalline and thin-film semiconductors. However, we find that when the standard XPS/UPS analysis is used for PbS, the results are often unrealistic due to the low density of states at the VBM. Instead, a parabolic band model is used to determine the VBM for the PbS QD films, which is based on the bulk PbS experimental spectrum and bulk GW calculations. Our analysis highlights the breakdown of the Brillioun zone representation of the band diagram for large band gap, highly quantum confined PbS QDs. We have also determined that in 1,2-ethanedithiol-treated PbS QD films the Fermi level position is dependent on the QD size; specifically, the smallest band gap QD films have the Fermi level near the conduction band minimum and the Fermi level moves away from the conduction band for larger band gap PbS QD films. This change in the Fermi level within the QD band gap could be due to changes in the Pb:S ratio. In addition, we use inverse photoelectron spectroscopy to measure the conduction band region, which has similar challenges in the analysis of PbS QD films due to a low density of states near the conduction band minimum

Charge-Transfer States at the Fullerene Interface Cause Nonradiative Recombination Losses in Sn-Based Perovskite Solar Cells

Tin-based perovskite solar cells (PSCs) are emerging as a more environmentally friendly alternative to traditional PSCs that typically contain toxic lead. In this work, we study the influence of the Sn-perovskite/fullerene interface on the open-circuit voltage (Voc). When the fullerene derivative ICBA is used as the electron transport layer, the Voc reaches 0.68 V, while the band gap of the Sn-perovskite is 1.44 eV, giving a voltage deficit of 0.76 V. Using PCBM as the electron transport layer, this deficit is 0.19 V higher. Herein, we identify through Fourier transform photocurrent spectroscopy and luminescence measurements that interfacial charge-transfer states at the Sn-perovskite/fullerene interface induce a nonradiative recombination channel. The energy of these states should be increased in order to mitigate voltage losses at the contacts

Targeted Ligand-Exchange Chemistry on Cesium Lead Halide Perovskite Quantum Dots for High-Efficiency Photovoltaics

The ability to manipulate quantum dot (QD) surfaces is foundational to their technological deployment. Surface manipulation of metal halide perovskite (MHP) QDs has proven particularly challenging in comparison to that of more established inorganic materials due to dynamic surface species and low material formation energy; most conventional methods of chemical manipulation targeted at the MHP QD surface will result in transformation or dissolution of the MHP crystal. In previous work, we have demonstrated record-efficiency QD solar cells (QDSCs) based on ligand-exchange procedures that electronically couple MHP QDs yet maintain their nanocrystalline size, which stabilizes the corner-sharing structure of the constituent PbI₆^4– octahedra with optoelectronic properties optimal for solar energy conversion. In this work, we employ a variety of spectroscopic techniques to develop a molecular-level understanding of the MHP QD surface chemistry in this system. We individually target both the anionic (oleate) and cationic (oleyl­ammonium) ligands. We find that atmospheric moisture aids the process by hydrolysis of methyl acetate to generate acetic acid and methanol. Acetic acid then replaces native oleate ligands to yield QD surface-bound acetate and free oleic acid. The native oleyl­ammonium ligands remain throughout this film deposition process and are exchanged during a final treatment step employing smaller cationsnamely, formamidinium. This final treatment has a narrow processing window; initial treatment at this stage leads to a more strongly coupled QD regime followed by transformation into a bulk MHP film after longer treatment. These insights provide chemical understanding to the deposition of high-quality, electronically coupled MHP QD films that maintain both quantum confinement and their crystalline phase and attain high photovoltaic performance