Lijia Liu

Dissociation of Methylammonium Cations in Hybrid Organic–Inorganic Perovskite Solar Cells

Organic-inorganic lead perovskites have shown great promise as photovoltaic materials, and within this class of materials (CH3NH3)PbI3-xClx is of particular interest. Herein we use soft X-ray spectroscopy and density functional theory calculations to demonstrate that the methylammonium cations in a typical photovoltaic layer may dissociate into a metastable arrangement of CH3I-Pb2 defects and trapped NH3. The possibility that other metastable configurations of the organic components in (CH3NH3)PbI3-xClx is rarely considered but adds an entirely new dimension in understanding the charge trapping, ionic transport, and structural degradation mechanisms in these materials. Understanding the influence of these other configurations is of critical importance for further improving the performance of these photovoltaics.

Iodomethane-Mediated Organometal Halide Perovskite with Record Photoluminescence Lifetime

Organometallic lead halide perovskites are excellent light harvesters for high-efficiency photovoltaic devices. However, as the key component in these devices, a perovskite thin film with good morphology and minimal trap states is still difficult to obtain. Herein we show that by incorporating a low boiling point alkyl halide such as iodomethane (CH3I) into the precursor solution, a perovskite (CH3NH3PbI3-xClx) film with improved grain size and orientation can be easily achieved. More importantly, these films exhibit a significantly reduced amount of trap states. Record photoluminescence lifetimes of more than 4 μs are achieved; these lifetimes are significantly longer than that of pristine CH3NH3PbI3-xClx films. Planar heterojunction solar cells incorporating these CH3I-mediated perovskites have demonstrated a dramatically increased power conversion efficiency compared to the ones using pristine CH3NH3PbI3-xClx. Photoluminescence, transient absorption, and microwave detected photoconductivity measurements all provide consistent evidence that CH3I addition increases the number of excitons generated and their diffusion length, both of which assist efficient carrier transport in the photovoltaic device. The simple incorporation of alkyl halide to enhance perovskite surface passivation introduces an important direction for future progress on high efficiency perovskite optoelectronic devices.

Self-Alignment of the Methylammonium Cations in Thin-Film Organometal Perovskites

A comparative study of the electronic structure of methylammonium (CH3NH3) in organometallic lead triiodide perovskite (CH3NH3PbI3) thin films synthesized using either one- or two-step deposition protocols is performed using angle-resolved C K-edge soft X-ray absorption spectroscopy (XAS) and model calculations. We find that our XAS measurements can be accurately related to the ground-state unoccupied orbitals using a simple crystal field model. We further find that films made by the one-step deposition protocol exhibit angle-dependent features, indicating long-range alignment of the CH3NH3 molecules, although the angle-dependency decreases as the film thickness increases. No angle-dependency was observed in the films made via the two-step deposition method.

Influence of crystal phase on TiO2 nanowire anodes in sodium ion batteries

Nanostructured TiO2 is a promising anode material for Na-ion batteries. In this work, we present a comparative study of anatase and B-phase TiO2 nanowires used for this purpose. We employ X-ray absorption spectroscopy and density functional theory in addition to standard characterization methods to reveal that Na is inserted into both anatase and B-phase nanowires, and that the reversible (de)sodiation capacity is almost the same for both. However the long-term stability of anatase-based Na-ion batteries is poorer than B-phase-based Na-ion batteries. We propose this is due to the irreversible formation of NaxTiO2 near the surface, which blocks Na diffusion. Improved Na-ion battery performance may therefore be obtained using TiO2(B) anodes and by choosing nanostructure geometries with rough surfaces, limiting the unwanted blocking ability of surface barrier layers.

A chlorine-free protocol for processing germanium

A quinone/catechol redox platform replaces Cl2 or HCl for processing germanium metal or germanium dioxide to germanes. Replacing molecular chlorine and hydrochloric acid with less energy- and risk-intensive reagents would markedly improve the environmental impact of metal manufacturing at a time when demand for metals is rapidly increasing. We describe a recyclable quinone/catechol redox platform that provides an innovative replacement for elemental chlorine and hydrochloric acid in the conversion of either germanium metal or germanium dioxide to a germanium tetrachloride substitute. Germanium is classified as a “critical” element based on its high dispersion in the environment, growing demand, and lack of suitable substitutes. Our approach replaces the oxidizing capacity of chlorine with molecular oxygen and replaces germanium tetrachloride with an air- and moisture-stable Ge(IV)-catecholate that is kinetically competent for conversion to high-purity germanes.

Reduced GeO2 Nanoparticles: Electronic Structure of a Nominal GeOx Complex and Its Stability under H2 Annealing.

A nominal GeOx (x ≤ 2) compound contains mixtures of Ge, Ge suboxides, and GeO2, but the detailed composition and crystallinity could vary from material to material. In this study, we synthesize GeOx nanoparticles by chemical reduction of GeO2, and comparatively investigate the freshly prepared sample and the sample exposed to ambient conditions. Although both compounds are nominally GeOx, they exhibit different X-ray diffraction patterns. X-ray absorption fine structure (XAFS) is utilized to analyse the detailed structure of GeOx. We find that the two initial GeOx compounds have entirely different compositions: the fresh GeOx contains large amorphous Ge clusters connected by GeOx, while after air exposure; the Ge clusters are replaced by a GeO2-GeOx composite. In addition, the two GeOx products undergo different structural rearrangement under H2 annealing, producing different intermediate phases before ultimately turning into metallic Ge. In the fresh GeOx, the amorphous Ge remains stable, with the GeOx being gradually reduced to Ge, leading to a final structure of crystalline Ge grains connected by GeOx. The air-exposed GeOx on the other hand, undergoes a GeO2→GeOx→Ge transition, in which H2 induces the creation of oxygen vacancies at intermediate stage. A complete removal of oxides occurs at high temperature.

Prospects for Mitigating Intrinsic Organic Decomposition in Methylammonium Lead Triiodide Perovskite

Organometallic lead halide perovskites seem to be on the threshold of becoming viable commercial photovoltaics; however, further improvements to the stability of these materials must be made before they can compete with existing photovoltaic technologies. Of the organometallic lead halide perovskites used in photovoltaics, methylammonium lead triiodide perovskite (MAPI) is perhaps the most studied, and understanding how MAPI degrades is crucial for developing strategies to improve stability. We discuss the experimental evidence behind several possible routes for MAPI to degrade into PbI2 and various organics, and how the decomposition path of MAPI may strongly depend on substrate, precursors, intrinsic organic defects, and morphology. Exploring the conditions required for MAPI to degrade according to a particular pathway is important not only from a fundamental materials chemistry perspective, but also for understanding intrinsic instability in MAPI-based photovoltaics and to develop strategies to improve stability.

Beyond Oxidation States: Distinguishing Chemical States of Gallium in Compounds with Multiple Gallium Centers

The electronic structures of a series of gallium complexes are examined using X-ray absorption spectroscopy (XAS) in combination with ab initio calculations. The chemical states of Ga are strongly affected by the ligands and the bonding environment. For complexes containing multiple gallium sites, we demonstrate that XAS can identify the chemical state of each unique gallium center. A reliable understanding of the chemical nature of the core element in a coordination complex with strong core-ligand interaction can be obtained only when both experimental and theoretical approaches are combined.