The electrochemical carbon dioxide reduction reaction (CORR) produces diverse chemical species. Cu clusters with a judiciously controlled surface coordination number (CN) provide active sites that simultaneously optimize selectivity, activity, and efficiency for CORR. Here we report a strategy involving metal-organic framework (MOF)-regulated Cu cluster formation that shifts CO electroreduction toward multiple-carbon product generation. Specifically, we promoted undercoordinated sites during the formation of Cu clusters by controlling the structure of the Cu dimer, the precursor for Cu clusters. We distorted the symmetric paddle-wheel Cu dimer secondary building block of HKUST-1 to an asymmetric motif by separating adjacent benzene tricarboxylate moieties using thermal treatment. By varying materials processing conditions, we modulated the asymmetric local atomic structure, oxidation state and bonding strain of Cu dimers. Using electron paramagnetic resonance (EPR) and in situ X-ray absorption spectroscopy (XAS) experiments, we observed the formation of Cu clusters with low CN from distorted Cu dimers in HKUST-1 during CO electroreduction. These exhibited 45% CH faradaic efficiency (FE), a record for MOF-derived Cu cluster catalysts. A structure-activity relationship was established wherein the tuning of the Cu-Cu CN in Cu clusters determines the CORR selectivity.

Control over carrier type and doping levels in semiconductor materials is key for optoelectronic applications. In colloidal quantum dots (CQDs), these properties can be tuned by surface chemistry modification, but this has so far been accomplished at the expense of reduced surface passivation and compromised colloidal solubility; this has precluded the realization of advanced architectures such as CQD bulk homojunction solids. Here we introduce a cascade surface modification scheme that overcomes these limitations. This strategy provides control over doping and solubility and enables n-type and p-type CQD inks that are fully miscible in the same solvent with complete surface passivation. This enables the realization of homogeneous CQD bulk homojunction films that exhibit a 1.5 times increase in carrier diffusion length compared with the previous best CQD films. As a result, we demonstrate the highest power conversion efficiency (13.3%) reported among CQD solar cells.

Colloidal nanocrystals combine size-and facet-dependent properties with solution processing. They offer thus a compelling suite of materials for technological

Understanding and controlling interfacial charge transfer at the heterojunction of optoelectronic devices is currently receiving extensive interest. Here, we study the parameters that can influence the electron extraction in planar perovskite solar cells (P-PSCs) using spin-coated SnO2 and TiO2, anodized-TiO2 (a-TiO2), and bilayered electron transport layers (ETL) composed of SnO2 and TiO2 or SnO2 on a-TiO2 (SnO2@a-TiO2). These are the varied free energy difference (ΔG) values between the ETL and perovskites, electron mobility (μe) of the ETL, and quality of physical contact between the ETL and fluorine-doped tin oxide (FTO). Among the various ETLs, the bilayered ETL (SnO2@a-TiO2) gives a large ΔG as well as defect-free physical contact. The resulting P-PSC exhibits a PCE of 21.1% and stabilized efficiency of 20.2% with reduced hysteresis. This result emphasizes that a large free energy difference (ΔG) value plays an important role in electron extraction. More importantly, the defect-free physical contact is also crucial for achieving improved electron extraction.

An electron transporting layer (ETL) plays an important role in extracting electrons from a perovskite layer and blocking recombination between electrons in the fluorine-doped tin oxide (FTO) and holes in the perovskite layers, especially in planar perovskite solar cells. Dense TiO2 ETLs prepared by a solution-processed spin-coating method (S-TiO2) are mainly used in devices due to their ease of fabrication. Herein, we found that fatal morphological defects at the S-TiO2 interface due to a rough FTO surface, including an irregular film thickness, discontinuous areas, and poor physical contact between the S-TiO2 and the FTO layers, were inevitable and lowered the charge transport properties through the planar perovskite solar cells. The effects of the morphological defects were mitigated in this work using a TiO2 ETL produced from sputtering and anodization. This method produced a well-defined nanostructured TiO2 ETL with an excellent transmittance, single-crystalline properties, a uniform film thickness, a large effective area, and defect-free physical contact with a rough substrate that provided outstanding electron extraction and hole blocking in a planar perovskite solar cell. In planar perovskite devices, anodized TiO2 ETL (A-TiO2) increased the power conversion efficiency by 22% (from 12.5 to 15.2%), and the stabilized maximum power output efficiency increased by 44% (from 8.9 to 12.8%) compared with S-TiO2. This work highlights the importance of the ETL geometry for maximizing device performance and provides insights into achieving ideal ETL morphologies that remedy the drawbacks observed in conventional spin-coated ETLs.

The tunable bandgap of colloidal quantum dots (CQDs) makes them an attractive material for photovoltaics (PV). The best present-day CQD PV devices employ zinc oxide (ZnO) as an electron transport layer; however, it is found herein that ZnO's surface defect sites and unfavorable electrical band alignment prevent devices from realizing their full potential. Here, chloride (Cl)-passivated ZnO generated from a solution of presynthesized ZnO nanoparticles treated using an organic-solvent-soluble Cl salt is reported. These new ZnO electrodes exhibit decreased surface trap densities and a favorable electronic band alignment, improving charge extraction from the CQD layer and achieving the best-cell power conversion efficiency (PCE) of 11.6% and an average PCE of 11.4 ± 0.2%.

No abstract

Wide-bandgap (WBG) formamidinium-cesium (FA-Cs) lead iodide-bromide mixed perovskites are promising materials for front cells well-matched with crystalline silicon to form tandem solar cells. They offer avenues to augment the performance of widely deployed commercial solar cells. However, phase instability, high open-circuit voltage (V ) deficit, and large hysteresis limit this otherwise promising technology. Here, by controlling the crystallization of FA-Cs WBG perovskite with the aid of a formamide cosolvent, light-induced phase segregation and hysteresis in perovskite solar cells are suppressed. The highly polar solvent additive formamide induces direct formation of the black perovskite phase, bypassing the yellow phases, thereby reducing the density of defects in films. As a result, the optimized WBG perovskite solar cells (PSCs) (E ≈ 1.75 eV) exhibit a high V of 1.23 V, reduced hysteresis, and a power conversion efficiency (PCE) of 17.8%. A PCE of 15.2% on 1.1 cm solar cells, the highest among the reported efficiencies for large-area PSCs having this bandgap is also demonstrated. These perovskites show excellent phase stability and thermal stability, as well as long-term air stability. They maintain ≈95% of their initial PCE after 1300 h of storage in dry air without encapsulation.