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Self-assembled monolayers of thiolates on metals as a form of nanotechnology.

Within the space of a few years, hybrid organic–inorganic perovskite solar cells have emerged as one of the most exciting material platforms in the photovoltaic sector. This review describes the rapid progress that has been made in this area.

The emergence of perovskite solar cells

Atomic layer deposition: an overview.

Because of the remarkably high theoretical energy output, metal–air batteries represent one class of promising power sources for applications in next-generation electronics, electrified transportation and energy storage of smart grids. The most prominent feature of a metal–air battery is the combination of a metal anode with high energy density and an air electrode with open structure to draw cathode active materials (i.e., oxygen) from air. In this critical review, we present the fundamentals and recent advances related to the fields of metal–air batteries, with a focus on the electrochemistry and materials chemistry of air electrodes. The battery electrochemistry and catalytic mechanism of oxygen reduction reactions are discussed on the basis of aqueous and organic electrolytes. Four groups of extensively studied catalysts for the cathode oxygen reduction/evolution are selectively surveyed from materials chemistry to electrode properties and battery application: Pt and Pt-based alloys (e.g., PtAu nanoparticles), carbonaceous materials (e.g., graphene nanosheets), transition-metal oxides (e.g., Mn-based spinels and perovskites), and inorganic–organic composites (e.g., metal macrocycle derivatives). The design and optimization of air-electrode structure are also outlined. Furthermore, remarks on the challenges and perspectives of research directions are proposed for further development of metal–air batteries (219 references).

Metal–air batteries: from oxygen reduction electrochemistry to cathode catalysts

In recent years, the record efficiency of perovskite solar cells (PSCs) has been updated from 9.7% to 20.1%. However, there has been very little study of the issue of stability, which restricts the outdoor application of PSCs. The issues of the degradation of perovskite and the stability of PSC devices should be urgently addressed to achieve good reproducibility and long lifetimes for PSCs with high conversion efficiency. Without studies on stability, exciting achievements cannot be transferred from the laboratory to industry and outdoor applications. In order to improve their stability, a basic understanding of the degradation process of PSCs in different conditions should be acquired via thorough study. This review summarizes recent studies of the relationship of the chemical stability of PSCs with their environment (oxygen and moisture, UV light, solution process, temperature) and corresponding possible solutions.

Review of recent progress in chemical stability of perovskite solar cells

Single Al2O3 atomic layer deposition (ALD) films on polymers have demonstrated excellent gas diffusion barrier properties. Further improvements can be achieved using multilayers of Al2O3 ALD layers with other inorganic layers. In this study, multilayers of Al2O3 ALD and rapid SiO2 ALD were grown on Kapton and heat-stabilized polyethylene naphthalate substrates. Transmission rates for tritium through the films were measured using the radioactive HTO tracer method. Comparison with previous Ca tests and tritium exchange experiments with alcohols indicated that the tritium in HTO may diffuse as either molecular HTO or atomic tritium. Assuming that the tritium diffuses only as HTO, single Al2O3 ALD films reduced the effective water vapor transmission rate (WVTR) to ∼1 × 10-3 g/m2/day. When the Al2O3 ALD film was directly exposed to the saturated H2O/HTO vapor pressure, the barrier properties deteriorated markedly after 4−5 days. Al2O3 ALD barriers that were not subjected to direct H2O/HTO exposure indefinitely...

Gas Diffusion Barriers on Polymers Using Multilayers Fabricated by Al2O3 and Rapid SiO2 Atomic Layer Deposition

The fabrication of many devices in modern technology requires techniques for growing thin films. As devices miniaturize, manufacturers will need to control thin film growth at the atomic level. Because many devices have challenging morphologies, thin films must be able to coat conformally on structures with high aspect ratios. Techniques based on atomic layer deposition (ALD), a special type of chemical vapor deposition, allow for the growth of ultra-thin and conformal films of inorganic materials using sequential, self-limiting reactions. Molecular layer deposition (MLD) methods extend this strategy to include organic and hybrid organic−inorganic polymeric materials. In this Account, we provide an overview of the surface chemistry for the MLD of organic and hybrid organic−inorganic polymers and examine a variety of surface chemistry strategies for growing polymer thin films. Previously, surface chemistry for the MLD of organic polymers such as polyamides and polyimides has used two-step AB reaction cycle...

Surface chemistry for molecular layer deposition of organic and hybrid organic-inorganic polymers.

Thin films grown by Al2O3 atomic layer deposition (ALD) and SiN plasma-enhanced chemical vapor deposition (PECVD) have been tested as gas diffusion barriers either individually or as bilayers on polymer substrates. Single films of Al2O3 ALD with thicknesses of ≥10 nm had a water vapor transmission rate (WVTR) of ≤5×10−5 g/m2 day at 38 °C/85% relative humidity (RH), as measured by the Ca test. This WVTR value was limited by H2O permeability through the epoxy seal, as determined by the Ca test for the glass lid control. In comparison, SiN PECVD films with a thickness of 100 nm had a WVTR of ∼7×10−3 g/m2 day at 38 °C/85% RH. Significant improvements resulted when the SiN PECVD film was coated with an Al2O3 ALD film. An Al2O3 ALD film with a thickness of only 5 nm on a SiN PECVD film with a thickness of 100 nm reduced the WVTR from ∼7×10−3 to ≤5×10−5 g/m2 day at 38 °C/85% RH. The reduction in the permeability for Al2O3 ALD on the SiN PECVD films was attributed to either Al2O3 ALD sealing defects in the SiN PE...

Gas diffusion ultrabarriers on polymer substrates using Al2O3 atomic layer deposition and SiN plasma-enhanced chemical vapor deposition

Six customized phenylene-ethynylene-based oligomers have been studied for their electronic properties using scanning tunneling microscopy to test hypothesized mechanisms of stochastic conductance switching. Previously suggested mechanisms include functional group reduction, functional group rotation, backbone ring rotation, neighboring molecule interactions, bond fluctuations, and hybridization changes. Here, we test these hypotheses experimentally by varying the molecular designs of the switches; the ability of the molecules to switch via each hypothetical mechanism is selectively engineered into or out of each molecule. We conclude that hybridization changes at the molecule-surface interface are responsible for the switching we observe.

Molecular Engineering and Measurements To Test Hypothesized Mechanisms in Single Molecule Conductance Switching

We have designed monolayers with weak intermolecular interactions for use as placeholders in intelligent self- and directed-assembly. We have shown that these 1-adamantanethiolate monolayers are labile with respect to displacement by exposing them to dilute solutions of alkanethiols. These self-assembled monolayers (SAMs) of 1-adamantanethiol on Au{111} were probed using ambient scanning tunneling microscopy (STM), and their assembled order was determined. Solution deposition of the molecules results in a highly ordered hexagonally close-packed molecular lattice with a measured nearest neighbor distance of 6.9 +/- 0.4 A. The SAMs exhibit several rotational domains, but lack the protruding domain boundaries typical of alkanethiolate SAMs, and are similarly stable at room temperature. Co-deposition of alkanethiol and 1-adamantanethiol from solution results in alkanethiolate SAMs, except when using extremely low alkanethiol to 1-adamantanethiol concentration ratios. Facile displacement of low interaction strength SAMs can be exploited to enhance patterning using soft nanolithography.

Arrelaine A. Dameron

Papers

Gas Diffusion Barriers on Polymers Using Multilayers Fabricated by Al2O3 and Rapid SiO2 Atomic Layer Deposition

Surface chemistry for molecular layer deposition of organic and hybrid organic-inorganic polymers.

Gas diffusion ultrabarriers on polymer substrates using Al2O3 atomic layer deposition and SiN plasma-enhanced chemical vapor deposition

Molecular Engineering and Measurements To Test Hypothesized Mechanisms in Single Molecule Conductance Switching

Structures and displacement of 1-adamantanethiol self-assembled monolayers on Au{111}.