Rafael Verduzco

High-efficiency two-dimensional Ruddlesden–Popper perovskite solar cells

Three-dimensional organic–inorganic perovskites have emerged as one of the most promising thin-film solar cell materials owing to their remarkable photophysical properties, which have led to power conversion efficiencies exceeding 20 per cent, with the prospect of further improvements towards the Shockley–Queisser limit for a single‐junction solar cell (33.5 per cent). Besides efficiency, another critical factor for photovoltaics and other optoelectronic applications is environmental stability and photostability under operating conditions. In contrast to their three-dimensional counterparts, Ruddlesden–Popper phases—layered two-dimensional perovskite films—have shown promising stability, but poor efficiency at only 4.73 per cent. This relatively poor efficiency is attributed to the inhibition of out-of-plane charge transport by the organic cations, which act like insulating spacing layers between the conducting inorganic slabs. Here we overcome this issue in layered perovskites by producing thin films of near-single-crystalline quality, in which the crystallographic planes of the inorganic perovskite component have a strongly preferential out-of-plane alignment with respect to the contacts in planar solar cells to facilitate efficient charge transport. We report a photovoltaic efficiency of 12.52 per cent with no hysteresis, and the devices exhibit greatly improved stability in comparison to their three-dimensional counterparts when subjected to light, humidity and heat stress tests. Unencapsulated two-dimensional perovskite devices retain over 60 per cent of their efficiency for over 2,250 hours under constant, standard (AM1.5G) illumination, and exhibit greater tolerance to 65 per cent relative humidity than do three-dimensional equivalents. When the devices are encapsulated, the layered devices do not show any degradation under constant AM1.5G illumination or humidity. We anticipate that these results will lead to the growth of single-crystalline, solution-processed, layered, hybrid, perovskite thin films, which are essential for high-performance opto-electronic devices with technologically relevant long-term stability.

Conjugated Block Copolymer Photovoltaics with near 3% Efficiency through Microphase Separation

Organic electronic materials have the potential to impact almost every aspect of modern life including how we access information, light our homes, and power personal electronics. Nevertheless, weak intermolecular interactions and disorder at junctions of different organic materials limit the performance and stability of organic interfaces and hence the applicability of organic semiconductors to electronic devices. Here, we demonstrate control of donor-acceptor heterojunctions through microphase-separated conjugated block copolymers. When utilized as the active layer of photovoltaic cells, block copolymer-based devices demonstrate efficient photoconversion well beyond devices composed of homopolymer blends. The 3% block copolymer device efficiencies are achieved without the use of a fullerene acceptor. X-ray scattering results reveal that the remarkable performance of block copolymer solar cells is due to self-assembly into mesoscale lamellar morphologies with primarily face-on crystallite orientations. Conjugated block copolymers thus provide a pathway to enhance performance in excitonic solar cells through control of donor-acceptor interfaces.

Vertically Aligned Single-Walled Carbon Nanotubes as Low-cost and High Electrocatalytic Counter Electrode for Dye-Sensitized Solar Cells

A novel dye-sensitized solar cell (DSSC) structure using vertically aligned single-walled carbon nanotubes (VASWCNTs) as the counter electrode has been developed. In this design, the VASWCNTs serve as a stable high surface area and highly active electrocatalytic counter-electrode that could be a promising alternative to the conventional Pt analogue. Utilizing a scalable dry transfer approach to form a VASWCNTs conductive electrode, the DSSCs with various lengths of VASWCNTs were studied. VASWCNTs-DSSC with 34 μm original length was found to be the optimal choice in the present study. The highest conversion efficiencies of VASWCNTs-DSSC achieved 5.5%, which rivals that of the reference Pt DSSC. From the electrochemical impedance spectroscopy analysis, it shows that the new DSSC offers lower interface resistance between the electrolyte and the counter electrode. This reproducible work emphasizes the promise of VASWCNTs as efficient and stable counter electrode materials in DSSC device design, especially taking into account the low-cost merit of this promising material.

Structural investigation of PAMAM dendrimers in aqueous solutions using small-angle neutron scattering: effect of generation.

We investigate a series of poly(amidoamine) starburst dendrimers (PAMAM) of different generations in acidic, aqueous solutions using small-angle neutron scattering (SANS). While the overall molecular size is found to be practically unaffected by a pD change, a strong generational dependence of counterion association is revealed. Upon increasing the dendrimer generation, the effective charge obtained from our SANS experiments only shows a small increase in contrast to the nearly exponential increase predicted by a recent atomic simulation. We also find that with the same degree of molecular protonation the specific counterion association, which is defined as the ratio of bound chloride anions to positively charged amines in solutions, is larger for higher-generation PAMAM dendrimer. The associated counterion density also increases upon increasing generation number.

Synthesis and crystallinity of all-conjugated poly(3-hexylthiophene) block copolymers

A simplified approach towards the synthesis of high molecular weight (Mw > 50 kg mol−1) poly(3-hexylthiophene) (P3HT)-based all-conjugated block copolymers is demonstrated and applied to prepare a series of all-conjugated block copolymers. Grazing-incidence X-ray scattering measurements show that P3HT crystallization is suppressed in all-conjugated block copolymers with low (<25 wt%) P3HT content.

Short-Range Smectic Order in Bent-Core Nematic Liquid Crystals

Small angle X-ray diffraction from the uniaxial nematic phase of certain bent-core liquid crystals is shown to be consistent with the presence of molecular clusters possessing short-range tilted smectic (smectic-C) order. Persistence of these clusters throughout the nematic phase, and even into the isotropic state, likely accounts for the unusual macroscopic behavior previously reported in bent-core nematics, including an anomalously large flexoelectric effect (∼ 1000 times that of conventional calamitic nematics), very large orientational and flow viscosities (∼ 10–100 and ∼ 100–1000 times, respectively, typical values for calamitics), and an extraordinary flow birefringence observed in the isotropic state.

Dynamic self-stiffening in liquid crystal elastomers

Biological tissues have the remarkable ability to remodel and repair in response to disease, injury, and mechanical stresses. Synthetic materials lack the complexity of biological tissues, and man-made materials which respond to external stresses through a permanent increase in stiffness are uncommon. Here, we report that polydomain nematic liquid crystal elastomers increase in stiffness by up to 90% when subjected to a low-amplitude (5%), repetitive (dynamic) compression. Elastomer stiffening is influenced by liquid crystal content, the presence of a nematic liquid crystal phase and the use of a dynamic as opposed to static deformation. Through rheological and X-ray diffraction measurements, stiffening can be attributed to a nematic director which rotates in response to dynamic compression. Stiffening under dynamic compression has not been previously observed in liquid crystal elastomers and may be useful for the development of self-healing materials or for the development of biocompatible, adaptive materials for tissue replacement.

Giant flexoelectricity in bent-core nematic liquid crystal elastomers

Recently ferroelectric ceramic and bent-core nematic liquid crystals have demonstrated flexoelectricity (coupling between curvature strains to electric polarization) up to 104 times larger than the previous standards. This may allow for usable electromechanical devices. However, ceramics are too rigid to withstand large bending and bent-core nematic fluids must be physically supported—their technological applicability is still limited. In this paper, we show that novel side-chain bent-core nematic elastomers not only produce giant flexoelectricity but are also robust and flexible enough for microscale parasitic power generation.

Quantitative analysis of structure and bandgap changes in graphene oxide nanoribbons during thermal annealing.

Graphene oxide nanoribbons (GONRs) are wide bandgap semiconductors that can be reduced to metallic graphene nanoribbons. The transformation of GONRs from their semiconductive to the metallic state by annealing has attracted significant interest due to its simplicity. However, the detailed process by which GONRs transform from wide-bandgap semiconductors to semimetals with a near zero bandgap is unclear. As a result, precise control of the bandgap between these two states is not currently achievable. Here, we quantitatively examine the removal of oxygen-containing groups and changes in the bandgap during thermal annealing of GONRs. X-ray photoelectron spectroscopy measurements show the progressive removal of oxygen-containing functional groups. Aberration-corrected scanning transmission electron microscopy reveals that initially small graphene regions in GONRs become large stacked graphitic layers during thermal annealing. These structural and chemical changes are correlated with progressive changes in the electrochemical bandgap, monitored by cyclic voltammetry. These results show that small changes in the thermal annealing temperature result in significant changes to the bandgap and chemical composition of GONRs and provide a straightforward method for tuning the bandgap in oxidized graphene structures.

Amphiphilic poly(alkylthiophene) block copolymers prepared via externally initiated GRIM and click coupling

Block copolymers with a poly(3-alkylthiophene) (P3AT) polymer block can self-organize into periodic, crystalline nanostructures that may be useful for organic electronic applications. However, reliable synthetic methods for the preparation of P3AT block copolymers are lacking. Here, we demonstrate a general method for the synthesis of P3AT rod-coil block copolymers via click-coupling of alkynyl-P3AT. Alkynyl-P3ATs are prepared via externally initiated Grignard metathesis polymerization (GRIM) using a modified nickel catalyst followed by end-group modification. The resulting alkynyl-P3ATs have improved stability and solubility compared with those previously reported. P3ATs are subsequently coupled to an azide-functionalized poly(ethylene glycol) through copper-catalyzed azide–alkyne click coupling, resulting in P3AT-b-PEG block copolymers. The advantages of this synthetic procedure are the improved stability of the alkynyl-P3AT macroreagent, the capability to synthesize high molecular weight P3AT polymer blocks, and facile determination of P3AT absolute molecular weight through 1H NMR analysis. This synthetic method is applied to prepare a series of P3AT-b-PEG block copolymers, with poly(3-hexyl thiophene) (P3HT), poly(3-dodecylthiophene) (P3DDT), and poly(3-(2′-ethyl)hexylthiophene) (P3EHT) polymer blocks. The resulting P3AT block copolymers are dispersed in water to form micelles with crystalline, hydrophobic cores. Absorbance measurements show that crystallization of P3DDT and P3EHT blocks is suppressed in micellar cores due to nanoscale confinement of the P3AT blocks.