U-Ser Jeng

Improving device efficiency of polymer/fullerene bulk heterojunction solar cells through enhanced crystallinity and reduced grain boundaries induced by solvent additives.

Polymer solar cells based on bulk heterojunction (BHJ) structures, featuring conjugated polymers as donors and fullerene derivatives as acceptors, [ 1 ] are being developed for their potential application in the low-cost fabrication of large-area devices. In recent reports, BHJ solar cells incorporating crystalline or low-bandgap conjugated polymers [ 2 ] and fullerene derivatives have exhibited maximum power conversion effi ciencies (PCEs) of up to 8%. [ 3 ] The morphology [ 4 ] of the active layer in a BHJ solar cell incorporating a polymer/fullerene thin fi lm plays a critical role affecting the device performance; phase-separated domains in the active layer provide not only interfaces for charge separation of photogenerated excitons but also percolation pathways for charge carrier transport to the respective electrodes, critically affecting the device’s PCE. The nanoscale morphology of a polymer/fullerene thin fi lm is greatly affected by (i) the fi lm processing conditions, [ 5 ] (ii) the molar ratio (composition) of the polymer and the fullerene, [ 6 ] and (iii) the nature of the solvent additive (if any). [ 7 ] In particular, BHJ polymer solar cells can exhibit improved device performance after undergoing thermal or solvent annealing or the incorporation of solvent additives, all of which alter the fi lm morphology to a more favorable state relative to that of the as-cast fi lm or the fi lm in the absence of the additive, presumably resulting from (i) self-organization of the polymer units into ordered structures and (ii) appropriate aggregation of fullerene domains to provide percolation networks for charge carrier transport. [ 6 , 8 ] Among these approaches, the addition of solvent additive during the processing of the active layer is the simplest and most effective means of optimizing a BHJ device’s morphology; it infl uences the size of the fullerene domains and enhances the crystallinity of the self-organized polymers by improving the solubility of

Competition between Fullerene Aggregation and Poly(3-hexylthiophene) Crystallization upon Annealing of Bulk Heterojunction Solar Cells

Concomitant development of [6,6]-phenyl-C(61)-butyric acid methyl ester (PCBM) aggregation and poly(3-hexylthiophene) (P3HT) crystallization in bulk heterojunction (BHJ) thin-film (ca. 85 nm) solar cells has been revealed using simultaneous grazing-incidence small-/wide-angle X-ray scattering (GISAXS/GIWAXS). With enhanced time and spatial resolutions (5 s/frame; minimum q ≈ 0.004 Å(-1)), synchrotron GISAXS has captured in detail the fast growth in size of PCBM aggregates from 7 to 18 nm within 100 s of annealing at 150 °C. Simultaneously observed is the enhanced crystallization of P3HT into lamellae oriented mainly perpendicular but also parallel to the substrate. An Avrami analysis of the observed structural evolution indicates that the faster PCBM aggregation follows a diffusion-controlled growth process (confined by P3HT segmental motion), whereas the slower development of crystalline P3HT nanograins is characterized by constant nucleation rate (determined by the degree of supercooling and PCBM demixing). These two competing kinetics result in local phase separation with space-filling PCBM and P3HT nanodomains less than 20 nm in size when annealing temperature is kept below 180 °C. Accompanying the morphological development is the synchronized increase in electron and hole mobilities of the BHJ thin-film solar cells, revealing the sensitivity of the carrier transport of the device on the structural features of PCBM and P3HT nanodomains. Optimized structural parameters, including the aggregate size and mean spacing of the PCBM aggregates, are quantitatively correlated to the device performance; a comprehensive network structure of the optimized BHJ thin film is presented.

A small/wide-angle X-ray scattering instrument for structural characterization of air-liquid interfaces, thin films and bulk specimens

At the National Synchrotron Radiation Research Center, a small/wide-angle X-ray scattering (SAXS/WAXS) instrument has been installed at the BL23A beamline with a superconducting wiggler insertion device. This beamline is equipped with double Si(111) crystal and double Mo/B4C multilayer monochromators, and an Si-based plane mirror that can selectively deflect the beam downwards for grazing-incidence SAXS (GISAXS) studies of air–liquid or liquid–liquid interfaces. The SAXS/WAXS instrument, situated in an experimental hutch, comprises collimation, sample and post-sample stages. Pinholes and slits have been incorporated into the beam collimation system spanning a distance of ∼5 m. The sample stage can accommodate various sample geometries for air–liquid interfaces, thin films, and solution and solid samples. The post-sample section consists of a 1 m WAXS section with two linear gas detectors, a vacuum bellows (1–4 m), a two-beamstop system and the SAXS detector system, all situated on a motorized optical bench for motion in six degrees of freedom. In particular, the vacuum bellows of a large inner diameter (260 mm) provides continuous changes of the sample-to-detector distance under vacuum. Synchronized SAXS and WAXS measurements are realized via a data-acquisition protocol that can integrate the two linear gas detectors for WAXS and the area detector for SAXS (gas type or Mar165 CCD); the protocol also incorporates sample changing and temperature control for programmable data collection. The performance of the instrument is illustrated via several different measurements, including (1) simultaneous SAXS/WAXS and differential scanning calorimetry for polymer crystallization, (2) structural evolution with a large ordering spacing of ∼250 nm in a supramolecular complex, (3) SAXS for polymer blends under in situ drawing, (4) SAXS and anomalous SAXS for unilamellar lipid vesicles and metalloprotein solutions, (5) anomalous GISAXS for oriented membranes of Br-labeled lipids embedded with peptides, and (6) GISAXS for silicate films formed in situ at the air–water interface.

Nanostructure and Hydrogen Spillover of Bridged Metal-Organic Frameworks

The metal-organic frameworks (MOF) with low and medium specific surface areas (SSA) were shown to be able to adsorb hydrogen via bridged spillover at room temperature (RT) up to an amount of full coverage of hydrogen in the MOF. Anomalous small-angle X-ray scattering was employed to investigate the key relationship between the structures and storage properties of the involved materials. It was found that the tunable imperfect lattice defects and the 3D pore network in the MOF crystal are the most critical structures for RT hydrogen uptake rather than the known micropores in the crystal, SSA, and Pt catalyst structure.

Enhancing transversal relaxation for magnetite nanoparticles in mr imaging using Gd3+-chelated mesoporous silica shells

A new magnetic nanoparticle was synthesized in the form of Gd(3+)-chelated Fe(3)O(4)@SiO(2). The Fe(3)O(4) nanoparticle was octahedron-structured, was highly magnetic (∼94 emu/g), and was the core of an encapsulating mesoporous silica shell. DOTA-NHS molecules were anchored to the interior channels of the porous silica to chelate Gd(3+) ions. Because there were Gd(3+) ions within the silica shell, the transverse relaxivity increased 7-fold from 97 s(-1) mM(-1) of Fe(3)O(4) to 681 s(-1) mM(-1) of Gd(3+)-chelated Fe(3)O(4)@SiO(2) nanoparticles with r(2)/r(1) = 486. The large transversal relaxivity of the Gd(3+)-chelated Fe(3)O(4)@SiO(2) nanoparticles had an effective magnetic resonance imaging effect and clearly imaged lymph nodes. Physiological studies of liver, spleen, kidney, and lung tissue in mice infused with these new nanoparticles showed no damage and no cytotoxicity in Kupffer cells, which indicated that Gd(3+)-chelated Fe(3)O(4)@SiO(2) nanoparticles are biocompatible.

Intermixing-seeded growth for high-performance planar heterojunction perovskite solar cells assisted by precursor-capped nanoparticles

This work proposes a novel approach to modulate the nucleation and growth of perovskite crystals in planar perovskite (CH3NH3PbI3−xClx) solar cells by intermixing precursor-capped inorganic nanoparticles of PbS. A small amount of dispersed PbS nanoparticles which were covered with perovskite precursor molecules of methylammonium iodide (CH3NH3I, MAI) through the ligand-exchange treatment functioned as effective seed-like nucleation sites to promote the formation of perovskite lattice structures. Through this intermixing-seeded growth technique, substantial morphological improvements, such as increased crystal domains, enhanced coverage, and uniformity, were realized in the perovskite thin films, and the corresponding solar cell devices exhibited a promising power conversion efficiency of 17.4%, showing an enhancement of approximately 25% compared to that of the controlled pristine solar cell device. The substantially enhanced crystal orientation, particularly along the direction perpendicular to the substrate, was evident from the synchrotron-based grazing incidence wide-angle X-ray scattering data. This observation was consistent with the enhanced carrier diffusion lengths and excellent reproducibility of high fill factors of the planar heterojunction perovskite devices fabricated through the proposed technique.

Complementary solvent additives tune the orientation of polymer lamellae, reduce the sizes of aggregated fullerene domains, and enhance the performance of bulk heterojunction solar cells

In this study we employed 1-chloronaphthalene (CN) and 1,8-diiodooctane (DIO) as binary additives exhibiting complementarily preferential solubility for processing the crystalline conjugated polymer poly[bis(dodecyl)thiophene-dodecyl-thieno[3,4-c]pyrrole-4,6-dione] (PBTC12TPD) and the fullerene [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) in chloroform. Using synchrotron grazing-incidence small-/wide-angle X-ray scattering and transmission electron microscopy to analyse the structure of the PBTC12TPD–PC71BM blend films, we found that the binary additives with different volume ratios in the processing solvent allow us to tune the relative population of face-on to edge-on PBTC12TPD lamellae and the size of PC71BM clusters in the blend films; the sizes of the fractal-like PC71BM clusters and the aggregated domains of PC71BM clusters increased and decreased, respectively, upon increasing the amount of DIO, whereas the relative ratio of face-on to edge-on PBTC12TPD lamellae increased upon increasing the amount of CN. When fabricating the photovoltaic devices, the short-circuit current density of the devices with the PBTC12TPD–PC71BM active layer having been processed with the binary additives is higher than that of the device incorporating an active layer processed without any additive. As a result, the power conversion efficiency of a device incorporating an active layer of PBTC12TPD–PC71BM (1 : 1.5, w/w) processed with binary additives of 0.5% DIO and 1% CN in chloroform increased to 6.8% from a value of 4.9%, a relative increase of 40%, for the corresponding device containing the same active layer but processed without any additive.

Non-volatile organic field-effect transistor memory comprising sequestered metal nanoparticles in a diblock copolymer film

In this study, we fabricated p-channel-type non-volatile organic field-effect transistor (OFET) memory devices featuring an asymmetric PS-b-P4VP diblock copolymer layer incorporating high- and low-work-function metal nanoparticles (NPs) in the hydrophilic and hydrophobic blocks, respectively. We chose the highly asymmetric diblock copolymer PS56k-b-P4VP8k as the polymer electret to create the memory windows, and used the different work functions of the ex situ-synthesized metal NPs to tune the memory window for either p- or n-channel applications. The transfer curves of non-volatile OFET memory devices incorporating an asymmetric PS56k-b-P4VP8k layer embedded with high-work-function Pt NPs (5.65 eV) in the P4VP block exhibited a positive threshold voltage shift and a large memory window (ca. 27 V). In contrast, the transfer curves of the corresponding non-volatile OFET memory devices featuring embedded low-work-function (4.26 eV) Ag NPs exhibited a negative threshold voltage shift and a smaller memory window (ca. 19 V). This approach provides a versatile way to fabricate p- or possibly n-channel-type non-volatile organic field-effect transistor (OFET) memory devices with the same processing procedure.

Surfactant-Directed Fabrication of Supercrystals from the Assembly of Polyhedral Au–Pd Core–Shell Nanocrystals and Their Electrical and Optical Properties

Au-Pd core-shell nanocrystals with cubic, truncated cubic, cuboctahedral, truncated octahedral, and octahedral structures have been employed to form micrometer-sized polyhedral supercrystals by both the droplet evaporation method and novel surfactant diffusion methods. Observation of cross-sectional samples indicates shape preservation of interior nanocrystals within a supercrystal. Low-angle X-ray diffraction techniques and electron microscopy have been used to confirm the presence of surfactant between contacting nanocrystals. By diluting the nanocrystal concentration or increasing the solution temperature, supercrystal size can be tuned gradually to well below 1 μm using the surfactant diffusion method. Rectangular supercrystal microbars were obtained by increasing the amounts of cubic nanocrystals and surfactant used. Au-Ag core-shell cubes and PbS cubes with sizes of 30-40 nm have also been fabricated into supercrystals, showing the generality of the surfactant diffusion approach to form supercrystals with diverse composition. Electrical conductivity measurements on single Au-Pd supercrystals reveal loss of metallic conductivity due to the presence of insulating surfactant. Cubic Au-Pd supercrystals show infrared absorption at 3.2 μm due to extensive plasmon coupling. Mie-type resonances centered at 9.8 μm for the Au-Pd supercrystals disappear once the Pd shells are converted into PdH after hydrogen absorption.

X-ray beamlines for structural studies at the NSRRC superconducting wavelength shifter

Using a superconducting-wavelength-shifter X-ray source with a photon flux density of 10(11)-10(13) photons s(-1) mrad(-1) (0.1% bandwidth)(-1) (200 mA)(-1) in the energy range 5-35 keV, three hard X-ray beamlines, BL01A, BL01B and BL01C, have been designed and constructed at the 1.5 GeV storage ring of the National Synchrotron Radiation Research Center (NSRRC). These have been designed for structure-related research using X-ray imaging, absorption, scattering and diffraction. The branch beamline BL01A, which has an unmonochromatized beam, is suitable for phase-contrast X-ray imaging with a spatial resolution of 1 microm and an imaging efficiency of one frame per 10 ms. The main beamline BL01B has 1:1 beam focusing and a medium energy resolution of approximately 10(-3). It has been designed for small-angle X-ray scattering and transmission X-ray microscopy, used, respectively, in anomalous scattering and nanophase-contrast imaging with 30 nm spatial resolution. Finally, the branch beamline BL01C, which features collimating and focusing mirrors and a double-crystal monochromator for a high energy resolution of approximately 10(-4), has been designed for X-ray absorption spectroscopy and high-resolution powder X-ray diffraction. These instruments, providing complementary tools for studying multiphase structures, have opened up a new research trend of integrated structural study at the NSRRC, especially in biology and materials. Examples illustrating the performances of the beamlines and the instruments installed are presented.