Wide-Range Near-Infrared Sensitizing 1 H-Benzo[ c, d]indol-2-ylidene-Based Squaraine Dyes for Dye-Sensitized Solar Cells.

NIR absorbing squaraine dyes SQ1-SQ7 having 1 H-benzo[ c, d]indol-2-ylidene as a donor moiety were designed for application in DSSCs. Annulation of the benzene ring to an 3 H-indolium-based anchor moiety led to a red-shifted and broadened absorption band on TiO2 film, which were reflected in the improved short-circuit current density of SQ2 (6.22 mA cm-2) compared to the nonbenzene fused derivative SQ1 (4.39 mA cm-2). Although the introduction of a butoxy (SQ4: 806 nm) or dialkylamino group (SQ5-SQ7: 815-820 nm) to the 1 H-benzo[ c, d]indol-2-ylidene-based donor moiety resulted in red-shifted absorption maxima in ethanol compared to the nonsubstituted derivative SQ2 (784 nm), the HOMO energy level of SQ4-SQ7 gave rise to an undesirable approximation to the redox potential of I-/I3-. Thus, the butoxy (SQ4: 0.56) and dialkylamino (SQ5-SQ7: 0.25-0.30) derivatives had relatively lower conversion efficiencies. Since the 2-ethylhexyl derivative SQ3 exhibited red-shifted absorption (λmax: 796 nm), suitable HOMO and LUMO energy levels, and relatively efficient restriction of charge recombination, this dye achieved the highest conversion efficiency (1.31%), along with a high IPCE response of over 20% over a wide range from 640 to 860 nm and an onset of IPCE at 1000 nm.

Simultaneous Li-Doping and Formation of SnO2-Based Composites with TiO2: Applications for Perovskite Solar Cells.

Tin oxide (SnO2) has been recognized as one of the beneficial components in the electron transport layer (ETL) of lead-halide perovskite solar cells (PSCs) due to its high electron mobility. The SnO2-based thin film serves for electron extraction and transport in the device, induced by light absorption at the perovskite layer. The focus of this paper is on the heat treatment of a nanoaggregate layer of single-nanometer-scale SnO2 particles in combination with another metal-dopant precursor to develop a new process for ETL in PSCs. The combined precursor solution of Li chloride and titanium(IV) isopropoxide (TTIP) was deposited onto the SnO2 layer. We varied the heat treatment conditions of the spin-coated films comprising double layers, i.e., an Li/TTIP precursor layer and SnO2 nanoparticle layer, to understand the effects of nanoparticle interconnection via sintering and the mixing ratio of the Li-dopant on the photovoltaic performance. X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HR-TEM) measurements of the sintered nanoparticles suggested that an Li-doped solid solution of SnO2 with a small amount of TiO2 nanoparticles formed via heating. Interestingly, the bandgap of the Li-doped ETL samples was estimated to be 3.45 eV, indicating a narrower bandgap as compared to that of pure SnO2. This observation also supported the formation of an SnO2/TiO2 solid solution in the ETL. The utilization of such a nanoparticulate SnO2 film in combination with an Li/TTIP precursor could offer a new approach as an alternative to conventional SnO2 electron transport layers for optimizing the performance of lead-halide perovskite solar cells.

Intermolecular interaction as the origin of red shifts in absorption spectra of zinc-phthalocyanine from first-principles.

We investigate electronic origins of a redshift in absorption spectra of a dimerized zinc phthalocyanine molecule (ZnPc) by means of hybrid density functional theoretical calculations. In terms of the molecular orbital (MO) picture, the dimerization splits energy levels of frontier MOs such as the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) of the constituent molecules. Consequently, the absorption wavelength seems to become longer than the monomer as the overlap between the monomers becomes larger. However, for a ZnPc dimer configuration with its cofacially stacked monomer arrangement, the calculated absorption spectra within the time-dependent density functional theory indicates no redshift but blueshift in the Q-band absorption spectrum, i.e., a typical H-aggregate. The origin of the apparently contradictory result is elucidated by the conventional description of the interaction between monomer transition dipoles in molecular dimers [Kasha, M. Radiat. Res. 1963, 20, 55]. The redshift is caused by an interaction between the two head-to-tail transition dipoles of the monomers, while the side-by-side arranged transition dipoles result in a blueshift. By tuning the dipole-dipole interaction based on the electronic natures of the HOMO and the LUMO, we describe a slipped-stacked ZnPc dimer configuration in which the Q-band absorption wavelength increases by as large as 144 nm relative to the monomer Q-band.

Growth and Dispersion Control of SnO2 Nanocrystals Employing an Amino Acid Ester Hydrochloride in Solution Synthesis: Microstructures and Photovoltaic Applications.

Tin oxide (SnO2) is a technologically important semiconductor with versatile applications. In particular, attention is being paid to nanostructured SnO2 materials for use as a part of the constituents in perovskite solar cells (PSCs), an emerging renewable energy technology. This is mainly because SnO2 has high electron mobility, making it favorable for use in the electron transport layer (ETL) in these devices, in which SnO2 thin films play a role in extracting electrons from the adjacent light-absorber, i.e., lead halide perovskite compounds. Investigation of SnO2 solution synthesis under diverse reaction conditions is crucial in order to lay the foundation for the cost-effective production of PSCs. This research focuses on the facile catalyst-free synthesis of single-nanometer-scale SnO2 nanocrystals employing an aromatic organic ligand (as the structure-directing agent) and Sn(IV) salt in an aqueous solution. Most notably, the use of an aromatic amino acid ester hydrochloride salt-i.e., phenylalanine methyl ester hydrochloride (denoted as L hereafter)-allowed us to obtain an aqueous precursor solution containing a higher concentration of ligand L, in addition to facilitating the growth of SnO2 nanoparticles as small as 3 nm with a narrow size distribution, which were analyzed by means of high-resolution transmission electron microscopy (HR-TEM). Moreover, the nanoparticles were proved to be crystallized and uniformly dispersed in the reaction mixture. The environmentally benign, ethanol-based SnO2 nanofluids stabilized with the capping agent L for the Sn(IV) ions were also successfully obtained and spin-coated to produce a SnO2 nanoparticle film to serve as an ETL for PSCs. Several SnO2 ETLs that were created by varying the temperature of nanoparticle synthesis were examined to gain insight into the performance of PSCs. It is thought that reaction conditions that utilize high concentrations of ligand L to control the growth and dispersion of SnO2 nanoparticles could serve as useful criteria for designing SnO2 ETLs, since hydrochloride salt L can offer significant potential as a functional compound by controlling the microstructures of individual SnO2 nanoparticles and the self-assembly process to form nanostructured SnO2 thin films.

1D Narrow-Bandgap Tin Oxide Materials: Systematic High-Resolution TEM and Raman Analysis.

We demonstrate for the first time the structure identification and narrow-bandgap property of 1D hybridized SnO/SnO2 nanoparticles derived from the calcination of a single-source precursor, i.e., tin(II) oxalate. Systematic Raman analysis together with high-resolution TEM (HR-TEM) measurements of the tin oxide samples were carried out by changing the calcination temperatures. These data revealed the simultaneous formation of 1D SnO/SnO2 in the rod particles that grew in air. It was also found that Sn(II) can be introduced by changing the concentration of Sn(II) salt in the precursor synthesis and the maximum temperature in calcination. Particles measuring 20~30 nm were sintered to produce tin oxide nanorods including tin monoxide, SnO. Photoabsorption properties associated with the formation of the SnO/SnO2 nanocomposites were also investigated. Tauc plots indicate that the obtained tin oxide samples had a lower bandgap of 2.9~3.0 eV originating from SnO in addition to a higher bandgap of around 3.5~3.7 eV commonly observed for SnO2. Such 1D SnOx/SnO2 hybrids via tin oxalate synthesis with this optical property would benefit new materials design for photoenergy conversion systems, such as photocatalysts.

Preparation of Nanostructured Sn/Ti Oxide Hybrid Films with Terpineol/PEG-Based Nanofluids: Perovskite Solar Cell Applications.

Tin oxide (SnO2) and titanium dioxide (TiO2) are recognized as attractive energy materials applicable for lead halide perovskite solar cells (PSCs). Sintering is one of the effective strategies for improving the carrier transport of semiconductor nanomaterials. Using the alternative metal-oxide-based ETL, nanoparticles are often used in a way that they are dispersed in a precursor liquid prior to their thin-film deposition. Currently, the creation of PSCs using nanostructured Sn/Ti oxide thin-film ETL is one of the topical issues for the development of high-efficiency PSCs. Here, we demonstrate the preparation of terpineol/PEG-based fluid containing both tin and titanium compounds that can be utilized for the formation of a hybrid Sn/Ti oxide ETL on a conductive substrate (F-doped SnO2 glass substrate: FTO). We also pay attention to the structural analysis of the Sn/Ti metal oxide formation at the nanoscale using a high-resolution transmission electron microscope (HR-TEM). The variation of the nanofluid composition, i.e., the concentration of tin and titanium sources, was examined to obtain a uniform transparent thin film by spin-coating and sintering processes. The maximum power conversion efficiency was obtained for the concentration condition of [SnCl2·2H2O]/[titanium tetraisopropoxide (TTIP)] = 25:75 in the terpineol/PEG-based precursor solution. Our method for preparing the ETL nanomaterials provides useful guidance for the creation of high-performance PSCs using the sintering method.

Manufacturing a TiO2-Based Semiconductor Film with Nanofluid Pool Boiling and Sintering Processes toward Solar-Cell Applications.

For the first time, nanofluid boiling was applied as a process for the creation of a semiconductor TiO2 nanoparticle film that can be deposited onto a conductive substrate (F-doped SnO2 glass: FTO). A steel-base device designed for pool boiling was used to deposit a TiO2-based nanofluid consisting of nanoparticles with an average size of about 20 nm. The boiling of the nanofluid directly on the FTO glass substrate allowed for the deposition of the nanoparticles onto the FTO surface. In principle, the surface responsible for transferring heat to the fluid can be covered with these nanoparticles when the nanofluid boils. Using the as-deposited films, crystal growth of the TiO2 nanoparticle was controlled by varying the strategies of the post-sintering profile. The maximum temperatures, periods, and ramping rates for the obtained samples were systematically changed. Scanning electron microscopy (SEM) revealed that a densely packed TiO2-nanoparticle layer was obtained for the as-deposited substrate via pool boiling. For the maximum temperature at 550 °C, the TiO2 grain sizes became larger (~50 nm) and more round-shaped TiO2 nanostructures were identified. Notably, we have demonstrated for the first time how the sintering of TiO2 nanoparticles proceeds for the nanoporous TiO2 films using high-resolution transmission electron microscopy (TEM) measurements. We found that the TiO2 nanoparticles fused with each other and crystal growth occurred through neighboring 2-4 nanoparticles for the 550 °C sample, which was proved by the TEM analysis that continuous lattice fringes corresponding to the (101) anatase phase were clearly observed through the entire area of some nanoparticles aligned horizontally. In addition, the loss of the TiO2 nanofluid (precursor solution) was completely avoided in our TiO2 deposition. Unlike the commonly used spin-coating method, nanofluid pool boiling would provide an alternative cost-effective approach to manufacture semiconductor layers for various applications, such as solar cells.

Elucidation of the Crystal Growth Characteristics of SnO2 Nanoaggregates Formed by Sequential Low-Temperature Sol-Gel Reaction and Freeze Drying.

SnO2 nanoparticles are regarded as attractive, functional materials because of their versatile applications. SnO2 nanoaggregates with single-nanometer-scale lumpy surfaces provide opportunities to enhance hetero-material interfacial areas, leading to the performance improvement of materials and devices. For the first time, we demonstrate that SnO2 nanoaggregates with oxygen vacancies can be produced by a simple, low-temperature sol-gel approach combined with freeze-drying. We characterize the initiation of the low-temperature crystal growth of the obtained SnO2 nanoaggregates using high-resolution transmission electron microscopy (HRTEM). The results indicate that Sn (II) hydroxide precursors are converted into submicrometer-scale nanoaggregates consisting of uniform SnO2 spherical nanocrystals (2~5 nm in size). As the sol-gel reaction time increases, further crystallization is observed through the neighboring particles in a confined part of the aggregates, while the specific surface areas of the SnO2 samples increase concomitantly. In addition, X-ray photoelectron spectroscopy (XPS) measurements suggest that Sn (II) ions exist in the SnO2 samples when the reactions are stopped after a short time or when a relatively high concentration of Sn (II) is involved in the corresponding sol-gel reactions. Understanding this low-temperature growth of 3D SnO2 will provide new avenues for developing and producing high-performance, photofunctional nanomaterials via a cost-effective and scalable method.

Iodine/iodide-free dye-sensitized solar cells.

Dye-sensitized solar cells (DSSCs) are built from nanocrystalline anatase TiO(2) with a 101 crystal face (nc-TiO(2)) onto which a dye is absorbed, ruthenium complex sensitizers, fluid I(-)/I(3)(-) redox couples with electrolytes, and a Pt-coated counter electrode. DSSCs have now reached efficiencies as high as 11%, and G24 Innovation (Cardiff, U.K.) is currently manufacturing them for commercial use. These devices offer several distinct advantages. On the basis of the electron lifetime and diffusion coefficient in the nc-TiO(2) layer, DSSCs maintain a diffusion length on the order of several micrometers when the dyed-nc-TiO(2) porous layer is covered by redox electrolytes of lithium and/or imidazolium iodide and their polyiodide salts. The fluid iodide/iodine (I(-)/I(3)(-)) redox electrolytes can infiltrate deep inside the intertwined nc-TiO(2) layers, promoting the mobility of the nc-TiO(2) layers and serving as a hole-transport material of DSSCs. As a result, these materials eventually give a respectable photovoltaic performance. On the other hand, fluid I(-)/I(3)(-) redox shuttles have certain disadvantages: reduced performance control and long-term stability and incompatibility with some metallic component materials. The I(-)/I(3)(-) redox shuttle shows a significant loss in short circuit current density and a slight loss in open circuit voltage, particularly in highly viscous electrolyte-based DSSC systems. Iodine can also act as an oxidizing agent, corroding metals, such as the grid metal Ag and the Pt mediator on the cathode, especially in the presence of water and oxygen. In addition, the electrolytes (I(-)/I(3)(-)) can absorb visible light (lambda = approximately 430 nm), leading to photocurrent loss in the DSSC. Therefore, the introduction of iodide/iodine-free electrolytes or hole-transport materials (HTMs) could lead to cost-effective alternatives to TiO(2) DSSCs. In this Account, we discuss the iodide/iodine-free redox couple as a substitute for the fluid I(-)/I(3)(-) redox shuttle. We also review the adaptation of solid-state HTMs to the iodide/iodine-free solid-state DSSCs with an emphasis on their pore filling and charge mobility in devices and the relationship of those values to the performance of the resulting iodide/iodine-free DSSCs. We demonstrate how the structures of the sensitizing dye molecules and additives of lithium or imidazolium salts influence device performance. In addition, the self-organizing molecular interaction for electronic contact of HTMs to dye molecules plays an important role in unidirectional charge diffusion at interfaces. The poly(3,4-ethylenedioxythiophene) (PEDOT)-based DSSCs, which we obtain through photoelectrochemical polymerization (PEP) using 3-alkylthiophen-bearing ruthenium dye, HRS-1, and bis-EDOT, demonstrates the importance of nonbonding interface contact (e.g., pi-pi-stacking) for the successful inclusion of HTMs.

A molten salt-based nitridation approach for synthesizing nanostructured InN electrode materials.

Single-phase InN nanocrystals were synthesized for the first time by a molten salt-based nitridation approach using InCl3 and LiNH2 as indium and nitrogen sources, respectively. A molten salt, KCl-LiCl, during nitridation, enabled us to obtain InN nanocrystals at relatively low temperatures ranging from 400 °C to 500 °C. SEM and HR-TEM measurements coupled with XRD data revealed that InN nanocrystals were formed with average grain sizes of approximately 50-60 nm. Notably, the photoelectrochemical cell fabricated using the InN nanocrystals synthesized at 450 °C exhibited a photocurrent response under light irradiation from 400 nm to 880 nm. The precise control of the growth of InN particles using our synthetic approach provides opportunities for developing versatile nitride nanocrystals.

Supramolecular Light-Harvesting Antennas of Metal-Coordinated Bis(8-Hydroxyquinoline)-Substituted Porphyrin Networks.

Artificial antenna complexes of metal-coordinated bis(8-hydroxyquinoline)-substituted porphyrin networks that mimic antenna chromophores in plants were organized on titanium dioxide electrodes in photoelectrochemical cells. The generated photocurrents can be optimized according to the two ways of porphyrin self-assembly due to the "antenna effect": changing the number of assembled porphyrin monolayers and the number of generations of the metal-coordinated porphyrin networks.

Effective and efficient photoluminescence of salicylate-ligating terbium(III) clusters stabilized by multiple phenyl-phenyl interactions.

A luminescent nonanuclear terbium(III) hydroxo cluster, Tb(9)(Hesa)(16)(mu-OH)(10)(NO(3)) (Hesa: hexyl salicylate), stabilized by unique two-way phenyl ring interactions, pi-pi stackings (d = 3.482-3.599 A) and C-H-pi interactions (d = 2.75-3.03 A) between adjacent pairs of salicylates, was structurally characterized based on X-ray analysis, and the favourable absorption change and efficient photoluminescent characteristic were rationalized as being due to J-type pi-pi stackings, which are dramatically enhanced by hexyl groups in hexyl salicylate ligands.

Electrochemical Self-Assembly of Nanostructured CuSCN/Rhodamine B Hybrid Thin Film and Its Dye-Sensitized Photocathodic Properties.

Nanostructured hybrid thin films of CuSCN and rhodamine B (RB) are electrochemically self-assembled (ESA) by cathodic electrolysis in an ethanol/water mixture containing Cu2+, SCN-, and RB. By selecting the solvent, Cu2+/SCN- ratio, and the concentration of RB, we demonstrate several control parameters in the film formation. High loading of RB into the film has been achieved to reach a CuSCN:RB volume ratio of approximately 2:1. The RB solid could almost completely be extracted from the hybrid film by soaking the film in dimethylacetamide (DMA), leading to a large increase of the surface area. The crystallographic orientation of the nanostructure with respect to the substrate can be controlled. Efficient quenching of fluorescence of RB has been observed for the CuSCN/RB hybrid film, implying hole injection from RB excited state to CuSCN. Photoelectrochemical study on the porous crystalline CuSCN obtained after the DMA treatment and sensitized with RB revealed sensitized photocathodic action under visible light illumination, indicating the potential usefulness of the porous CuSCN electrodes for construction of tandem dye-sensitized solar cells.

A phenyl-capped aniline tetramer for Z907/tert-butylpyridine-based dye-sensitized solar cells and molecular modelling of the device.

Z907-sensitized solar cells incorporating a phenyl-capped aniline tetramer (EPAT) as a substitute of the iodine/iodide redox couple in the electrolytes produce an enhanced open-circuit voltage and short circuit photocurrent density when tert-butylpyridine (TBP) is added to the electrolyte.

Size-controlled synthesis of anisotropic TiO2 single nanocrystals using microwave irradiation and their application for dye-sensitized solar cells.

A microwave hydrothermal reaction of colloidal titanates is presented as a cost-effective synthesis to produce TiO(2) single nanocrystals. The photoelectrode consisting of anisotropic nanorods and V-shaped twins has a significant advantage for achieving an appreciable incident photon-to-current conversion efficiency of 85.6% for the dye-sensitized solar cell.

Solid-state dye-sensitized solar cells fabricated by coupling photoelectrochemically deposited poly(3,4-ethylenedioxythiophene) (PEDOT) with silver-paint on cathode.

A PEDOT-based dye-sensitized solar cell (DSC) is successfully improved by coupling photoelectrochemically deposited PEDOT layer with an Ag paste-paint on the cathode. With a 9.3 µm thick mesoscopic nanocrystalline TiO(2) film, a maximum cell performance of 3.2% with relatively high V(oc) of around 780 mV is achieved.