Isomer Effects of Fullerene Derivatives on Organic Photovoltaics and Perovskite Solar Cells.

Solar energy conversion is one of the most important issues for creating and maintaining a future sustainable society. In this regard, photovoltaic technologies have attracted much attention because of their potential to solve energy and environmental issues. In particular, thin-film solar cells, such as organic photovoltaics (OPVs) and perovskite solar cells (PSCs), are highly promising owing to their flexibility, light weight, and low-cost production. One of the most important factors used to evaluate solar-cell performance is the power conversion efficiency (PCE), which is the ratio of the output electric power divided by the input light power. The PCEs of PSCs have become comparable to those of multicrystalline silicon solar cells in a laboratory level, but the PCEs of OPVs have yet to catch up with them and still need to be improved. The insufficient durability of PSCs and OPVs is also a challenge that needs to be addressed. Fullerene derivatives have been utilized as electron acceptors and electron-transport materials in OPVs and PSCs. However, the use of fullerene derivatives requires attention to their isomers if they are multiadducts or even monoadducts produced from fullerenes with low symmetry. Their nonuniform structures and electronic properties may exert a negative effect on photovoltaic properties. However, most researchers in the field of OPVs and PSCs have been unaware of the importance of the isomerism. Even the most prevalent, high-performance fullerene acceptor, [6,6]-phenyl-C71-butyric acid methyl ester ([70]PCBM), has been used as an isomer mixture. In this Account, we summarize recent studies on the effects of isomer separation of fullerene derivatives on the device performances of OPVs and PSCs. Largely, fullerene derivatives containing various isomers are categorized into [60]fullerene bisadducts, [70]fullerene bisadducts, and [70]fullerene monoadducts. In all cases, the difference in isomerism was found to have a large impact on PCEs. The miscibility with polymer donors and film-forming property of fullerene derivatives were affected by the isomer separations, which exert the most potent influence on device performances. Although the disorders in energy levels among isomers are not definitely influencing on photovoltaic properties of isomer mixtures, the molecular packing structures of fullerene derivatives make a significant effect on their photovoltaic properties. Notably, isomerically pure fullerene derivatives often-but not always-exhibit higher PCEs than the isomer mixture. The search for the best isomers of fullerene derivatives and their optimal compositional ratios, which extensively depend on their roles and the combined materials, will be an indispensable step to achieving consistently higher device performances for OPVs and PSCs.

Noncovalent Functionalization of Few-Layered Antimonene with Fullerene Clusters and Photoinduced Charge Separation in the Composite.

Few-layered antimonene (FLSb) nanosheets were noncovalently functionalized with fullerene C60 clusters by quick addition of a poor solvent (i.e., acetonitrile) into a mixed dispersion of FLSb and C60 in a good solvent (i.e., toluene). In a flash-photolysis time-resolved microwave conductivity (FP-TRMC) measurement, the FLSb-C60 composite, (FLSb+C60 )m , showed a rapid rise in transient conductivity, whereas no conductivity signal was observed in the single components, FLSb and C60 . This demonstrated the occurrence of photoinduced charge separation between FLSb and C60 in (FLSb+C60 )m . Furthermore, a photoelectrochemical device with an electrophoretically deposited (FLSb+C60 )m film exhibited an enhanced efficiency of photocurrent generation, compared to those of the single-components, FLSb and C60 , due to the photoinduced charge separation between FLSb and C60 . This work provides a promising approach for fabrication of antimonene-organic molecule composites and paves the way for their application in optoelectronics.

Glassy Porphyrin/C60 Composites: Morphological Engineering of C60 Fullerene with Liquefied Porphyrins.

Morphological control of C60 fullerene using liquefied porphyrins (1 and 2) as the host matrices was explored. Slow evaporation of the solvent of the equimolar mixture of porphyrin and C60 in toluene afforded the porphyrin/C60 composite with a 3:1 molar ratio. The stoichiometric binding behaviors suggest that specific porphyrin-C60 interactions operate the formation of the porphyrin/C60 composites, as corroborated by spectroscopic and thermal properties, and glazing-incidence wide-angle X-ray diffraction. Under the bulk conditions, the conventional thermodynamic advantage of multiple binding cooperativity for molecular recognition is unlikely to explain the stoichiometric binding behaviors. Instead, we propose a size-matching effect on the porphyrin-C60 interaction in the bulk porphyrin matrices, i.e., "supramolecular solvation". The glassy nature of the porphyrin matrices was transmitted to C60 through the specific interaction, and the porphyrin/C60 composites adopted glassy states at room temperature.

Unique Tube-Ring Interactions: Complexation of Single-Walled Carbon Nanotubes with Cycloparaphenyleneacetylenes.

Carbon nanotubes (CNTs) interlocked by cyclic compounds through supramolecular interaction are promising rotaxane-like materials applicable as 2D and 3D networks of nanowires and disease-specific theranostic agents having multifunctionalities. Supramolecular complexation of CNTs with cyclic compounds in a "ring toss'' manner is a straightforward method to prepare interlocked CNTs; however, to date, this has not been reported on. Here, the "ring toss" method to prepare interlocked CNTs by using π-conjugated carbon nanorings: [8]-, [9]-, and [10]cycloparaphenyleneacetylene (CPPA) is reported. CPPAs efficiently interact with CNTs to form CNT@CPPA complexes, while uncomplexed CPPAs can be recovered without decomposition. CNTs, which tightly fit in the cavities of CPPAs through convex-concave interaction, efficiently afford "tube-in-ring"-type CNT@CPPA complexes. "Tube-in-ring"-type and "ring-on-tube"-type complexation modes are successfully distinguished by spectroscopic, thermogravimetric, and microscopic analyses.

Formation and Photodynamic Behavior of Transition Metal Dichalcogenide Nanosheet-Fullerene Inorganic/Organic Nanohybrids on Semiconducting Electrodes.

Composite films that consisted of C60 and well-exfoliated nanosheets of transition metal dichalcogenides (TMDs), such as MoS2 or WS2 , with a bulk heterojunction structure were easily fabricated onto a semiconducting SnO2 electrode via a two-step methodology: self-assembly into their composite aggregates by injection of a poor solvent into a good solvent with the dispersion, and subsequent electrophoretic deposition. Upon photoexcitation, the composites on SnO2 exhibited enhanced transient conductivity in comparison with single components of TMDs or C60 , which demonstrates that the bulk heterojunction nanostructure of TMD and C60 promoted the charge separation (CS). In addition, the decoration of the TMD nanosheets with C60 hindered the undesirable charge recombination (CR) between an electron in SnO2 and a hole in the TMD nanosheets. Owing to the accelerated CS and suppressed CR, photoelectrochemical devices based on the MoS2 -C60 and WS2 -C60 composites achieved remarkably improved incident photon-to-current efficiencies (IPCEs) as compared with the single-component films. Despite more suppressed CR in WS2 -C60 than MoS2 -C60 , the IPCE value of the device with WS2 -C60 was smaller than that with MoS2 -C60 owing to its inhomogeneous film structure.

Geometries, Electronic Couplings, and Hole Dissociation Dynamics of Photoinduced Electron-Hole Pairs in Polyhexylthiophene-Fullerene Dyads Rigidly Linked by Oligophenylenes.

To shed a light on fundamental molecular functions of photoinduced charge conductions by organic photovoltaic materials, it is important to directly observe molecular geometries of the intermediate charges just after the photoinduced electron-transfer reactions. However, highly inhomogeneous molecular environments at the bulk heteojunction interfaces in the photoactive layers have prevented us from understanding the mechanism of the charge conductions. We have herein investigated orbital geometries, electronic couplings, and hole-dissociation dynamics of photoinduced charge-separated (CS) states in a series of poly(3-hexylthiophene)-fullerene linked dyads bridged by rigid oligo-p-phenylene spacers by using time-resolved EPR spectroscopy. It has been revealed that one-dimensional intramolecular hole-dissociations exothermically take place from localized holes in initial CS states, following bridge-mediated, photoinduced charge-separations via triplet exciton diffusions in the conjugated polymer-backbones. This molecular wire property of the photoinduced charges in solution at room temperature demonstrates the potential utility of the covalently bridged polymer molecules applied for the molecular devices.

Effect of carbazochrome sodium sulfonate on refractory chronic prostatitis.

OBJECTIVES: To study the effect of carbazochrome sodium sulfonate, an agent that reduces capillary permeability, on refractory chronic prostatitis. METHODS: Patients with prostatitis refractory to at least 8 weeks of routine therapy and with urinalysis positive for microhematuria were considered for the present study. In addition to their prior therapy, the patients received carbazochrome at a dose of 30 mg three times a day. The severity of pain (score 0-10), daytime and night-time frequency, international prostate symptom score, global self-assessment, urine occult blood positivity, and adverse events were assessed after 4 and 8 weeks of treatment, and compared with baseline findings. RESULTS: A total of 50 patients (mean age 68.6 ± 8.5 years) were evaluable. The pain score decreased significantly from 3.2 ± 2.1 at baseline to 1.7 ± 1.4 after 4 weeks of treatment and to 1.1 ± 1.8 after 8 weeks. Daytime and night-time frequency, storage symptoms, post-micturition symptoms, and urine occult blood positivity also significantly improved. More than 36% of the patients gave a global self-assessment rating of "improved" or "better" after both 4 and 8 weeks of treatment. Mild adverse events occurred in three patients; one had nausea and two developed drug rash. CONCLUSIONS: Carbazochrome seems to effectively improve pain as well as storage and post-micturition symptoms in patients with refractory chronic prostatitis.

Boosting charge separation in organic photovoltaics: unveiling dipole moment variations in excited non-fullerene acceptor layers.

The power conversion efficiency (PCE) of organic photovoltaics (OPVs) has reached more than 19% due to the rapid development of non-fullerene acceptors (NFAs). To compete with the PCEs (26%) of commercialized silicon-based inorganic photovoltaics, the drawback of OPVs should be minimized. This drawback is the intrinsic large loss of open-circuit voltage; however, a general approach to this issue remains elusive. Here, we report a discovery regarding highly efficient NFAs, specifically ITIC. We found that charge-transfer (CT) and charge dissociation (CD) can occur even in a neat ITIC film without the donor layer. This is surprising, as these processes were previously believed to take place exclusively at donor/acceptor heterojunctions. Femtosecond time-resolved visible to mid-infrared measurements revealed that in the neat ITIC layers, the intermolecular CT immediately proceeds after photoirradiation (<0.1 ps) to form weakly-bound excitons with a binding energy of 0.3 eV, which are further dissociated into free electrons and holes with a time-constant of 56 ps. Theoretical calculations indicate that stacking faults in ITIC (i.e., V-type molecular stacking) induce instantaneous intermolecular CT and CD in the neat ITIC layer. In contrast, J-type stacking does not support such CT and CD. This previously unknown pathway is triggered by the larger dipole moment change on the excited state generated at the lower symmetric V-type molecular stacking of ITIC. This is in sharp contrast with the need of sufficient energy offset for CT and CD at the donor-acceptor heterojunction, leading to the significant voltage loss in conventional OPVs. These results demonstrate that the rational molecular design of NFAs can increase the local dipole moment change on the excited state within the NFA layer. This finding paves the way for a groundbreaking route toward the commercialization of OPVs.

An emissive charge-transfer excited-state at the well-defined hetero-nanostructure interface of an organic conjugated molecule and two-dimensional inorganic nanosheet.

Precise engineering of excited-state interactions between an organic conjugated molecule and a two-dimensional semiconducting inorganic nanosheet, specifically the manipulation of charge-transfer excited (CTE) states, still remains a challenge for state-of-the-art photochemistry. Herein, we report a long-lived, highly emissive CTE state at structurally well-defined hetero-nanostructure interfaces of photoactive pyrene and two-dimensional MoS2 nanosheets via an N-benzylsuccinimide bridge (Py-Bn-MoS2). Spectroscopic measurements reveal that no charge-transfer state is formed in the ground state, but the locally-excited (LE) state of pyrene in Py-Bn-MoS2 efficiently generates an unusual emissive CTE state. Theoretical studies elucidate the interaction of MoS2 vacant orbitals with the pyrene LE state to form a CTE state that shows a distinct solvent dependence of the emission energy. This is the first example of organic-inorganic 2D hetero-nanostructures displaying mixed luminescence properties by an accurate design of the bridge structure, and therefore represents an important step in their applications for energy conversion and optoelectronic devices and sensors.

Photodynamic and photothermal effects of semiconducting and metallic-enriched single-walled carbon nanotubes.

Semiconducting and metallic single-walled carbon nanotubes (s-SWNTs and m-SWNTs) were enriched by agarose gel chromatography and their photothermal and photodynamic effects were compared in H(2)O. Under near-infrared laser irradiation, s-SWNTs generated reactive oxygen species (ROS) more than m-SWNTs, whereas m-SWNTs produced heat more efficiently than s-SWNTs. More importantly, cancer cell killing by PDE of s-SWNTs has been disclosed for the first time.

Preparation and photophysical and photoelectrochemical properties of a covalently fixed porphyrin-chemically converted graphene composite.

Chemically converted graphene (CCG) covalently linked with porphyrins has been prepared by a Suzuki coupling reaction between iodophenyl-functionalized CCG and porphyrin boronic ester. The covalently linked CCG-porphyrin composite was designed to possess a short, rigid phenylene spacer between the porphyrin and the CCG. The composite material formed stable dispersions in DMF and the structure was characterized by spectroscopic, thermal, and microscopic measurements. In steady-state photoluminescence spectra, the emission from the porphyrin linked to the CCG was quenched strongly relative to that of the porphyrin reference. Fluorescence lifetime and femtosecond transient absorption measurements of the porphyrin-linked CCG revealed a short-lived porphyrin singlet excited state (38 ps) without yielding the porphyrin radical cation, thereby substantiating the occurrence of energy transfer from the porphyrin excited state to the CCG and subsequent rapid decay of the CCG excited state to the ground state. Consistently, the photocurrent action spectrum of a photoelectrochemical device with a SnO(2) electrode coated with the porphyrin-linked CCG exhibited no photocurrent response from the porphyrin absorption. The results obtained here provide deep insight into the interaction between graphenes and π-conjugated systems in the excited and ground states.

Segregated donor-acceptor columns in liquid crystals that exhibit highly efficient ambipolar charge transport.

Liquid crystalline donor (i.e., phthalocyanine) was covalently linked to acceptor (i.e, fullerene) to achieve efficient charge-transport properties in a liquid crystalline phase. The columnar structure exhibited highly efficient ambipolar charge-transport character, demonstrating the potential utility of the strategy in organic electronics.

Electron transfer cascade by organic/inorganic ternary composites of porphyrin, zinc oxide nanoparticles, and reduced graphene oxide on a tin oxide electrode that exhibits efficient photocurrent generation.

A bottom-up strategy has been developed to construct a multiple electron transfer system composed of organic/inorganic ternary composites (porphyrin, zinc oxide nanoparticles, reduced graphene oxide) on a semiconducting electrode without impairing the respective donor-acceptor components. The hierarchical electron transfer cascade system exhibited remarkably high photocurrent generation with an incident-photon-to-current efficiency of up to ca. 70%.

Long-Range Interfacial Charge Carrier Trapping in Halide Perovskite-C60 and Halide Perovskite-TiO2 Donor-Acceptor Films.

Interfacial electron transfer across perovskite-electron acceptor heterojunctions plays a significant role in the power-conversion efficiency of perovskite solar cells. Thus, electron donor-acceptor thin films of halide perovskite nanocrystals receive considerable attention. Nevertheless, understanding and optimizing distance- and thickness-dependent electron transfer in perovskite-electron acceptor heterojunctions are important. We reveal the distance-dependent and diffusion-controlled interfacial electron transfer across donor-acceptor heterojunction films formed by formamidinium or cesium lead bromide (FAPbBr3/CsPbBr3) perovskite nanocrystals with TiO2/C60. Self-assembled nanocrystal films prepared from FAPbBr3 show a longer photoluminescence lifetime than a solution, showing a long-range carrier migration. The acceptors quench the photoluminescence intensity but not the lifetime in a solution, revealing a static electron transfer. Conversely, the electron transfer in the films changes from dynamic to static by moving toward the donor-acceptor interface. While radiative recombination dominates the electron transfer at 800 µm or farther, the acceptors scavenge the photogenerated carriers within 100 µm. This research highlights the significance of interfacial electron transfer in perovskite films.

Large pi-aromatic molecules as potential sensitizers for highly efficient dye-sensitized solar cells.

Recently, dye-sensitized solar cells have attracted much attention relevant to global environmental issues. Thus far, ruthenium(II) bipyridyl complexes have proven to be the most efficient TiO(2) sensitizers in dye-sensitized solar cells. However, a gradual increment in the highest power conversion efficiency has been recognized in the past decade. More importantly, considering that ruthenium is a rare metal, novel dyes without metal or using inexpensive metal are desirable for highly efficient dye-sensitized solar cells. Large pi-aromatic molecules, such as porphyrins, phthalocyanines, and perylenes, are important classes of potential sensitizers for highly efficient dye-sensitized solar cells, owing to their photostability and high light-harvesting capabilities that can allow applications in thinner, low-cost dye-sensitized solar cells. Porphyrins possess an intense Soret band at 400 nm and moderate Q bands at 600 nm. Nevertheless, the poor light-harvesting properties relative to the ruthenium complexes have limited the cell performance of porphyrin-sensitized TiO(2) cells. Elongation of the pi conjugation and loss of symmetry in porphyrins cause broadening and a red shift of the absorption bands together with an increasing intensity of the Q bands relative to that of the Soret band. On the basis of the strategy, the cell performance of porphyrin-sensitized solar cells has been improved intensively by the enhanced light absorption. Actually, some push-pull-type porphyrins have disclosed a remarkably high power conversion efficiency (6-7%) that was close to that of the ruthenium complexes. Phthalocyanines exhibit strong absorption around 300 and 700 nm and redox features that are similar to porphyrins. Moreover, phthalocyanines are transparent over a large region of the visible spectrum, thereby enabling the possibility of using them as "photovoltaic windows". However, the cell performance was poor, owing to strong aggregation and lack of directionality in the excited state. Novel unsymmetrical zinc phthalocyanine sensitizers with "push" and "pull" groups have made it possible to reduce the aggregation on a TiO(2) surface, tune the level of the excited state, and strengthen the electronic coupling between the phthalocyanine core and the TiO(2) surface. As a result, the power conversion efficiency of up to 3.5% has been achieved. Perylenes are well-known as chemically, thermally, and photophysically stable dyes and have been used in various optical devices and applications. Nevertheless, the power conversion efficiency remained low compared to other organic dyes. The origin of such limited cell performance is the poor electron-donating abilities of the perylenes, which makes it difficult to inject electrons from the excited singlet state of the perylenes to the conduction band of the TiO(2) electrode efficiently. Strongly electron-donating perylene carboxylic acid derivatives with amine substituents at their perylene core have allowed us to increase the power conversion efficiency of up to approximately 7% in perylene-sensitized solar cells. The efficiency of large pi-aromatic molecule-sensitized solar cells could be improved significantly if the dyes with larger red and near-infrared absorption could be developed.

Efficient light-harvesting, energy migration, and charge transfer by nanographene-based nonfullerene small-molecule acceptors exhibiting unusually long excited-state lifetime in the film state.

Electron-acceptor small-molecules possessing a long exciton lifetime and a narrow energy band gap, opposing the energy gap law, are highly desirable for high-performance organic photovoltaics (OPVs) by realizing their efficient light-harvesting ability (LH), exciton diffusion (ED), and charge transfer (CT). Toward this goal, we designed an acceptor-donor-acceptor (A-D-A) type nonfullerene acceptor (NFA), TACIC, having an electron-donating, self-assembling two-dimensional (2D) nanographene unit, thienoazacoronene, at the center with electron-withdrawing groups at both ends. The TACIC film exhibited a narrow band gap (1.59 eV) with excellent LH. Surprisingly, the TACIC film showed an extremely long exciton lifetime (1.59 ns), suppressing undesirable nonradiative decay by its unique self-assembling behavior. When combined with a conjugated polymer donor, PBDB-T, slow ED and CT were observed (60 ps) with the excitation of TACIC owing to the large TACIC domain sizes. Nevertheless, the unusually high efficiencies of ED and CT (96% in total) were achieved by the long TACIC exciton lifetime. Additionally, unusual energy transfer (EnT) from the excited PBDB-T to TACIC was seen, demonstrating its dual LH role. The OPV device with PBDB-T and TACIC showed a high incident photon-to-current efficiency (IPCE) exceeding 70% at up to 710 nm and a power conversion efficiency of ∼10%. This result will open up avenues for a rational strategy of OPVs where LH, ED, and CT from the acceptor side as well as LH, EnT, ED, and CT from the donor side can be better designed by using 2D nanographene as a promising building block for high-performance A-D-A type NFAs.

Efficient Exciton Diffusion in Micrometer-Sized Domains of Nanographene-Based Nonfullerene Acceptors with Long Exciton Lifetimes in Blend Films with Conjugated Polymer.

Phase-separated structures in photoactive layers composed of electron donors and acceptors in organic photovoltaics (OPVs) generally exert a profound impact on the device performance. In this study, nonfullerene acceptors (NFAs) where a heteronanographene central core was furnished with branched alkoxy chains of different lengths, TACIC-EH, TACIC-BO, and TACIC-HD, were prepared to adjust the aggregation tendency and systematically probe the relationships of film structures with photophysical and photovoltaic properties. The side-chain length showed negligible effects on the absorption properties and energy levels of TACICs. In addition, regardless of the chain length, all TACIC films exhibited characteristically long singlet exciton lifetimes (1330-2330 ps) compared to those in solution (≤220 ps). Using a conjugated polymer donor, PBDB-T, the best OPV performance was achieved with TACIC-BO that contained medium-length chains, exhibiting a power conversion efficiency (PCE) of 9.92%. TACIC-HD with the longest chains showed deteriorated electron mobility due to the long insulating alkoxy groups. Therefore, the PBDB-T:TACIC-HD-based device revealed a low charge collection efficiency and PCE (8.21%) relative to the PBDB-T:TACIC-BO-based device, but their film morphologies were analogous. Meanwhile, TACIC-EH with the shortest chains showed low solubility and formed micrometer-sized large aggregates in the blend film with PBDB-T. Although the charge collection efficiency of PBDB-T:TACIC-EH was lower than that of PBDB-T:TACIC-BO, the efficiencies of exciton diffusion to the donor-acceptor interface were sufficiently high (>98%) owing to the elongated singlet exciton lifetime of TACIC-EH. The PCE of the PBDB-T:TACIC-EH-based device remained moderate (7.10%). Therefore, TACICs with the long singlet exciton lifetimes in the films provide a clear guideline for NFAs with low sensitivity of OPV device performance to the blend film structures, which is advantageous for large-scale OPV production with high reproducibility.

Supramolecular donor-acceptor heterojunctions by vectorial stepwise assembly of porphyrins and coordination-bonded fullerene arrays for photocurrent generation.

A novel strategy for constructing a vertical arrangement of bicontinuous donor-acceptor arrays on a semiconducting electrode has been developed. The relationship between the film structure and the photoelectrochemical properties has been elucidated as a function of the number of donor layers for the first time. The maximum incident photon-to-current efficiency value (21%) is comparable to the highest value (20%) reported for vertical arrangements of bicontinuous donor-acceptor arrays on electrodes.

Spontaneous Complexation of Fullerene Aggregates on Nanodiamond Aggregates and Their Enhanced Photocurrent Generation.

Supramolecular composites composed of fullerene C60 and carbon nanodiamond (ND) were constructed through spontaneous complexation of C60 aggregates onto the surface of ND aggregates in N-methylpyrrolidone (NMP). The resulting C60 -ND composite was assembled onto a nanostructured SnO2 electrode by an electrophoretic deposition method. Formation of the C60 -ND composite was confirmed by dynamic light scattering (DLS) and field-emission scanning electron microscopy (FESEM). The C60 -ND composite on the SnO2 electrode showed high incident photon-to-current efficiencies (IPCEs) in the visible region as compared with the single component system of C60 or ND. The improved photocurrent generation of the C60 -ND composite may result from the photoinduced charge separation at the interface between C60 and ND. These results obtained here will provide valuable information on the design of optoelectronic devices based on all-nanocarbon materials.