Yishi Wu

Near-Infrared Lasing from Small-Molecule Organic Hemispheres

Near-infrared (NIR) lasers are key components for applications, such as telecommunication, spectroscopy, display, and biomedical tissue imaging. Inorganic III-V semiconductor (GaAs) NIR lasers have achieved great successes but require expensive and sophisticated device fabrication techniques. Organic semiconductors exhibit chemically tunable optoelectronic properties together with self-assembling features that are well suitable for low-temperature solution processing. Major blocks in realizing NIR organic lasing include low stimulated emission of narrow-bandgap molecules due to fast nonradiative decay and exciton-exciton annihilation, which is considered as a main loss channel of population inversion for organic lasers under high carrier densities. Here we designed and synthesized the small organic molecule (E)-3-(4-(di-p-tolylamino)phenyl)-1-(1-hydroxynaphthalen-2-yl)prop-2-en-1-one (DPHP) with amphiphilic nature, which elaborately self-assembles into micrometer-sized hemispheres that simultaneously serves as the NIR emission medium with a photoluminescence quantum efficiency of ∼15.2%, and the high-Q (∼1.4 × 10(3)) whispering gallery mode microcavity. Moreover, the radiative rate of DPHP hemispheres is enhanced up to ∼1.98 × 10(9) s(-1) on account of the exciton-vibrational coupling in the solid state with the J-type molecular-coupling component, and meanwhile the exciton-exciton annihilation process is eliminated. As a result, NIR lasing with a low threshold of ∼610 nJ/cm(2) is achieved in the single DPHP hemisphere at room temperature. Our demonstration is a major step toward incorporating the organic coherent light sources into the compact optoelectronic devices at NIR wavelengths.

Photoinduced Intramolecular Electron Transfer in Conjugated Perylene Bisimide-Dithienothiophene Systems: A Comparative Study of a Small Molecule and a Polymer

The solution photophysical properties of two conjugated dithienothiophene (DTT)-perylene bisimide (PBI) systemsa polymer, poly{[N,N-bis(2-decyl-tetradecyl)-3,4,9,10-perylene diimide-1,7-diyl]-alt-(dithieno[3,2-b:2,3-d]thiophene-2,6-diyl)}, and a small molecule, 1,7-bis(dithieno[3,2-b:2,3-d]thiophene-2-yl)-N,N-bis(2-decyl-tetradecyl)-3,4,9,10-perylene diimidein solution have been investigated. Strong quenching of the fluorescence of the PBI moiety was observed in both DTT-PBI systems, suggesting the possibility of an efficient intramolecular electron-transfer process. The kinetics of photoinduced electron transfer in the DTT-PBI polymer and monomer in solutions were explored by femtosecond time-resolved transient absorption spectra. It was found that both the rates of charge separation and charge recombination in the DTT-PBI polymer were approximately double those in the small molecule. This indicates that electronic coupling plays an important role in the electron-transfer process in a polymer system.

Cross-sectional electron microscopy observation on the amorphized indentation region in 001 single-crystal silicon

The amorphized region of single-crystal silicon (c-Si) induced by Vickers indentation has been studied cross-sectionally by transmission electron microscopy (TEM) and high-resolution electron microscopy (HREM). A comparison between the V-shaped profile of the amorphous region and the stress isobars under the indenter shows that the deviatoric stress plays a significant role in the formation of amorphous silicon (a-Si). A number of defects near the crystalline/amorphous (c/a) interface, and the refinement and rotation of grains at local regions, are observed by HREM. The distortion of lattice fringes in the c-Si region and the domains characterized by distorted lattice in the a-Si region near the interface as well as continuous transition from the crystalline to the amorphous region at the interface are also observed. A possible mechanism of defect-induced or heavy-deformation-induced amorphization of silicon under indentation is suggested.

Role of ligand-to-metal charge transfer state in nontriplet photosensitization of luminescent europium complex.

We have investigated, by means of steady-state and time-resolved optical spectroscopies, the excited-state dynamics of the luminescent europium complex Eu(III)(tta)(3)dpbt (tta = henoyltrifluoroacetonate; dbpt = 2-(N,N-diethylanilin-4-yl)-4,6-bis(3,5-dimethylpyrazol-1-yl)-1,3,5-triazine) with Gd(III)(tta)(3)dpbt and Tb(III)(tta)(3)dpbt as the reference complexes that cannot be photosensitized. In the Eu(III)(tta)(3)dpbt complex, the ligand dpbt exhibited biphasic fluorescence decay kinetics; the faster component (decay time constant, 8.5 ps) is ascribed to the rapid conversion of the lowest-lying singlet excited state of dpbt (S(1) or (1)dpbt*) to a ligand-to-metal charge transfer singlet state of the complex ((1)LMCT*), whereas the slower one (1.8 ns) is shown by temperature-dependent luminescence spectroscopy to be delayed fluorescence due to the LMCT-to-dpbt backward energy transfer and represents the time scale of efficient excitation energy flow from the (1)LMCT* state to the (5)D(1) state of Eu(III). On the basis of the spectroscopic results of the Ln(III)(tta)(3)dpbt complexes (Ln = Eu, Gd, and Tb), the crucial role of the (1)LMCT* state in photosensitization of the Eu(III)(tta)(3)dpbt complex is established, and a LMCT-mediated nontriplet sensitization mechanism is proposed, which is advantageous in high efficiency and low excitation photon energy as well as in low susceptibility against oxygen quenching.

Tunable Morphology of the Self-Assembled Organic Microcrystals for the Efficient Laser Optical Resonator by Molecular Modulation

Organic single-crystalline micro/nanostructures can effectively generate and carry photons due to their smooth morphologies, high photoluminescence quantum efficiency, and minimized defects density and therefore are potentially ideal building blocks for the optical circuits in the next generation of miniaturized optoelectronics. However, the tailor-made organic molecules can be generally obtained by organic synthesis, ensuring that the organic molecules aggregate in a specific form and generate micro/nanostructures with desirable morphology and therefore act as the efficient laser optical resonator remains a great challenge. Here, the molecular modulation of the morphology on the laser optical resonator properties has been investigated through the preparation of the elongated hexagonal microplates (PHMs) and the rectangular microplates (ORMs), respectively, from two model isomeric organic molecules of 1,4-bis(4-methylstyryl)benzene (p-MSB) and 1,4-bis(2-methylstyryl)benzene (o-MSB). Significantly, fluorescence resonance phenomenon was only observed in the individual ORM other than the PHM. It indicates that the rectangular resonators possess better light-confinement property over the elongated hexagonal resonators. More importantly, optically pumped lasing action was observed in the o-MSB rectangular morphology microplates resonator with a high Q ≈ 1500 above a threshold of ∼540 nJ/cm(2). The excellent optical properties of these microstructures are associated with the morphology, which can be precisely modulated by the organic molecular structure. These self-assembled organic microplates with different morphologies can contribute to the distinct functionality of photonics elements in the integrated optical circuits at micro/nanoscale.

Impact of Intermolecular Distance on Singlet Fission in a Series of TIPS Pentacene Compounds

Singlet fission has attracted considerable interest for its potential application in organic photovoltaics. However, the underlying microscopic mechanism is not well understood and the molecular parameters that govern SF efficiency remain unclear. We herein study the primary exciton photogeneration and evolution in the thin film of a series of pentacene derivatives (TIPS-Pn and ADPD-Pn) using femtosecond transient absorption spectroscopy. With a favorable long-edge on packing motif, the singlet-excited slip-stacked TIPS-Pn and ADPD-Pn molecules undergo ultrafast fission to produce triplet excitonic states with time constants of ∼0.3 ps. More importantly, the ADPD-Pn compound features a considerably higher triplet yield than TIPS-Pn (162 ± 10% vs 114 ± 15%). The enhanced electronic coupling as a result of closer interchromophore distance (3.33 Å for ADPD-Pn vs 3.40 Å for TIPS-Pn) is suggested to account for the much higher triplet yield for ADPD-Pn relative to that for TIPS-Pn, proving SF can be readily modulated by adjusting the intermolecular distance.

Water-miscible organic J-aggregate nanoparticles as efficient two-photon fluorescent nano-probes for bio-imaging

Many two-photon absorption (TPA) organic dyes are water insoluble and suffer from strong fluorescence quenching in aqueous media due to the self-aggregation effect. This seriously limits their applications as two-photon fluorescence (TPF) probes in bio-imaging. By employing a reprecipitation method, we prepared ultrabright water-miscible organic nanoparticles (ONPs) of 1,4-dimethoxy-2,5-di[4-(cyano)styryl]benzene (COPV). The single-crystal structure reveals that the cooperation between pi-pi stacking and hydrogen-bonding interactions drives COPV molecules into a brickwork arrangement of J-aggregates, in which the coherent excitation delocalization reaches 2-3 molecules. Due to the superradiance of J-aggregates, COPV ONPs are highly emissive in aqueous media with a quantum yield >0.4; meanwhile, their TPA cross-section is greatly enhanced, probably due to exciton-vibration coupling. As TPF probes, COPV J-aggregate ONPs are 3-4 orders of magnitude brighter than conventional fluorescent dyes and an order of magnitude brighter than quantum dots. Moreover, these ONPs exhibit no obvious cytotoxicity at concentrations as high as 100 mu g mL(-1). Our results demonstrate that ultrabright J-aggregate ONPs of COPV provide a new strategy to construct efficient TPF nano-probes for bio-imaging.

Photocurrent Enhancement of BODIPY-Based Solution-Processed Small-Molecule Solar Cells by Dimerization via the Meso Position

Three 4,4-difluoro-4-bora-3a,4a-diaza-s-indancene (BODIPY)-based small molecule donors H-T-BO, Br-T-BO, and DIMER were synthesized and fully characterized. Although modification at the meso position has a subtle influence on the light-harvesting ability, energy levels, and phase sizes, it has a striking effect on the packing behavior in solid film as two-dimension grazing incidence X-ray diffraction (2D GIXRD) and X-ray diffraction (XRD) confirm. Br-T-BO exhibits better packing ordering than H-T-BO in pristine film, which is beneficial from reinforced intermolecular interaction from halogen atoms. However, when [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM) is blended, no diffraction patterns corresponding to the monomeric donor can be seen from the XRD data and both H-T-BO- and Br-T-BO-based blend films give a slightly blue-shifting absorption peak with respect to their neat ones, both of which imply destruction of the crystalline structure. As for DIMER, the enhancement of the intermolecular interaction arises not only from the expansion of the backbone but the steric pairing effect brought on by its twisted structure. When blended with PC71BM, the diffraction patterns of DIMER are, however, kept well and the absorption peak position remains unchanged, which indicates the ordered packing of DIMER is held well in blend film. In coincidence with the fact that packing ordering improves from H-T-BO to Br-T-BO and DIMER in pristine films and the ordered packing of DIMER even in blend film, DIMER-based devices show the highest and most balanced hole/electron mobility of 1.16 × 10(-3)/0.90 × 10(-3) cm(2) V(-1) s(-1)with respect to Br-T-BO (4.71 × 10(-4)/2.09 × 10(-4) cm(2) V(-1) s(-1)) and H-T-BO (4.27 × 10(-5)/1.00 × 10(-5) cm(2) V(-1) s(-1)) based ones. The short-circuit current density of the three molecule-based cells follows the same trend from H-T-BO (6.80) to Br-T-BO (7.62) and then to DIMER (11.28 mA cm(-2)). Finally, the H-T-BO-, Br-T-BO-, and DIMER-based optimal device exhibits a power conversion efficiency of 1.56%, 1.96%, and 3.13%, respectively.

Excessive Exoergicity Reduces Singlet Exciton Fission Efficiency of Heteroacenes in Solutions

The energy difference between a singlet exciton and twice of a triplet exciton, ΔESF, provides the thermodynamic driving force for singlet exciton fission (SF). This work reports a systematic investigation on the effect of ΔESF on SF efficiency of five heteroacenes in their solutions. The low-temperature, near-infrared phosphorescence spectra gave the energy levels of the triplet excitons, allowing us to identify the values of ΔESF, which are -0.58, -0.34, -0.31, -0.32, and -0.34 eV for the thiophene, benzene, pyridine, and two tetrafluorobenzene terminated molecules, respectively. Corresponding SF efficiencies of the five heteroacenes in 0.02 M solutions were determined via femtosecond transient absorption spectroscopy to be 117%, 124%, 140%, 132%, and 135%, respectively. This result reveals that higher ΔESF is not, as commonly expected, always beneficial for higher SF efficiency in solution phase. On the contrary, excessive exoergicity results in reduction of SF efficiency in the heteroacenes due to the promotion of other competitive exciton relaxation pathways. Therefore, it is important to optimize thermodynamic driving force when designing organic materials for high SF efficiency.

Self-Assembled Microdisk Lasers of Perylenediimides.

Organic solid-state lasers (OSSLs) have been a topic of intensive investigations. Perylenediimide (PDI) derivatives are widely used in organic thin-film transistors and solar cells. However, OSSLs based on neat PDIs have not been achieved yet, owing to the formation of H-aggregates and excimer trap-states. Here, we demonstrated the first PDI-based OSSL from whispering-gallery mode (WGM) hexagonal microdisk (hMD) microcavity of N,N-bis(1-ethylpropyl)-2,5,8,11-tetrakis(p-methyl-phenyl)-perylenediimide (mp-PDI) self-assembled from solution. Single-crystal data reveal that mp-PDI molecules stack into a loosely packed twisted brickstone arrangement, resulting in J-type aggregates that exhibit a solid-state photoluminescence (PL) efficiency φ > 15%. Moreover, we found that exciton-vibration coupling in J-aggregates leads to an exceptional ultrafast radiative decay, which reduces the exciton diffusion length, in turn, suppresses bimolecular exciton annihilation (bmEA) process. These spectral features, plus the optical feedback provided by WGM-hMD microcavity, enable the observation of multimode lasing as evidenced by nonlinear output, spectral narrowing, and temporal coherence of laser emission. With consideration of high carrier-mobility associated with PDIs, hMDs of mp-PDI are attractive candidates on the way to achieve electrically driven OSSL.