Optically Transparent Lead Halide Perovskite Polycrystalline Ceramics.

We utilize room-temperature uniaxial pressing at applied loads achievable with low-cost, laboratory-scale presses to fabricate freestanding CH3NH3PbX3 (X- = Br-, Cl-) polycrystalline ceramics with millimeter thicknesses and optical transparency up to ∼70% in the infrared. As-fabricated perovskite ceramics can be produced with desirable form factors (i.e., size, shape, and thickness) and high-quality surfaces without any postprocessing (e.g., cutting or polishing). This method should be broadly applicable to a large swath of metal halide perovskites, not just the compositions shown here. In addition to fabrication, we analyze microstructure-optical property relationships through detailed experiments (e.g., transmission measurements, electron microscopy, X-ray tomography, optical profilometry, etc.) as well as modeling based on Mie theory. The optical, electrical, and mechanical properties of perovskite polycrystalline ceramics are benchmarked against those of single-crystalline analogues through spectroscopic ellipsometry, Hall measurements, and nanoindentation. Finally, γ-ray scintillation from a transparent MAPbBr3 ceramic is demonstrated under irradiation from a 137Cs source. From a broader perspective, scalable methods to produce freestanding polycrystalline lead halide perovskites with comparable properties to their single-crystal counterparts could enable key advancements in the commercial production of perovskite-based technologies (e.g., direct X-ray/γ-ray detectors, scintillators, and nonlinear optics).

Interstitial Nature of Mn2+ Doping in 2D Perovskites.

Halide perovskites doped with magnetic impurities (such as the transition metals Mn2+, Co2+, Ni2+) are being explored for a wide range of applications beyond photovoltaics, such as spintronic devices, stable light-emitting diodes, single-photon emitters, and magneto-optical devices. However, despite several recent studies, there is no consensus on whether the doped magnetic ions will predominantly replace the octahedral B-site metal via substitution or reside at interstitial defect sites. Here, by performing correlated nanoscale X-ray microscopy, spatially and temporally resolved photoluminescence measurements, and magnetic force microscopy on the inorganic 2D perovskite Cs2PbI2Cl2, we show that doping Mn2+ into the structure results in a lattice expansion. The observed lattice expansion contrasts with the predicted contraction expected to arise from the B-site metal substitution, thus implying that Mn2+ does not replace the Pb2+ sites. Photoluminescence and electron paramagnetic resonance measurements confirm the presence of Mn2+ in the lattice, while correlated nano-XRD and X-ray fluorescence track the local strain and chemical composition. Density functional theory calculations predict that Mn2+ atoms reside at the interstitial sites between two octahedra in the triangle formed by one Cl- and two I- atoms, which results in a locally expanded structure. These measurements show the fate of the transition metal dopants, the local structure, and optical emission when they are doped at dilute concentrations into a wide band gap semiconductor.

Synthesis and photophysics of gold(i) alkynyls bearing a benzothiazole-2,7-fluorenyl moiety: a comparative study analyzing influence of ancillary ligand, bridging moiety, and number of metal centers on photophysical properties.

Three new gold(i) alkynyl complexes (Au-ABTF(0-2)) containing a benzothiazole fluorenyl moiety, with either an organic phosphine or N-heterocyclic carbene as ancillary ligand, have been synthesized and photophysically characterized. All three complexes display highly structured ground-state absorption and luminescence spectra. Dual-luminescence is observed in all three complexes at room temperature in toluene after three freeze-pump-thaw cycles. The phosphine complexes (Au-ABTF(0-1)) exhibit similar photophysics with fluorescent quantum yields ∼0.40, triplet-state quantum yields ∼0.50, and fluorescent lifetimes ∼300 ps. The carbene complex Au-ABTF2 displays different behavior; having a fluorescent quantum yield of 0.23, a triplet-state quantum yield of 0.61, and a fluorescent lifetime near 200 ps, demonstrating that the ancillary ligand alters excited-state dynamics. The compounds exhibit strong (on the order of 105 M-1 cm-1) and positive excited-state absorption in both their singlet and triplet excited states spanning the visible region. Delayed fluorescence resulting from triplet-triplet annihilation is also observed in freeze-pump-thaw deaerated samples of all the complexes in toluene. DFT calculations (both static and time-resolved) agree with the photophysical data where phosphine complexes have slightly larger S1-T2 energy gaps (0.28 eV and 0.26 eV) relative to the carbene complex (0.21 eV). Comparison of the photophysical properties of Au-ABTF(0-2) to previously published dinuclear gold(i) complexes and mononuclear gold(i) aryl complexes bearing the same benzothiazole-2,7-fluorenyl moiety are made. Structure-property relationships regarding ancillary ligand, bridging moiety, and number of metal centers are drawn.

Designing CdS-Based Ternary Heterostructures Consisting of Co-Metal and CoOx Cocatalysts for Photocatalytic H2 Evolution under Visible Light.

Heterostructure formation is an effective method used for designing photocatalysts that solve problems caused by photoexcited charge recombination phenomena associated with the photocatalytic water redox reaction. This work reports a new Co-metal-incorporated ternary heterostructured photocatalyst, CdS/CoOx/Co-metal, which enhanced charge separation to increase photocatalytic H2 evolution 30.5-fold in comparison to pure CdS under visible light. This work demonstrates for the first time the effect of the Co metal on photocatalytic H2 evolution using the CdS/CoOx/Co-metal ternary heterostructure. In the ternary heterostructure, Co metal and CoOx act as photogenerated electron- and hole-capturing cocatalysts, respectively. Results from photoelectrochemical studies along with photocatalytic H2 evolution data proved the enhancement of charge transfer and separation in the CdS/CoOx/Co-metal heterostructure due to the addition of Co metal and CoOx. Hence, the synergistic charge separation improvement achieved by the combination of CoOx and the Co metal with CdS produced a photocatalytic H2 evolution rate of 9.54 µmol/h, which is the highest reported H2 evolution rate for a CdS-based system under l sun solar irradiance (>420 nm) to the best of our knowledge.

Effect of chloride substitution on interfacial charge transfer processes in MAPbI3 perovskite thin film solar cells: planar versus mesoporous.

For photovoltaic devices based on hybrid organic-inorganic perovskite thin films, the cell architecture is a vital parameter in defining the macroscopic performance. However, the understanding of the correlation between architecture and carrier dynamics in perovskite thin films has remained elusive. In this work, we utilize concerted materials characterization and optical measurements to investigate the role of chloride addition in PSC devices with two different architectures. Perovskite thin films, prepared with varying ratios of methylammonium halide MACl : MAI (0 : 1, 0.5 : 1, 1 : 1, and 2 : 1), were coated on either planar or mesoporous TiO2/FTO substrates. X-ray diffraction analysis reveals that with increasing the ratio of the Cl- precursor, there is an increasing preferential directional growth of the perovskite film in both configurations. Time-resolved photoluminescence spectroscopy was applied to investigate the electron injection dynamics from the photoexcited perovskites to the TiO2. It is found that the interfacial electron injection rate from perovskite to planar TiO2 is accelerated with increasing Cl- content, which explains the increased power conversion efficiencies using Cl--modified perovskites as photoactive materials. In contrast, Cl- addition demonstrate no discernable influence on electron injection to mesoporous TiO2, suggesting the interfacial charge recombination rather than electron injection give rise to the improved performance observed in the mesoporous configuration. The results presented here, provide a deeper understanding of the mechanism of chloride addition to MAPbI3 solar cells with different architectures.

Manipulating triplet states: tuning energies, absorption, lifetimes, and annihilation rates in anthanthrene derivatives.

The photophysical properties of anthanthrene, four anthanthrene derivatives containing varying phenyl and p-tBu-phenyl substituents, and two anthanthrones with phenyl and p-tBu-phenyl substituents are examined. In general, as the anthanthrenes and anthanthrones become more substituted, red-shifts are observed in the peak maxima of the ground- and excited-state absorption and fluorescence spectra. The anthanthrones have large (>0.8) intersystem crossing (ISC) quantum yields (ΦT) likely caused by nπ* character in the ground or excited states. A bromo-substituted anthanthrene has a unity ISC yield due to an ISC rate constant of 2.5 × 1010 s-1 caused by heavy-atom induced, spin-orbit coupling. This leads to low fluorescence quantum yields (ΦF) in these three derivatives. The parent anthanthrene and remaining derivatives behave much differently. All have ΦF values from 0.58-0.84 with lower ΦT values as radiative decay outcompetes ISC. The anthanthrones have remarkable excited-state absorption with strong, broad transitions across the visible region with weaker transitions extending to nearly two µm. The anthanthrenes have very similar-shaped, broad transitions in the visible which can be shifted ∼60 nm by controlling the substituents. The triplet lifetimes range from 31-1200 µs and increase as the ISC yields decrease; the bromo-substituted anthanthrene is the shortest, followed by the anthanthrones then the other anthanthrenes. The rate of triplet-triplet annihilation is also affected by the presence of substituents; as the amount of steric bulk is increased, the rate of annihilation decreases.

Optoelectronic Dichotomy of Mixed Halide CH3NH3Pb(Br1- xCl x)3 Single Crystals: Surface versus Bulk Photoluminescence.

In this work, the spatially dependent recombination kinetics of mixed-halide hybrid perovskite CH3NH3Pb(Br1- xCl x)3 (0 ≤ x ≤ 0.19) single crystals are investigated using time-resolved photoluminescence spectroscopy with one- and two-photon femtosecond laser excitation. The introduction of chloride by substituting a fraction of the bromide leads to a decreased lattice constant compared to pure bromide perovskite ( x = 0) and a higher concentration of surface defects. The measured kinetics under one-photon excitation (1PE) shows that increasing the chloride addition quenches the photoluminescence (PL) lifetimes, due to substitution-induced surface defects. In stark contrast, upon 2PE, the PL lifetimes measured deeper in the bulk become longer with increasing chloride addition, until the halide substitution reaches the critical concentration of ∼19%. At x = 19% Cl concentration, a significant reversal of this behavior is observed indicating a change in crystal structure beyond the continuous trends observed at lower percentages of halide substitution ( x ≤ 11%). The observed opposing trends, based on 1PE versus 2PE, highlight a dichotomy between extrinsic (surface) and intrinsic (bulk) effects of chloride substitution on the carrier dynamics in lead bromide perovskites. We discuss the physical relation between halide exchange and bulk carrier lifetimes in CH3NH3PbBr3 in terms of the Rashba effect. We propose that the latter is suppressed at the surface due to disorder in the alignment of the MA and that it increases in the bulk with Cl concentration because of the reduction in lattice parameters, which compresses the space available for the MA orientational degrees of freedom.

Stable 2D Bisthienoacenes: Synthesis, Crystal Packing, and Photophysical Properties.

Two novel 2D bisthienoacenes with annulated thiophene units at different positions were developed. Both 1,2- and 1,4-addition of the α,ß-unsaturated ketone moieties lead to the major formation of four-fold alkylsilylethynyl substituted 2D heteroacenes (namely BTT-4TIPS and BTP-4TIPS). The photophysical, electrochemical properties, crystal packing structures, and charge carrier transport performances were investigated in detail.

Prostate-Specific Membrane Antigen Targeted Gold Nanoparticles for Theranostics of Prostate Cancer.

Prostate cancer is one of the most common cancers and among the leading causes of cancer deaths in the United States. Men diagnosed with the disease typically undergo radical prostatectomy, which often results in incontinence and impotence. Recurrence of the disease is often experienced by most patients with incomplete prostatectomy during surgery. Hence, the development of a technique that will enable surgeons to achieve a more precise prostatectomy remains an open challenge. In this contribution, we report a theranostic agent (AuNP-5kPEG-PSMA-1-Pc4) based on prostate-specific membrane antigen (PSMA-1)-targeted gold nanoparticles (AuNPs) loaded with a fluorescent photodynamic therapy (PDT) drug, Pc4. The fabricated nanoparticles are well-characterized by spectroscopic and imaging techniques and are found to be stable over a wide range of solvents, buffers, and media. In vitro cellular uptake experiments demonstrated significantly higher nanoparticle uptake in PSMA-positive PC3pip cells than in PSMA-negative PC3flu cells. Further, more complete cell killing was observed in Pc3pip than in PC3flu cells upon exposure to light at different doses, demonstrating active targeting followed by Pc4 delivery. Likewise, in vivo studies showed remission on PSMA-expressing tumors 14 days post-PDT. Atomic absorption spectroscopy revealed that targeted AuNPs accumulate 4-fold higher in PC3pip than in PC3flu tumors. The nanoparticle system described herein is envisioned to provide surgical guidance for prostate tumor resection and therapeutic intervention when surgery is insufficient.

Excitonic Interactions in Bacteriochlorin Homo-Dyads Enable Charge Transfer: A New Approach to the Artificial Photosynthetic Special Pair.

Excitonically coupled bacteriochlorin (BC) dimers constitute a primary electron donor (special pair) in bacterial photosynthesis and absorbing units in light-harvesting antenna. However, the exact nature of the excited state of these dyads is still not fully understood. Here, we report a detailed spectroscopic and computational investigation of a series of symmetrical bacteriochlorin dimers, where the bacteriochlorins are connected either directly or by a phenylene bridge of variable length. The excited state of these dyads is quenched in high-dielectric solvents, which we attribute to photoinduced charge transfer. The mixing of charge transfer with the excitonic state causes accelerated (within 41 ps) decay of the excited state for the directly linked dyad, which is reduced by orders of magnitude with each additional phenyl ring separating the bacteriochlorins. These results highlight the origins of the excited-state dynamics in symmetric BC dyads and provide a new model for studying the primary processes in photosynthesis and for the development of artificial, biomimetic systems for solar energy conversion.

Complete Conversion of PbI2 to Methyl Ammonium PbI3 Improves Perovskite Solar Cell Efficiency.

One major disadvantage to the two-step deposition method of perovskite films is the incomplete conversion from PbI2 to perovskite resulting in the presence of a thick PbI2 layer, which hinders charge carrier transportation. In this study, a quaternary ammonium salt has been used to manipulate the crystallization of PbI2 in the first deposition step, which leads to facile incorporation of the methylammonium iodide into the Pb-I lattice and promotes the conversion of PbI2 to perovskite leading to improved device performance.

Photoinduced Homolytic Bond Cleavage of the Central Si-C Bond in Porphyrin Macrocycles Is a Charge Polarization Driven Process.

Photoinduced cleavage of the bond between the central Si atom in porphyrin macrocycles and the neighboring carbon atom of an axial alkyl ligand is investigated by both experimental and computational tools. Photolysis and electron paramagnetic resonance measurements indicate that the Si-C bond cleavage of Si-phthalocyanine occurs through a homolytic process. The homolytic process follows a low-lying electronic excitation of about 1.8 eV that destabilizes the carbide bond of similar bond dissociation energy. Using electronic structure calculations, we provide insight into the nature of the excited state and the resulting photocleavage mechanism. We explain this process by finding that the electronic excited state is of a charge transfer character from the axial ligand toward the macrocycle in the reverse direction of the ground state polarization. We find that the homolytic process yielding the radical intermediate is energetically the most stable mechanistic route. Furthermore, we demonstrate using our computational approach that changing the phthalocyanine to smaller ring system enhances the homolytic photocleavage of the Si-C bond by reducing the energetic barrier in the relevant excited states.

Identification and characterization of the intermediate phase in hybrid organic-inorganic MAPbI3 perovskite.

Perovskite films were prepared using single step solution deposition at different annealing temperatures and annealing times. The crystal structure, phases and grain size were investigated with XRD, XPS and SEM/EDX. The prepared films show a typical orientation of tetragonal perovskite phase and a gradual transition at room temperature from the yellow intermediate phase to the black perovskite phase. Films with high purity were obtained by sintering at 100 °C. In addition, the chemical composition and crystal structure of intermediate phase were investigated in detail. FTIR, UV-vis and NMR spectra revealed the occurance of DMF complexes. Interestingly, the intermediate phase could be transformed to the black perovskite phase upon X-ray irradiation. In addition, the recovery of the aged perovskite films from a yellow intermediate phase back to the black perovskite was shown to be viable via heating and X-ray irradiation.

Heteroleptic cationic iridium(III) complexes bearing naphthalimidyl substituents: synthesis, photophysics and reverse saturable absorption.

Three heteroleptic cationic iridium(iii) complexes containing a cyclometalating 2-[3-(7-naphthalimidylfluoren-2'-yl)phenyl]pyridine ligand and different diimine (N^N) ligands (N^N = 2,2'-bipyridine (bpy, ), 1,10-phenanthroline (phen, ), and 5,5'-bis[7-(benzothiazol-2'-yl)fluoren-2'-yl]-2,2'-bipyridine (BTF-bpy, )) were synthesized and characterized. The photophysics of these complexes was systematically investigated via spectroscopic methods and by time-dependent density functional theory (TDDFT). All complexes possess a very weak charge-transfer tail at ca. 450-570 nm; and two intense absorption bands in the region of 290-350 nm and 350-450 nm, respectively. The emission of in CH2Cl2 emanates predominantly from the C^N ligand-localized (3)π,π* state. These emitting excited states also give rise to broadband triplet excited-state absorption in the visible to the near-IR region (i.e. 420-800 nm for and , and 460-800 nm for ). The kinetics of fs transient absorption (TA) reveals that the lowest singlet excited-state lifetimes of these complexes vary from 1.43 ps to 142 ps. The stronger excited-state absorption of compared to their respective ground-state absorption in the visible spectral range leads to strong reverse saturable absorption (RSA) at 532 nm for ns laser pulses. The trend of transmission signal decrease follows > > . Extending the π-conjugation of the N^N ligand increases the strength of RSA. In addition, the naphthalimidyl (NI) substitution at the cyclometalating ligand dramatically increases the triplet excited-state lifetimes and broadens the triplet excited-state absorption to the NIR region compared to the respective Ir(iii) complexes with a benzothiazolyl substituent on the cyclometalating ligand.

Femtosecond time-resolved transient absorption spectroscopy of CH3NH3PbI3 perovskite films: evidence for passivation effect of PbI2.

CH3NH3PbI3 perovskite layered films deposited on substrates with and without a titania support structure have been prepared and studied using time-resolved femtosecond transient absorption (fs-TA) spectroscopy in the visible light range (450-800 nm). The electron injection dynamics from the photoexcited perovskite layers to the neighboring film structures could be directly monitored via the transient bleaching dynamics of the perovskite at ∼750 nm and thus systematically studied as a function of the layer-by-layer architecture. In addition, for the first time we could spectrally distinguish transient bleaching at ∼750 nm from laser-induced fluorescence that occurs red-shifted at ∼780 nm. We show that an additional bleach feature at ∼510 nm appears when PbI2 is present in the perovskite film. The amplitudes of the PbI2 and perovskite TA peaks were compared to estimate relative amounts of PbI2 in the samples. Kinetic analysis reveals that perovskite films with less PbI2 show faster relaxation rates than those containing more PbI2. These fast dynamics are attributed to charge carrier trapping at perovskite grain boundaries, and the slower dynamics in samples containing PbI2 are due to a passivation effect, in line with other recently reported work.