Time-resolved Emission Spectroscopy Research Articles

Influence of donor-to-acceptor ratio on excited-state electron transfer within covalently tethered CdSe/CdTe quantum dot colloidal heterostructures.

Carbodiimide-mediated coupling chemistry was used to synthesize heterostructures of CdSe and CdTe quantum dots (QDs) with varying ratios of electron-donating CdTe QDs and electron-accepting CdSe QDs. Heterostructures were assembled via the formation of amide bonds between the terminal functional groups of CdTe-adsorbed 4-aminothiophenol (4-ATP) ligands and CdSe-adsorbed N-hydroxysuccinimide (NHS) ligands. The number of charge acceptors on the surfaces of QDs can greatly influence the rate constant of excited-state charge transfer with QDs capable of accommodating far more acceptors than molecular chromophores. We report here on excited-state electron transfer within heterostructure-forming mixtures of 4-ATP-capped CdTe and NHS-capped CdSe QDs with varying molar ratios of CdTe to CdSe. Photophysical properties and charge transfer were characterized using UV-vis absorption, steady-state emission, and time-resolved emission spectroscopy. As the relative concentration of electron-accepting CdSe QDs within mixtures of 4-ATP-capped CdTe and NHS-capped CdSe QDs increased, the rate and efficiency of electron transfer increased by 100-fold and 7.4-fold, respectively, as evidenced by dynamic quenching of band-edge emission from CdTe QDs. In contrast, for non-interacting mixtures of thiophenol capped CdTe QDs and NHS-capped CdSe QDs, which served as control samples, photophysical properties of the constituent QDs were unperturbed and excited-state charge transfer between the QDs was negligible. Our results reveal that carbodiimide-mediated coupling chemistry can be used to control the relative number of donor and acceptor QDs within heterostructures, which, in turn, enables fine-tuning of charge-transfer dynamics and yields. These amide-bridged dual-QD heterostructures are, thus, intriguing for light harvesting, charge transfer, and photocatalysis.

Spectroscopic and computational analysis of the oxygen evolving complex of photosystem II

The oxygen evolving activity of the Photosystem II protein sustains the biosphere. In the final catalytic step (S3 to S0 transition, duration ∼1-2 ms) within the oxygen evolving complex, an O-O bond is formed via an intricate multielectron catalysis. Using time-resolved X-ray emission spectroscopy, a method uniquely sensitive to the electronic structure of the Mn4Ca catalytic center, we demonstrate altered electronic structure very early (∼50 μs) in this transition. Suprisingly, this rapid change is unimpeded when protein functions in a D2O buffer.

Harvesting Light from BaHfO3/Eu3+ through Ultraviolet, X-ray, and Heat Stimulation: An Optically Multifunctional Perovskite.

Materials with optical multifunctionality such as photoluminescence (PL), radioluminescence, and thermoluminescence (TL) are a boon for a sustainable society. BaHfO3 (barium hafnium oxide [BHO]) under UV irradiation demonstrated visible PL endowed by oxygen vacancies (OVs). Eu3+ doping in BHO (BHOE) introduces f-state impurity levels just below the conduction band for both Eu@Ba and Eu@Hf sites, causing efficient host-to-dopant energy transfer, generating intense 5D0 → 7F1 magnetic dipole transitions (MDT) with internal quantum yield of ∼70%. X-ray photoelectron spectroscopy and electron paramagnetic resonance showed the formation of OVs in both BHO and BHOE samples with more vacancies in the doped sample. The positron lifetime measurements suggested that Eu3+ ions are distributed at both Ba2+ and Hf4+ sites. The association of OVs with Hf4+ and Eu3+ ions due to high charge/radius ratio is considered to be responsible for lowering the symmetry around Eu3+ ions to C4v in BHOE. Density functional theory studies of defect formation energy justified the same. Time-resolved emission spectroscopy showed distinct spectra for Eu@Ba and Eu@Hf sites corresponding to symmetric and asymmetric environments, respectively. This could be highly relevant in designing color tunable phosphor by forcing dopant ions at one specific site because Eu@Ba displayed orange emission whereas Eu@Hf displayed red emission. We could further harness BHOE for X-ray scintillator application by designing a thin film, which showed efficient conversion of high-energy X-ray into visible light. Under beta irradiation; both BHO and BHOE showed distinct TL glow curves as shallow traps were formed in the former and deep traps in the latter, which could have long-term implications in harnessing this material for persistent luminescence. We believe that BHO/BHOE demonstrated an extraordinary credential as a perovskite for multifunctional applications in the area of defect-induced light emission, UV phosphor, X-ray scintillator, and TL crystals.

Aromatic heterobicycle-fused porphyrins: impact on aromaticity and excited state electron transfer leading to long-lived charge separation.

A new synthetic method to fuse benzo[4,5]imidazo[2,1-a]isoindole to the porphyrin periphery at the β,β-positions has been developed, and its impact on the aromaticity and electronic structures is investigated. Reactivity investigation of the fused benzoimidazo-isoindole component reveals fluorescence quenching of a zinc porphyrin (AMIm-2) upon treatment with a Brønsted acid. The reaction of the zinc porphyrin (AMIm-2) with methyl iodide initiated a new organic transformation, resulting in the ring-opening of isoindole with the formation of an aldehyde and dimethylation of the benzoimidazo component. The fused benzoimidazo-isoindole component acted as a good ligand to bind platinum(ii), forming novel homobimetallic and heterobimetallic porphyrin complexes. The fusion of benzoimidazo-isoindole on the porphyrin ring resulted in bathochromically shifted absorptions and emissions, reflecting the extended conjugation of the porphyrin π-system. Time-resolved emission and transient absorption spectroscopy revealed stable excited state species of the benzoimidazo-isoindole fused porphyrins. Zinc porphyrin AMIm-2 promoted excited state electron transfer upon coordinating with an electron acceptor, C60, generating a long-lived charge-separated state, in the order of 37.4 μs. The formation of the exceptionally long-lived charge-separated state is attributed to the involvement of both singlet and triplet excited states of AMIm-2, which is rarely reported in porphyrins.

Deposition phenomena of diamond-like carbon coating on inner surface of circular metal tube by nanopulse plasma chemical vapor deposition

A method of depositing a diamond-like carbon (DLC) film on the inner surface of a circular metal tube by chemical vapor deposition using a nanopulse power source was developed. Because the nanopulse power source can supply rapidly rising and falling high-voltage nanopulses of nanosecond order, a stable plasma can be obtained even in small-diameter tubes by applying a high gas pressure of more than 100 Pa. DLC films were successfully deposited on the inner surfaces of metal tubes of 14 mm diameter and 300 mm length (21% aspect ratio), and of 40 mm diameter and 300 mm length. To understand the plasma state inside the tubes to determine appropriate DLC film deposition conditions, wavelength- and time-resolved optical emission spectroscopy of the plasma generated inside the tubes and numerical simulation were performed. Results of these investigations and characterization clarified that one nanopulse power source introduced to tubes generates glow and after-glow discharges at μs time intervals. It was further clarified that these discharges in combination with high-repetition pulses, suggested together contribute to the effective ionization of gas. Thus, the high speed and high source gas yield of DLC film deposition inside the tubes were confirmed.

Study by Optical Spectroscopy of Bismuth Emission in a Nanosecond-Pulsed Discharge Created in Liquid Nitrogen.

Time-resolved optical emission spectroscopy of nanosecond-pulsed discharges ignited in liquid nitrogen between two bismuth electrodes is used to determine the main discharge parameters (electron temperature, electron density and optical thickness). Nineteen lines belonging to the Bi I system and seven to the Bi II system could be recorded by directly plunging the optical fibre into the liquid in close vicinity to the discharge. The lack of data for the Stark parameters to evaluate the broadening of the Bi I lines was solved by taking advantage of the time-resolved information supported by each line to determine them. The electron density was found to decrease exponentially from 6.5 ± 1.5 × 1016 cm−3 200 ns after ignition to 1.0 ± 0.5 × 1016 cm−3 after 1050 ns. The electron temperature was found to be 0.35 eV, close to the value given by Saha’s equation.

Understanding the Efficiency of Mn4+ Phosphors: Study of the Spinel Mg2Ti1–xMnxO4

We present a spectroscopic study of Mn-doped Mg2TiO4 as a function of pressure and temperature to check its viability as a red-emitting phosphor. The synthesis following a solid-state reaction route yields not only the formation of Mn4+ but also small traces of Mn3+. Although we show that Mn4+ photoluminescence is not appreciably affected by the presence of Mn3+, its local structure at the substituted Ti4+ host site causes a reduction of the Mn4+ pumping efficiency yielding a drastic quantum-yield reduction at room temperature. By combining Raman and time-resolved emission and excitation spectroscopies, we propose a model for explaining the puzzling nonradiative and inefficient pumping processes attained in this material. In addition, we unveil a structural phase transition above 14 GPa that worsens their photoluminescence capabilities. The decrease of emission intensity and lifetime with increasing temperature following different thermally activated de-excitation pathways is mostly related to relatively small activation energies and the electric–dipole transition mechanism associated with coupling to odd-parity vibrational modes. A thorough model based on the configurational energy level diagram to the A1g normal mode fairly accounts for the observed excitation and emission─the quantum yield─of this material.

Enhancement of the ion flux to the substrate through high-voltage biasing in an electron cyclotron resonance plasma and its application to high-speed deposition of conductive carbon film

A method for enhancing ion flux to the substrate via high-voltage pulse biasing is investigated in an electron cyclotron resonance plasma. When high-voltage pulse biases above 500 V are applied to the stage, an increase in the stage current is observed, especially in the case of diverging magnetic field configurations in front of the bias stage. The growth and decay time constants of the plasma density and emission intensity are evaluated using a time-resolved Langmuir probe and emission spectroscopy while the pulse is on, and the enhancement of the ionization rate during the bias application is estimated using the zero-dimensional global model. The estimated density enhancement from the model is in good agreement with the measured one. From the numerical simulation of secondary electron trajectory, it is concluded that the electron confinement from the magnetic field is the key factor in plasma density enhancement during stage biasing. Using the high-density plasma produced by the bias voltage, conductive carbon is deposited at a high deposition rate of ∼4 nm s−1.

Plasma plume evolution of a capillary discharge based pulsed plasma thruster: An optical diagnosis study

This paper studied the plasma plume evolution process of a capillary discharge based pulsed plasma thruster. Time-resolved imaging and optical emission spectroscopy were applied to investigate the plume morphology and plasma species characteristics. It showed that ionized particles (mainly C II and F II) were accelerated early in the pulse and neutral particles (mainly C I and F I) later. An optical time-of-flight (OTOF) method was developed using a photodiode array combined with narrow bandpass filters. The equivalent streaming velocity of the plasma plume was evaluated with the OTOF technique. Measurements of individual species showed that both the ionized and the neutral species could be effectively accelerated by gasdynamic forces, and the ionized particles could reach a higher velocity. A Doppler shift measurement of the plasma plume was also performed to compare it with the findings from the OTOF method. The plasma plume streaming velocity of a thruster with a discharge energy of 5 J was measured and found to be (25.34 ± 0.17) km/s (OTOF) and (22.36 ± 4.02) km/s (Doppler shift). In addition, differences between the operation processes of the capillary discharge based pulsed plasma thruster and the electromagnetic pulsed plasma thruster were analyzed.

In-Depth Studies of Ground- and Excited-State Properties of Re(I) Carbonyl Complexes Bearing 2,2':6',2″-Terpyridine and 2,6-Bis(pyrazin-2-yl)pyridine Coupled with π-Conjugated Aryl Chromophores.

In the current work, comprehensive photophysical and electrochemical studies were performed for eight rhenium(I) complexes incorporating 2,2′:6′,2″-terpyridine (terpy) and 2,6-bis(pyrazin-2-yl)pyridine (dppy) with appended 1-naphthyl-, 2-naphthyl-, 9-phenanthrenyl, and 1-pyrenyl groups. Naphthyl and phenanthrenyl substituents marginally affected the energy of the MLCT absorption and emission bands, signaling a weak electronic coupling of the appended aryl group with the Re(I) center. The triplet MLCT state in these complexes is so low lying relative to the triplet 3ILaryl that the thermal population of the triplet excited state delocalized on the organic chromophore is ineffective. The attachment of the electron-rich pyrenyl group resulted in a noticeable red shift and a significant increase in molar absorption coefficients of the lowest energy absorption of the resulting Re(I) complexes due to the contribution of intraligand charge-transfer (ILCT) transitions occurring from the pyrenyl substituent to the terpy/dppy core. At 77 K, the excited states of [ReCl(CO)3(Ln-κ2N)] with 1-pyrenyl-functionalized ligands were found to have predominant 3ILpyrene/3ILCTpyrene→terpy character. The 3IL/3ILCT nature of the lowest energy excited state of [ReCl(CO)3(4′-(1-pyrenyl)-terpy-κ2N)] was also evidenced by nanosecond transient absorption and time-resolved emission spectroscopy. Enhanced room-temperature emission lifetimes of the complexes [ReCl(CO)3(Ln-κ2N)] with 1-pyrenyl-substituted ligands are indicative of the thermal activation between 3MLCT and 3IL/3ILCT excited states. Deactivation pathways occurring upon light excitation in [ReCl(CO)3(4′-(1-naphthyl)-terpy-κ2N)] and [ReCl(CO)3(4′-(1-pyrenyl)-terpy-κ2N)] were determined by femtosecond transient absorption studies.

Robust Heterogeneous Photocatalyst for Visible-Light-Driven Hydrogen Evolution Promotion: Immobilization of a Fluorescein Dye-Encapsulated Metal-Organic Cage on TiO2.

The design of artificial photocatalytic devices that simulates the ingenious and efficient photosynthetic systems in nature is promising. Herein, a metal-organic cage [Pd6(NPyCzPF)12]12+ (MOC-PC6) integrating 12 organic ligands NPyCzBP and 6 Pd2+ catalytic centers is designed, which is well defined to include organic dye fluorescein (FL) for constructing a supramolecular photochemical molecular device (SPMD) FL@MOC-PC6. Photoinduced electron transfer (PET) between MOC-PC6 and the encapsulated FL has been observed by steady-state and time-resolved emission spectroscopy. FL@MOC-PC6 is successfully heterogenized with TiO2 by a facile sol-gel method to achieve a robust heterogeneous FL@MOC-PC6-TiO2. The close proximity between the Pd2+ catalytic site and FL included in the cage enables PET from the photoexcited FL to Pd2+ sites through a powerful intramolecular pathway. The photocatalytic hydrogen production assessments of the optimized 4 wt % FL@MOC-PC6-TiO2 demonstrate an initial H2 production rate of 2402 μmol g-1 h-1 and a turnover number of 4356 within 40 h, enhanced by 15-fold over that of a homogeneous FL@MOC-PC6. The effect of the MOC content on photocatalytic H2 evolution (PHE) is investigated and the inefficient comparison systems, such as MOC-PC6, MOC-PC6-TiO2, FL-sensitized MOC-PC6/FL-TiO2, and analogue FL/MOC-PC6-TiO2 with free FL, are evaluated. This study provides a creative and distinctive approach for the design and preparation of novel heterogeneous SPMD catalysts based on MOCs.

A rapid and label-free DNA-based interference reduction nucleic acid amplification strategy for viral RNA detection

Common reference methods for COVID-19 diagnosis include thermal cycling amplification (e.g. RT-PCR) and isothermal amplification methods (e.g. LAMP and RPA). However, they may not be suitable for direct detection in environmental and biological samples due to background signal interference. Here, we report a rapid and label-free interference reduction nucleic acid amplification strategy (IR-NAAS) that exploits the advantages of luminescent iridium(III) probes, time-resolved emission spectroscopy (TRES) and multi-branch rolling circle amplification (mbRCA). Using IR-NAAS, we established a luminescence approach for diagnosing COVID-19 RNAs sequences RdRp, ORF1ab and N with a linear range of 0.06–6.0 × 105 copies/mL and a detection limit of down to 7.3 × 104 copies/mL. Moreover, the developed method was successfully applied to detect COVID-19 RNA sequences from various environmental and biological samples, such as domestic sewage, and mice urine, blood, feces, lung tissue, throat and nasal secretions. Apart from COVID-19 diagnosis, IR-NAAS was also demonstrated for detecting other RNA viruses, such as H1N1 and CVA10, indicating that this approach has great potential approach for routine preliminary viral detection.

Power-Dependent Photoluminescence Efficiency in Manganese-Doped 2D Hybrid Perovskite Nanoplatelets.

Substitutional metal doping is a powerful strategy for manipulating the emission spectra and excited state dynamics of semiconductor nanomaterials. Here, we demonstrate the synthesis of colloidal manganese (Mn2+)-doped organic-inorganic hybrid perovskite nanoplatelets (chemical formula: L2[APb1-xMnxBr3]n-1Pb1-xMnxBr4; L, butylammonium; A, methylammonium or formamidinium; n (= 1 or 2), number of Pb1-xMnxBr64- octahedral layers in thickness) via a ligand-assisted reprecipitation method. Substitutional doping of manganese for lead introduces bright (approaching 100% efficiency) and long-lived (>500 μs) midgap Mn2+ atomic states, and the doped nanoplatelets exhibit dual emission from both the band edge and the dopant state. Photoluminescence quantum yields and band-edge-to-Mn intensity ratios exhibit strong excitation power dependence, even at a very low incident intensity (<100 μW/cm2). Surprisingly, we find that the saturation of long-lived Mn2+ dopant sites cannot explain our observation. Instead, we propose an alternative mechanism involving the cross-relaxation of long-lived Mn-site excitations by freely diffusing band-edge excitons. We formulate a kinetic model based on this cross-relaxation mechanism that quantitatively reproduces all of the experimental observations and validate the model using time-resolved absorption and emission spectroscopy. Finally, we extract a concentration-normalized microscopic rate constant for band edge-to-dopant excitation transfer that is ∼10× faster in methylammonium-containing nanoplatelets than in formamidinium-containing nanoplatelets. This work provides fundamental insight into the interaction of mobile band edge excitons with localized dopant sites in 2D semiconductors and expands the toolbox for manipulating light emission in perovskite nanomaterials.

Intramolecular Relaxation Dynamics Mediated by Solvent-Solute Interactions of Substituted Fluorene Derivatives. Solute Structural Dependence.

Several fluorene derivatives exhibit excited-state reactivity and relaxation dynamics that remain to be understood fully. We report here the spectral relaxation dynamics of two fluorene derivatives to evaluate the role of structural modification in the intramolecular relaxation dynamics and intermolecular interactions that characterize this family of chromophores. We have examined the time-resolved spectral relaxation dynamics of two compounds, NCy-FR0 and MK-FR0, in protic and aprotic solvents using steady-state and time-resolved emission spectroscopy and quantum chemical computations. Both compounds exhibit spectral relaxation characteristics similar to those seen in FR0, indicating that hydrogen bonding interactions between the chromophore and solvent protons play a significant role in determining the relaxation pathways available to three excited electronic states.

Development of digitally processed DC reactive sputtering and its application to the synthesis of (Er0.1Y0.9)2SiO5 layered crystalline thin film

We have developed a digitally processed DC reactive sputtering (DPDRS) system that enables synthesis of arbitrarily designed atomically precise deposition of metal oxide compounds. Pulsed-DC sputtering employing a digital pulse pattern generator can perform the temporally alternating process of multiple metal sputtering and oxidation. High-speed switching of the pulsed-DC sputtering process driven by the digital signal processing was confirmed from time-resolved plasma emission spectroscopy. Metal sputtering, which was temporally separated from the oxidation process, resulted in a deposition rate higher than 1 μm/h. It was also found that the temporally separated radical oxidation at the deposited metal surface could control the oxidation process. The DPDRS was applied to layer-by-layer synthesis of (Er0.1Y0.9)2SiO5 (EYSO) films oriented to the ⟨100⟩ direction. The deposition rate for each metal target (Er and Y) was adjusted to 0.86 nm/cycle corresponding to a d-spacing of the (100) plane by changing independently the duty ratio of the base pulse for plasma generation. X-ray diffraction measurements indicated a formation of ⟨100⟩ highly oriented (Er0.1Y0.9)2SiO5 crystalline thin films. Photoluminescence spectra and the decay characteristics also showed synthesis of high crystalline quality EYSO films better than those obtained by pulsed laser deposition.

Time-resolved optical emission spectroscopy in CO2 nanosecond pulsed discharges

Nanosecond repetitively pulsed discharges at atmospheric pressure have shown comparatively high performances for CO2 reduction to CO and O2. However, mechanisms of CO2 dissociation in these transient discharges are still a matter of discussion. In the present work, we have used time-resolved optical emission spectroscopy to investigate the CO2 discharge progression from the initial breakdown event to the final post-discharge. We discover a complex temporal structure of the spectrally resolved light, which gives some insights into the underlying electron and chemical kinetics. We could estimate the electron density using the Stark broadening of O and C lines and the electron temperature with C+ and C++ lines. By adding a small amount of nitrogen, we could also monitor the time evolution of the gas temperature using the second positive system bands of N2. We conclude that the discharge evolves from a breakdown to a spark phase, the latter being characterised by a peak electron density around 1018 cm−3 and a mean electron temperature around 2 eV. The spark phase offers beneficial conditions for vibrationally enhanced dissociation, which might explain the high CO2 conversion observed in these plasma discharges.

Spatial characteristics of nanosecond pulsed micro-discharges in atmospheric pressure He/H2O mixture by optical emission spectroscopy

Atmospheric pressure micro-discharges in helium gas with a mixture of 0.5% water vapor between two pin electrodes are generated with nanosecond overvoltage pulses. The temporal and spatial characteristics of the discharges are investigated by means of time-resolved imaging and optical emission spectroscopy with respect to the discharge morphology, gas temperature, electron density, and excited species. The evolution of micro-discharges is captured by intensified CCD camera and electrical properties. The gas temperature is diagnosed by a two-temperature fit to the ro-vibrational OH(A2Σ+–X2Π, 0–0) emission band and is found to remain low at 425 K during the discharge pulses. The profile of electron density performed by the Stark broadening of H α 656.1-nm and He I 667.8-nm lines is uniform across the discharge gap at the initial of discharge and reaches as high as 1023 m−3. The excited species of He, OH, and H show different spatio-temporal behaviors from each other by the measurement of their emission intensities, which are discussed qualitatively in regard of their plasma kinetics.

Monitoring the microenvironment inside polymeric micelles using the fluorescence probe 6-propionyl-2-dimethylaminonaphthalene (PRODAN)

6-propionyl-2-dimethylaminonaphthalene (PRODAN) is a fluorescent molecule with sensitivity to environmental polarity and hydrogen bond interactions. Although it has been extensively used to study organized systems such as vesicles and reverse micelles, its potential application to characterize polymeric micelles remains largely unexplored. Molecular probes can provide valuable information about the physicochemical properties of these micelles, and thus about the environment they offer to solubilize cargos. The present study aimed to find out what new insights could be gained by using PRODAN for such a purpose. The model systems chosen were D-α-tocopheryl polyethylene glycol 1000 succinate (TPGS) and polyvinyl caprolactam-polyvinyl acetate-poly-ethylene glycol (Soluplus®) micelles. Steady-state and time-resolved fluorescence emission spectroscopy revealed that PRODAN was wholly incorporated into the micelles when the polymer concentration exceeded 9.9x10-4 M (TGPS) and 2.1x10-5 M (Soluplus®). The probe sensed a less polar environment inside Soluplus® micelles, whose core was found to be more fluid than that of TGPS micelles through red edge excitation shift (REES) experiments. A calculation of the well-known polarity parameter ET(30) confirmed that the environment was less polar within Soluplus® micelles than within TGPS ones. These results correlate well with the known loading capacity of both systems to solubilize different drugs, and therefore demonstrate that PRODAN is a powerful probe to characterize polymeric micelles.

Terahertz Generation via Picosecond Spin-to-Charge Conversion in IrMn3/Ni−Fe Heterojunction

Experimental investigations of ultrafast electro-optical properties in magnetic materials manifest their great potential for emerging spintronic optoelectronic devices. Here, using time-resolved terahertz emission spectroscopy, we construct a spintronic terahertz emitter consisting of an ${\mathrm{Ir}\mathrm{Mn}}_{3}/\mathrm{Ni}\ensuremath{-}\mathrm{Fe}$ heterojunction. A femtosecond spin current pulse is generated in the thin film of the $\mathrm{Ni}\ensuremath{-}\mathrm{Fe}$ layer when it absorbs a femtosecond laser pulse, and then the spin current is converted into a transient charge current by the metallic ${\mathrm{Ir}\mathrm{Mn}}_{3}$ layer on picosecond timescales. We timely record the terahertz emission associated with this ultrafast conversion process by means of electro-optic sampling. Besides, the spin-to-charge conversion efficiency of the ${\mathrm{Ir}\mathrm{Mn}}_{3}/\mathrm{Ni}\ensuremath{-}\mathrm{Fe}$ heterojunction is determined via quantitative analysis of the spin torque ferromagnetic resonance results. We have both optically verified and electrically studied the spin-to-charge conversion of the ${\mathrm{Ir}\mathrm{Mn}}_{3}/\mathrm{Ni}\ensuremath{-}\mathrm{Fe}$ heterojunction. Our results enlarge the material choice range of spintronic terahertz emitters, which may promote further investigations of ultrafast spin-to-charge conversion in different heterojunction materials.

Highly Emissive Biological Bilirubin Molecules: Shedding New Light on the Phototherapy Scheme.

Bilirubin (BR) is the main end-product of the hemoglobin catabolism. For decades, its photophysics has been mainly discussed in terms of ultrafast deactivation of the excited state in solution, where, indeed, BR shows a very low green emission quantum yield (EQY), 0.03%, resulting from an efficient nonradiative isomerization process. Herein, we present, for the first time, unique and exceptional photophysical properties of solid-state BR, which amend by changing the type of crystal, from a closely packed α crystal to an amorphous loosely packed β crystal. BR α crystals show a very bright red emission with an EQY of ca. 24%, whereas β crystals present, in addition, a low green EQY of ca. 0.5%. By combining density functional theory (DFT) calculations and time-resolved emission spectroscopy, we trace back this dual emission to the presence of two types of BR molecules in the crystal: a “stiff” monomer, M1, distorted by particularly strong internal H-bonds and a “floppy” monomer, M2, having a structure close to that of BR in solution. We assign the red strong emission of BR crystals to M1 present in both the α and β crystals, while the low green emission, only present in the amorphous (β) crystal, is interpreted as M2 emission. Efficient energy-transfer processes from M2 to M1 in the closely packed α crystal are invoked to explain the absence of the green component in its emission spectrum. Interestingly, these unique photophysical properties of BR remain in polar solvents such as water. Based on these unprecedented findings, we propose a new model for the phototherapy scheme of BR inside the human body and highlight the usefulness of BR as a strong biological fluorescent probe.