ABSTRACT
Organic-inorganic perovskites such as CH3NH3PbI3 are promising materials for a variety of optoelectronic applications, with certified power conversion efficiencies in solar cells already exceeding 21%. Nevertheless, state-of-the-art films still contain performance-limiting non-radiative recombination sites and exhibit a range of complex dynamic phenomena under illumination that remain poorly understood. Here we use a unique combination of confocal photoluminescence (PL) microscopy and chemical imaging to correlate the local changes in photophysics with composition in CH3NH3PbI3 films under illumination. We demonstrate that the photo-induced 'brightening' of the perovskite PL can be attributed to an order-of-magnitude reduction in trap state density. By imaging the same regions with time-of-flight secondary-ion-mass spectrometry, we correlate this photobrightening with a net migration of iodine. Our work provides visual evidence for photo-induced halide migration in triiodide perovskites and reveals the complex interplay between charge carrier populations, electronic traps and mobile halides that collectively impact optoelectronic performance.
Subject(s)
Calcium Compounds/radiation effects , Iodides/radiation effects , Oxides/radiation effects , Titanium/radiation effects , Calcium Compounds/chemistry , Iodides/chemistry , Iodine/chemistry , Iodine/radiation effects , Lead/chemistry , Lead/radiation effects , Light , Luminescent Measurements/methods , Methylamines/chemistry , Methylamines/radiation effects , Microscopy, Confocal/methods , Oxides/chemistry , Spectrometry, Mass, Secondary Ion/methods , Titanium/chemistryABSTRACT
We report the first experimental demonstration of vibrational mode-dependent enhancement in photodissociation and photoionization of a seven atom molecule, methylamine (CH(3)NH(2)). The fundamental C-H stretches and the overtones or combinations of CH(3) bends were prepared via stimulated Raman excitation (SRE) prior to their 243.135 nm one-photon dissociation or two-photon ionization. The photodissociation or photoionization of the vibrationally excited molecules was achieved via 10 ns delayed or temporally overlapping SRE and UV pulses, respectively. It is shown that bending modes are more effective than stretches in promoting photodissociation and photoionization, since their UV excitation is favored by larger Franck Condon factors. This behavior provides clear evidence for vibrational mode-dependence in a relatively large molecule with a torsional degree of freedom, indicating that these modes survive intramolecular vibrational redistribution on a time scale considerably longer than hitherto inferred from previous studies.
Subject(s)
Methylamines/chemistry , Photolysis , Light , Methylamines/radiation effects , Spectrum Analysis, Raman , Time Factors , VibrationABSTRACT
The research objective was to adapt the ultraviolet (UV)-photolysis method to determine dissolved organic nitrogen (DON) in aqueous extracts of aerosol samples. DON was assumed to be the difference in total concentration of inorganic nitrogen forms before and after sample irradiation. Using a 2(2) factorial design the authors found that the optimal conversion of urea, amino acids (alanine, aspartic acid, glycine, and serine), and methylamine for a reactor temperature of 44 degrees C occurred at pH 2.0 with a 24-hr irradiance period at concentrations <33 microM of organic nitrogen. Different decomposition mechanisms were evident: the photolysis of amino acids and methylamine released mainly ammonium (NH4+), but urea released a near equimolar ratio of NH4+ and nitrate (NO3-). The method was applied to measure DON in the extracts of aerosol samples from Tampa, FL, over a 32-day sampling period. Average dissolved inorganic (DIN) and DON concentrations in the particulate matter fraction PM10 were 78.1 +/- 29.2 nmol-Nm(-3) and 8.3 +/- 4.9 nmol-Nm(-3), respectively. The ratio between DON and total dissolved nitrogen ([TDN] = DIN + DON) was 10.1 +/- 5.7%, and the majority of the DON (79.1 +/- 18.2%) was found in the fine particulate matter (PM2.5) fraction. The average concentrations of DIN and DON in the PM2.5 fraction were 54.4 +/- 25.6 nmol-Nm(-3) and 6.5 +/- 4.4 nmol-Nm(-3), respectively.
Subject(s)
Aerosols/radiation effects , Air Pollutants/radiation effects , Environmental Monitoring/methods , Nitrogen/analysis , Aerosols/analysis , Air Pollutants/analysis , Amino Acids/radiation effects , Hydrogen-Ion Concentration , Methylamines/radiation effects , Nitrates/analysis , Photolysis , Quaternary Ammonium Compounds/analysis , Ultraviolet Rays , Urea/radiation effectsABSTRACT
Site-specific modification of single-stranded DNA by oligonucleotide derivatives of p-azido-O-(4-aminobutyl)tetrafluorobenzaldoxime sensitized by an oligonucleotide derivative of pyrenylethylamine was studied. Upon irradiation with the long-wave UV light (365-390 nm) of a DNA target-oligonucleotide reagent complementary complex, a considerable increase in the rate of sensitized photomodification at the G11 residue of the target relative to the direct photomodification was observed owing to the singlet-single energy transfer from the sensitizer onto the photoreagent. Upon simultaneous irradiation of the complex with UV and visible light in the region of the triplet-triplet absorption of pyrene (360-580 nm), an additional increase in the modification rate and a change in its site-direction (from the G11 to T13 residue) occurred through the two-photon triplet-triplet sensitization. The total extent of the structure photomodification amounted to 80%.
