• Energy Research

Resonance energy transfer from tris(2,2'-bipyridyl)ruthenium (II) ([Ru(bpy)3](2+)) to nile blue A is demonstrated in aqueous solution in the presence of sodium dodecyl sulfate (SDS). At SDS concentrations below the critical micelle concentration, aggregates that permit energy transfer between these dyes at optically dilute (10 microM) concentrations with nearly 100% efficiency are formed. The disparity between the lifetimes of the donor and acceptor results in the lengthening of the photoluminescence lifetime of the sensitized emission observed from nile blue A. Time-resolved luminescence measurements confirm that the long-lived components of the emission originate from sensitized acceptor emission.

The impact of moisture and heat treatment on the microstructural, chemical, and electrical properties of Cu(In,Ga)Se2 films and their collective effect on the solar cell device performance was studied. X-ray photoelectron spectroscopy and secondary ion mass spectroscopy measurements show that water exposure causes surface modification and alters the alkali metal distribution, while no composition or structural effect was observed. Deep level transient and optical spectroscopies revealed that the trap densities ( NT ) for both the EV + 0.65 eV and EV + 0.98 eV traps increase after water exposure, while the majority carrier concentration ( NA ) decreases. Time-resolved photoluminescence (PL) and steady-state PL measurements indicated the presence of static, not dynamic, quenching. Reduction of open-circuit voltage ( V OC) and fill factor (FF) was observed for the devices but was not associated with a change of recombination mechanism, which remains in the absorber space charge region. A small increase in series resistance and shunt conductance accounts for most of the FF change, while the modification in both NA and NT yield most of the change in V OC. A gradient of majority carrier concentration, related to the alkali profile, also yields a small voltage-dependent current collection after moisture and heat treatment.

Thermally activated delayed photoluminescence (TADPL) generated from organic chromophore-functionalized quantum dots (QDs) is potentially beneficial for persistent light generation, QD-based PL sensors, and photochemical synthesis. While previous research demonstrated that naphthoic acid-functionalized InP QDs can be employed as low-toxicity, blue-emissive TADPL materials, the electron trap states inherent in these nanocrystals inhibited the observation of TADPL emerging from the higher-lying bright states. Here, we address this challenge by employing the heterocyclic aromatic compound 8-quinolinecarboxylic acid (QCA), whose triplet energy is strategically positioned to bypass the electron trap states in InP QDs. Transient absorption and photoluminescence spectroscopies revealed the generation of bright-state TADPL from QCA-functionalized InP QDs resulting from a nearly quantitative Dexter-like triplet-triplet energy transfer (TTET) from photoexcited InP QDs to surface-anchored QCA chromophores followed by reverse TTET from these bound molecules to the InP QDs. This modification resulted in a 119-fold increase in the average PL intensity decay time with respect to the as-synthesized InP QDs.

Numerous visible-light absorbing homogeneous photocatalytic compositions are shown to produce copious amounts of hydrogen gas from pure water.

Hydrothermal synthesis utilizing aqueous alkaline reaction conditions was employed for the preparation of TiO2 nanotubes. The ultimate material morphology was found to be extremely sensitive to the nature of the reaction conditions including the chemical nature of the reactor itself—well-defined TiO2 nanotubes were obtained only when the reaction was carried out in a Teflon reactor/autoclave assembly, as ascertained by electron microscopy imaging. In addition, it was shown that the nanomaterial morphology heavily impacted the performance of dye-sensitized photovoltaic devices based on these materials; devices assembled from well-defined TiO2 nanotubes exhibited marked overall improvement in the power conversion efficiency. Several individual experimental parameters including hydrothermal synthesis temperature, film thickness, TiO2 paste composition, and sintering temperature were shown to affect the photovoltaic properties of the resultant solar cells. Upon sensitization with Ru(dcbpyH2)2(NCS)2, optimized devices showed an average power conversion efficiency of 3.76 ± 0.25% under AM1.5G one sun illumination, seemingly limited by low dye surface coverages.

Photochemical upconversion (UC) through triplet-triplet annihilation (TTA), which employs a visible absorbing triplet photosensitizer and an annihilator, is a process that generates a high energy photon from two lower energy photons. TTA-UC has been largely developed in pure organic solvents and solid-state polymeric constructs while featuring near exclusive use of rare and expensive metals within the photosensitizer. In this current investigation, we demonstrate that TTA-UC from the long lifetime earth-abundant photosensitizer [Cu(dsbtmp)2](PF)6 (dsbtmp = 2,9-di(sec-butyl)-3,4,7,8-tetramethyl-1,10-phenanthroline), abbreviated as Cu-PS, functions in water through encapsulation within a cationic-based assembly. Cetyltrimethylammonium bromide was the surfactant of choice as it electrostatically binds the negatively charged water-soluble 10-phenylanthracene-9-carboxylate (PAC) acceptor/annihilator and ultimately facilitates energy transfer across the interface. Efficient triplet-triplet energy transfer (TTET) from Cu-PS to the PAC acceptor was achieved in this aqueous assembly. Unfortunately, the hindered mobility of the PAC moieties ultimately hampered the annihilation process, and this was reflected in attenuated TTA rates and efficiencies. The combined experimental data illustrated that the water-soluble PAC acceptor was able to vectorially deliver the excited-state energy stored in Cu-PS across the interface into the bulk aqueous solution by engaging in excited-state electron transfer with methyl viologen acceptors. These results are important for remotely operating photoredox reactions in water while rendering a photosensitizer spatially isolated in the hydrophobic core of a micelle.

Photochemical upconversion is performed using champion sensitizers and annihilators to achieve high efficiencies under one sun.

In this paper, we studied the effect of rubidium fluoride (RbF) post-deposition treatment (PDT) on the properties of Cu(In,Ga)Se2 (CIGS) solar cells. Specifically, the recombination mechanisms were analyzed by a series of characterizations including thermal and optical defect spectroscopies, temperature dependent current density–voltage measurements, and time resolved photoluminescence. It was found that the main effect of RbF PDT on the solar cell was an increase of the open circuit-voltage, $V_{{\text{oc}}}$ , by 30 mV due to a decrease of the values of the diode quality factor and reverse saturation current. Recombination mechanisms were identified as being in the CIGS space charge region, likely at the grain boundaries and near the CIGS surface. Breakdown of contributions to the $V_{{\text{oc}}}$ increase showed that part of it is due to an increase of the majority carrier concentration (16 mV) and another to the increase in the minority carrier lifetime (1 mV). The latest is mostly due to a reduction in the EV+0.99 eV deep-level trap density. An additional CIGS surface modification (contributing 13 mV), observed by the secondary ion mass spectrometry, is essential to explain the full change in $V_{{\text{oc}}}$ .