Upconversion (UC) of low-energy photons into high-energy light can in principle increase the efficiency of solar devices by converting photons with energies below the energy absorption threshold into radiation that can be utilized. Among UC mechanisms, the sensitized triplet–triplet annihilation-based upconversion (sTTA-UC) is the most recent that would be applied in solar technologies. sTTA-UC was demonstrated using sunlight in 2006, and due to its high efficiency at low excitation intensities with noncoherent light, it is considered a promising strategy for the recovering of subbandgap photons. Here, we describe briefly the working principle of the sTTA-UC, and we review the most recent advances of its use in solar applications.
A crucial limit of solar devices is their inability to harvest the full solar spectrum. Currently, sensitized up-conversion based on triplet-tripled annihilation (STTA-UC) in bi-component organic systems is the most promising technique to recover sub-bandgap photons, showing good efficiencies also at excitation intensities comparable to the solar irradiance. In STTA-UC, high-energy light is generated through annihilation of metastable triplet states of molecules acting as emitters, which are populated via resonant energy transfer from a light-harvesting sensitizer. However, suitable sensitizers show narrow absorption bands, limiting the fraction of recoverable photons, therefore preventing the application of STTA-UC to real-world devices. Here we demonstrate how to overcome the described limit by using multiple sensitizers that work cooperatively to broaden the overall system absorption band. This is obtained using an additional sensitizer that transfers the extra harvested energy to the main one (sensitization of the sensitizer), or a set of properly designed complementary absorbing sensitizers all able to excite simultaneously the same emitter (multi-sensitizers). In both cases STTA-UC performances result strongly enhanced compared to the corresponding mono-sensitizer system, increasing the up-converted light intensity generated at AM 1.5 up to two times. Remarkably, by coupling our light converters to a DSSC we prove its operation by exploiting exclusively sub-bandgap photons. A detailed modeling of the photophysical processes involved in these complex systems allows us to draw the guidelines for the design of the next generation STTA-UC materials, encouraging their application to photovoltaic technologies.
Sensitized up-conversion (SUC) based on bi-component systems is currently indicated as a potential method to improve
the efficiency of PV and PC technologies by photon energy managing. Although high SUC yields have been already
demonstrated in solution by using low power non-coherent excitation sources, its application in real devices is still far.
Indeed the conversion yield drops dramatically at solid state, where the short diffusion length of excitation energy
strongly inhibits the diffusion controlled mechanisms which rule SUC photophysics. A general discussion to analyze the
main environmental parameters affecting SUC quantum yield is presented here to find out the guidelines for the
fabrication of high performance SUC materials.
We present the spectroscopic study of the mechanisms of excitation transfer between rare earth ions excited by energy transfer from SnO<sub>2</sub> nanocrystals in silica. Bulk samples of pure and Er-doped silica with SnO<sub>2</sub> nanoparticles were prepared by a sol gel technique and further thermal sintering process. Transmission electron microscopy (TEM) reveals the formation of spherical nanoclusters with a size distribution strongly determined by erbium doping. Small angle neutron scattering (SANS) experiments confirm and detail the TEM data evidencing the existence of a interphase region at the cluster boundaries where a SnOlike phase compensates the structural mismatch between the crystalline lattice in SnO<sub>2</sub> nanoparticles and the amorphous silica network. The analysis of the SANS patterns show what kind of modification of the interphase morphology of SnO<sub>2</sub> nanoparticles in silica brings to the passivation of interfacial defects. Surface states, which may preclude the exploitation of UV excitonic emission, are reduced after doping by rare earth ions. We demonstrate, by means of transmission-electron-microscopy and small-angle-neutron-scattering data, that a smooth interphase with a non negligible thickness takes the place of the fractal and discontinuous boundary observed in undoped material. The time resolved photoluminescence spectra of erbium in the infrared region show the spectral profile ascribable to ions in a ordered environment. Moreover, the absence of the broad contribution of the radiative decay of erbium ions dispersed in the silica amorphous matrix indicates that the excitation transfer follows paths enveloped in the interphase region. The spectroscopic analysis allows us to conclude that the excitation is transferred from ion to ion within a quasi-crystalline region where each site is surrounded by a different distribution of PL quenching sites which are responsible for the multi-exponential decay kinetics.