The influence of SiO2/TiO2 nanocomposites (STNCs) content on non-radiative energy transfer (Förster-type) from poly (9,9'-dioctylfluorene-2,7-diyl) (PFO) to poly [2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) using steady-state and time-resolved photoluminescence spectroscopies was investigated at room temperature. The improved energy transfer from PFO to MEH-PPV upon an increment of the STNCs was achieved by examining absorbance, emission (PL) and photoluminescence excitation (PLE) spectra. The shorter values of the quantum yield (φDA) and lifetime (τDA) of the PFO in the hybrid thin films compared with the pure PFO, indicating efficient energy transfer from PFO to MEH-PPV with the increment of STNCs in the hybrid. The energy transfer parameters can be tuned by increment of the STNCs in the hybrid of PFO/MEH-PPV. The Stern-Volmer value (kSV), quenching rate value (kq), Förster radius (R0), distance between the molecules of PFO and MEH-PPV (RDA), energy transfer lifetime (τET), energy transfer rate (kET), total decay rate of the donor (TDR), critical concentration (Ao), and conjugation length (Aπ) were calculated. The gradually increasing donor lifetime and decreasing acceptor lifetime, upon increasing the STNCs content, prove the increase in conjugation length and meanwhile enhance in the energy transfer.
Tuning the emission spectrum of both binary hybrids of poly (9,9'-di-n-octylfluorenyl-2,7-diyl) (PFO) with each poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) and poly[2-methoxy-5-(3,7-dimethyl-octyloxy)-1,4-phenylenevinylene] end-capped with Dimethyl phenyl (MDMO-PPV-DMP) by a systematic doping strategy was achieved. Both binary hybrid thin films of PFO/MEH-PPV and PFO/MDMO-PPV-DMP with various weight ratios were prepared via solution blending method prior to spin coating onto the glass substrates. The conjugation length of the PFO was tuned upon addition of acceptors (MEH-PPV or MDMO-PPV-DMP), as proved from shifting the emission and absorption peaks of the binary hybrids toward the acceptor in addition to enhancing the acceptor emission and reducing the absorbance of the PFO. Förster resonance energy transfer (FRET) is more efficient in the binary hybrid of PFO/MDMO-PPV-DMP than in the PFO/MEH-PPV. The efficient FRET in both hybrid thin films played the major role for controlling their emission and producing white emission from optimum ratio of both binary hybrids. Moreover, the tuning of the emission color can be attributed to the cascade of energy transfer from PFO to MEH-PPV, and then to MDMO-PPV-DMP.
Methylammonium lead iodide (MAPbI3) is a benchmark absorber for low-cost, high-efficiency perovskite solar cells (PSCs), but its practical deployment is constrained by small grain sizes, high defect densities, and moisture-sensitive surfaces that limit both efficiency and stability. Here, we demonstrate that covalent organic frameworks (COFs) built from commercially available building blocks provide a powerful, multifunctional route to overcome these limitations by simultaneously regulating crystallization, passivating defects, and tuning surface properties in MAPbI3 thin films. Three hydrazone-linked and β-ketoenamine frameworks, denoted DMTH-COF, Boc-PDA-COF and Tp-COF, were prepared by condensing 2,5-dimethoxyterephthalohydrazide (DMTH), Boc-PDA-phenylenediamine (Boc-PDA), and 1,3,5-triformylphloroglucinol (Tp), respectively, and were incorporated at low loading into the MAPbI3 precursor solution. X-ray diffraction and FE-SEM reveal that all three additives preserve the tetragonal perovskite phase while enlarging the grain size from a few hundred nanometers in pristine films to about 1 μm for DMTH-modified layers, accompanied by narrowed diffraction peaks and reduced microstrain. Raman and FTIR spectroscopy show COF-induced modifications of Pb-I and CH3NH3+ vibrational modes, indicating specific coordination and hydrogen-bonding interactions that stabilize the lattice and reduce trap density. UV-Vis spectra confirm strong visible-light absorption at an unchanged optical bandgap of 1.56 eV across all films, while steady-state PL and EQE measurements evidence enhanced radiative efficiency and improved photon-to-current conversion, particularly at longer wavelengths. X-ray photoelectron spectroscopy confirms that the framework is retained within the film after annealing, the modified absorber showing a N 1s component at 399.7 eV that is absent from the pristine reference, while the Pb 4f and I 3d core levels shift in parallel with their spin-orbit splittings preserved and no metallic lead detected. These material-level improvements translate into substantial device gains in n-i-p PSCs (FTO/c-TiO2/m-TiO2/COF:MAPbI3/Spiro-OMeTAD/Au). Relative to pristine MAPbI3 cells (PCE ≈ 14.7%), COF-modified devices exhibit higher Voc, Jsc, and FF, with DMTH-COF-modified cells achieving Voc = 1.183 V, Jsc = 22.98 mA cm-2, FF = 76.46%, and PCE = 20.78%, alongside reduced series resistance, increased shunt resistance, and improved device-to-device reproducibility. Water-contact-angle and EDX analyses confirm that COF addition increases surface hydrophobicity and preserves near-ideal Pb:I stoichiometry, supporting enhanced environmental stability. This study introduces bulk COF doping as a simple, scalable strategy to engineer MAPbI3 microstructure, energetics, and surface chemistry in a single processing step, and identifies DMTH-COF as the most effective of the three frameworks. More broadly, it positions COF-perovskite hybrids as a tunable platform for high-efficiency, durable perovskite optoelectronics.