Photonics / Fotonik
Permanent URI for this collectionhttps://hdl.handle.net/11147/2590
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Article Citation - WoS: 7Citation - Scopus: 7Breaking the Boundaries of the Goldschmidt Tolerance Factor With Ethylammonium Lead Iodide Perovskite Nanocrystals(American Chemical Society, 2024) Güvenç, Çetin Meriç; Toso, Stefano; Ivanov, Yurii P.; Saleh, Gabriele; Balcı, Sinan; Divitini, Giorgio; Manna, LiberatoWe report the synthesis of ethylammonium lead iodide (EAPbI3) colloidal nanocrystals as another member of the lead halide perovskites family. The insertion of an unusually large A-cation (274 pm in diameter) in the perovskite structure, hitherto considered unlikely due to the unfavorable Goldschmidt tolerance factor, results in a significantly larger lattice parameter compared to the Cs-, methylammonium- and formamidinium-based lead halide perovskite homologues. As a consequence, EAPbI3 nanocrystals are highly unstable, evolving to a nonperovskite delta-EAPbI3 polymorph within 1 day. Also, EAPbI3 nanocrystals are very sensitive to electron irradiation and quickly degrade to PbI2 upon exposure to the electron beam, following a mechanism similar to that of other hybrid lead iodide perovskites (although degradation can be reduced by partially replacing the EA+ ions with Cs+ ions). Interestingly, in some cases during this degradation the formation of an epitaxial interface between (EA x Cs1-x )PbI3 and PbI2 is observed. The photoluminescence emission of the EAPbI3 perovskite nanocrystals, albeit being characterized by a low quantum yield (similar to 1%), can be tuned in the 664-690 nm range by regulating their size during the synthesis. The emission efficiency can be improved upon partial alloying at the A site with Cs+ or formamidinium cations. Furthermore, the morphology of the EAPbI3 nanocrystals can be chosen to be either nanocube or nanoplatelet, depending on the synthesis conditions.Article Citation - WoS: 6Citation - Scopus: 6Polar Solvent-Free Room Temperature Synthesis of Cspbx3 (x = Br, Cl) Perovskite Nanocubes(Royal Society of Chemistry, 2023) Güvenç, Çetin Meriç; Kocabaş, Aşkın; Balcı, SinanConventionally, colloidal lead halide perovskite nanocubes have been synthesized by the hot-injection or ligand-assisted reprecipitation (LARP) methods. We herein demonstrate a polar solvent-free room temperature method for the synthesis of CsPbX3 (X = Br, Cl) nanocubes. In addition to the commonly used ligand pair of oleylamine and oleic acid, guanidinium (GA) has been used to passivate the surface of the nanocrystals. Our study demonstrates that GA inhibits the formation of low dimensional structures such as nanowires and nanoplatelets and further supports the formation of perovskite nanocubes. In fact, GA diminishes the restricted monomer-addition effect of long-chain oleylammonium (OLAM) ions to the nanocrystal. We show that above a critical GA/OLAM molar ratio, the synthesis yields homogeneous CsPbX3 (X = Br, Cl) nanocubes. Importantly, we observe the nucleation and growth kinetics of the GA-assisted CsPbBr3 nanocube formation by using in situ absorption and photoluminescence (PL) measurements. Small nanocrystals with an excitonic absorption peak at around 435 nm and photoluminescence (PL) maxima at 447 nm were nucleated and continuously shifted to longer wavelengths during the growth period. Crucially, our method allows the synthesis of CsPbCl3 nanocubes at room temperature without using polar organic solvents. The synthesized CsPbBr3, CsPb(Cl0.5Br0.5)3, and CsPbCl3 nanocubes have PL peaks at 508 nm, 443 nm, and 405 nm, photoluminescence quantum yields (PLQY) of 85%, 58% and 5%, and lifetimes of 18.98 ns, 18.97 ns, and 14.74 ns, respectively.Article Citation - WoS: 2Citation - Scopus: 31-Octanol Is a Functional Impurity Modifying Particle Size and Photophysical Properties of Colloidal Zncdsse/Zns Nanocrystals(American Chemical Society, 2021) Sevim Ünlütürk, Seçil; Çağır, Ali; Varlıklı, Canan; Özçelik, SerdarImpurities in trioctylphophine (TOP) strongly affect nanocrystal synthesis. 1-Octanol among other contaminants in TOP is identified for the first time as a functional impurity by H-1 NMR. The deliberate addition of 1-octanol into trioctylphosphine reduced particle size and modified photophysical properties of ZnCdSSe/ZnS colloidal nanocrystals. NMR analysis furthermore revealed that 1-octanol is bonded to the nanocrystal surfaces. The ratio of integrals for the O-CH2 protons of 1-octanol, which is the lowest compared to the other ligands, suggests that 1-octanol plays a critical role to tune the particle size of nanocrystals. The increased amount of 1-octanol added into TOP reduces the particle size from 9.8 to 7.2 nm, causing a progressive blue shift in the UV-vis and PL spectra but leaving the alloy composition unaffected. The rate of nonradiative processes is enhanced with the amount of 1-octanol added into TOP, correlating with higher dislocation density observed in the nanocrystals. As a conclusion, 1-octanol is proposed as a functional impurity that varies particle size and nonradiative photophysical processes in the ZnCdSSe/ZnS colloidal nanocrystals.
