Structural tunability and switchable exciton emission in inorganic-organic hybrids with mixed halides

Room-temperature tunable excitonic photoluminescence is demonstrated in alloy-tuned layered Inorganic-Organic (IO) hybrids, (C12H 25NH3)2PbI4(1-y)Br4y (y = 0 to 1). These perovskite IO hybrids adopt structures with alternating stacks of low-dimensional inorganic and organic layers, considered to be naturally self-assembled multiple quantum wells. These systems resemble stacked monolayer 2D semiconductors since no interlayer coupling exists. Thin films of IO hybrids exhibit sharp and strong photoluminescence (PL) at room-temperature due to stable excitons formed within the low-dimensional inorganic layers. Systematic variation in the observed exciton PL from 510 nm to 350 nm as the alloy composition is changed, is attributed to the structural readjustment of crystal packing upon increase of the Br content in the Pb-I inorganic network. The energy separation between exciton absorption and PL is attributed to the modified exciton density of states and diffusion of excitons from relatively higher energy states corresponding to bromine rich sites towards the lower energy iodine sites. Apart from compositional fluctuations, these excitons show remarkable reversible flips at temperature-induced phase transitions. All the results are successfully correlated with thermal and structural studies. Such structural engineering flexibility in these hybrids allows selective tuning of desirable exciton properties within suitable operating temperature ranges. Such wide-range PL tunability and reversible exciton switching in these novel IO hybrids paves the way to potential applications in new generation of optoelectronic devices. © 2013 AIP Publishing LLC.

Controlled amine functionality in self-assembled monolayers via the hidden amine route: chemical and electronic tunability.

A synthetic strategy for fabricating a dense amine functionalized self-assembled monolayer (SAM) on hydroxylated surfaces is presented. The assembly steps are monitored by X-ray photoelectron spectroscopy, Fourier transform infrared- attenuated total reflection, atomic force microscopy, variable angle spectroscopic ellipsometry, UV-vis surface spectroscopy, contact angle wettability, and contact potential difference measurements. The method applies alkylbromide-trichlorosilane for the fabrication of the SAM followed by surface transformation of the bromine moiety to amine by a two-step procedure: S(N)2 reaction that introduces the hidden amine, phthalimide, followed by the removal of the protecting group and exposing the free amine. The use of phthalimide moiety in the process enabled monitoring the substitution reaction rate on the surface (by absorption spectroscopy) and showed first-order kinetics. The simplicity of the process, nonharsh reagents, and short reaction time allow the use of such SAMs in molecular nanoelectronics applications, where complete control of the used SAM is needed. The different molecular dipole of each step of the process, which is verified by DFT calculations, supports the use of these SAMs as means to tune the electronic properties of semiconductors and for better synergism between SAMs and standard microelectronics processes and devices.