Concerted Photoluminescence of Electrochemically Self-Assembled CuSCN / Stilbazolium Dye Hybrid Thin Films
Authors: Uda Kyota , Tsuda Yuki , Okada Shuji , Yamakado Ryohei , Sun Lina , Suzuri Yoshiyuki , White Matthew Schuette , Furis Madalina , Stadler Philipp , Dimitriev Oleg , Yoshida Tsukasa 
Published: May 2020

Whether they are inorganic or organic, the key words for creation of new functional materials should be (1) solution, (2) low temperature, and (3) rare-element-free for sustainable development. As a leading example, we explore electrochemical self-assembly (ESA) of inorganic / organic hybrid thin films. In addition to the interests to study evolution of unique hybrid structures, concerted new functionalities are anticipated due to intimate interaction between the inorganic and organic constituents. Herein, we report ESA of CuSCN / 4-(N,N-dimethylamino)-4’-(N’-methyl)stilbazolium (DAS) hybrid thin films and its concerted photoluminescence (PL) behavior [1].
Hybrid thin films of crystalline CuSCN/DAS in three distinctively different nanostructures were obtained by ESA from a single pot containing all the chemical ingredients. Adsorption of DAS during the electrochemical precipitation of CuSCN result in significant change of film morphology, crystal structure and its orientation, as DAS “occluded” into crystal grains of β-CuSCN, DAS phase separated nano-“haircomb” shape β-CuSCN, and DAS phase-separated in nano-“scale” shape α-CuSCN, by simply increasing DAST concentration in the bath [2]. Their optical properties for UV-vis-NIR absorption, photoluminescence (PL), and PL excitation (PLE) spectra were examined between 77 and 298 K, in comparison with solution and solid powder of DAS tosylate (DAST). While all the fluorescent dyes we previously found to hybridize with CuSCN underwent quenching due to hole injection from dye excited state to the valence band of CuSCN, DAS presented the first and only example to exhibit PL when combined with CuSCN [3].
DAST exhibited a strong exciton-phonon coupling to weaken, broaden, and red shift PL at room temperature, so that it inversely is strongly enhanced, sharpened, and blue-shifted at 77 K. However, the PL of the same dye in the hybrid thin film shows a slight red shift and not much intensified. Dielectric environment as well as ordered alignment of DAS greatly stabilize exciton against thermalization loss by suppressing twisted intramolecular charge transfer (TICT) and exciton-phonon coupling. The smallest temperature dependence, thus to be interpreted as the strongest exciton stabilization, was found for the “haircomb” β-CuSCN/DAS hybrid.
The PLE spectra of the “scale” α-CuSCN/DAS hybrid show a prominent sharp peak at 380 nm and another double-peak between 400 and 450 nm by cooling temperature. The former corresponds to the band-edge absorption of CuSCN, while the latter being similar to the LMCT absorption of [Cu(SCN)]+ complex. It has been confirmed that those peaks in PLE spectra indicate the contribution of CuSCN thin film without DAS for the generation of PL. These contributions of the light absorption by CuSCN to the PL from DAS clearly indicate energy transfer from CuSCN to DAS as a concerted PL mechanism. Concerted PL by energy transfer from CuSCN to DAS has also been found to occur efficiently, especially for the “scale” α-CuSCN/DAS with the largest contact area due to interpenetrating hybrid nanostructure in the smallest domain size. Those hybrid thin film having the concerted PL mechanism (Fig. 1) can possibly make these materials useful as LEDs.
[1] K. Uda et al., ACS Omega, 2019, 4 (2), 4056-4062.
[2] Y. Tsuda et al., Chem., 2017, 148, 845-854.
[3] K. Uda et al., ECS Trans., 2019, 88, 323-333.

Figure 1