H2O-NH4+-Induced Emission Modulation in Sb3+-Doped (NH4)2InCl5·H2O.

Lead-based metal halide perovskites have received widespread attention for their promising application prospects in the field of lighting and display due to their excellent optical properties. However, the toxicity of lead may hinder their further commercial application. Herein, a zero-dimensional (0D) metal halide (NH4)2InCl5·H2O with an orthorhombic structure and the Pnma space group was produced. With doping with Sb3+, these products exhibit one highly efficient and wide yellow emission band (∼450-850 nm) in their photoluminescence (PL) spectra, which covers almost the entire visible spectral range at room temperature; however, they give two emission bands with long decay lifetimes (microseconds) at low temperature. Temperature-dependent steady-state PL, transient PL spectroscopy, temperature-dependent Raman spectra characterization, and theoretical band structure calculations confirm that the dual-band emission at low temperature originates from the dual vibronic levels of the self-trapped exciton (STE) in the hole-vibration state, whose vibration energy is related to the H2O-NH4+ connection in the valence band. This result proves that the vibronic state in STE formation involves both electrons and holes in the excited states, the opposite of this happens in the electron-vibration band in most perovskite halides. These results provide new insight into the luminescent mechanism of Sb3+ in halide perovskites, especially used for emission color modulation by the temperature-dependent electron- or hole-vibration processes.

A Zero-Dimensional Organic Lead Bromide of (TPA)2PbBr4 Single Crystal with Bright Blue Emission.

Blue-luminescence materials are needed in urgency. Recently, zero-dimensional (0D) organic metal halides have attractive much attention due to unique structure and excellent optical properties. However, realizing blue emission with near-UV-visible light excitation in 0D organic metal halides is still a great challenge due to their generally large Stokes shifts. Here, we reported a new (0D) organic metal halides (TPA)2PbBr4 single crystal (TPA+ = tetrapropylammonium cation), in which the isolated [PbBr4]2- tetrahedral clusters are surrounded by organic ligand of TPA+, forming a 0D framework. Upon photoexcitation, (TPA)2PbBr4 exhibits a blue emission peaking at 437 nm with a full width at half-maximum (FWHM) of 50 nm and a relatively small Stokes shift of 53 nm. Combined with density functional theory (DFT) calculations and spectral analysis, it is found that the observed blue emission in (TPA)2PbBr4 comes from the combination of free excitons (FEs) and self-trapped exciton (STE), and a small Stokes shift of this compound are caused by the small structure distortion of [PbBr4]2- cluster in the excited state confined by TPA molecules, in which the multi-phonon effect take action. Our results not only clarify the important role of excited state structure distortion in regulating the STEs formation and emission, but also focus on 0D metal halides with bright blue emission under the near-UV-visible light excitation.

Efficient Yellow Self-Trapped Exciton Emission in Sb3+-Doped RbCdCl3 Metal Halides.

Metal halide perovskites have flexible crystal and electronic structures and adjustable emission characteristics, which have very broad applications in the optoelectronic field. Among them, all-inorganic perovskites have attracted more attention than others in recent years because of their characteristics of large diffusion length, high luminescence efficiency, and good stability. In this work, Sb3+-doped RbCdCl3 crystalline powder was synthesized by a simple hydrothermal method, and its luminescence properties were studied, which showed a broad emission band with a large Stokes shift and efficient yellow light emission at about 596 nm at room temperature with a photoluminescence quantum yield of 91.7%. The emission came from the transition of the self-trapped exciton 1 (STE1) out of 3Pn (n = 0, 1, and 2) to S0 due to strong electron-phonon coupling, which scaled with increasing temperature. Moreover, its emission color became white at low temperatures due to the occurrence of transition of other self-trapped exciton 0 (STE0) state emission out of the 1S states of Sb ions to S0 in the lattice. These emission color changes may be used for temperature sensing, and this Sb3+-doped RbCdCl3 material expands the knowledge of the efficient luminescent inorganic material family for further applications of all-inorganic perovskites.

Pure White Emission with 91.9% Photoluminescence Quantum Yield of [(C3H7)4N]2Cu2I4 out of Polaronic States and Ultra-High Color Rendering Index.

Recently, cuprous halide perovskite-type materials have drawn tremendous attention for their intriguing optical properties. Here, a zero-dimensional (0D) Cu(I)-based compound of [(C3H7)4N]2Cu2I4 ([C3H7)4N]+ = tetrapropylammonium cation) was synthesized by a facile solution method, a monoclinic system of P21/n symmetry with a Cu2I42- cluster as the confined structure. The as-synthesized [(C3H7)4N]2Cu2I4 exhibits bright dual-band pure white emission with a photoluminescence quantum yield (PLQY) of 91.9% and CIE color coordinates of (0.33, 0.35). Notably, this compound also exhibits an ultrahigh color rendering index (CRI) of 92.2, which is comparable to the highest value of single-component metal halides reported recently. Its Raman spectra provide a clear spectral profile of strong electron-phonon interaction after [(C3H7)4N]+ incorporation, favoring the self-trapped exciton (STE) formation. [(C3H7)4N]2Cu2I4 can give dual-STE bands at the same time because of the Cu-Cu metal bond in a Cu2I42- cluster, whose populations could be scaled by temperature, together with the local dipole orientation modulation of neighboring STEs and phase transition related emission color coordinate change. Particularly, the outstanding chemical- and antiwater stability of this compound was also demonstrated. This work illustrates the potential of such cuprous halide perovskite-type materials in multifunctional applications, such as lighting in varied environments.

Highly Efficient Cool-White Photoluminescence of (Gua)3Cu2I5 Single Crystals: Formation and Optical Properties.

Zero-dimensional lead-free organic-inorganic hybrid metal halides have drawn attention as a result of their local metal ion confinement structure and photoelectric properties. Herein, a lead-free compound of (Gua)3Cu2I5 (Gua = guanidine) with a different metal ion confinement has been discovered, which possesses a unique [Cu2I5]3- face-sharing tetrahedral dimer structure. First-principles calculation demonstrates the inherent nature of a direct band gap for (Gua)3Cu2I5, and its band gap of ∼2.98 eV was determined by experiments. Worthy of note is that (Gua)3Cu2I5 exhibits a highly efficient cool-white emission peaking at 481 nm, a full-width at half-maximum of 125 nm, a large Stokes shift, and a photoluminescence quantum efficiency of 96%, originating from self-trapped exciton emission. More importantly, (Gua)3Cu2I5 single crystals have a reversible thermoinduced luminescence characteristic due to a structural transition scaled by the electron-phonon coupling coefficients, which can be converted back and forth between cool-white and yellow color emission by heating or cooling treatment within a short time. In brief, as-synthesized (Gua)3Cu2I5 shows great potential for application both in single-component white solid-state lighting and sensitive temperature scaling.