Luminescent Mechanism and Anti-Counterfeiting Application of Hydrophilic, Undoped Room-Temperature Phosphorescent Silicon Nanocrystals.

Silicon nanocrystals (SiNCs) have attracted extensive attention in many advanced applications due to silicon's high natural abundance, low toxicity, and impressive optical properties. However, these applications are mainly focused on fluorescent SiNCs, little attention is paid to SiNCs with room-temperature phosphorescence (RTP) and their relative applications, especially water-dispersed ones. Herein, this work presents water-dispersible RTP SiNCs (UA-SiNCs) and their optical applications. The UA-SiNCs with a uniform particle size of 2.8 nm are prepared by thermal hydrosilylation between hydrogen-terminated SiNCs (H-SiNCs) and 10-undecenoic acid (UA). Interestingly, the resultant UA-SiNCs can exhibit tunable long-lived RTP with an average lifetime of 0.85 s. The RTP feature of the UA-SiNCs is confirmed to the n-π* transitions of their surface C═O groups. Subsequently, new dual-modal emissive UA-SiNCs-based ink is fabricated by blending with sodium alginate (SA) as the binder. The customized anticounterfeiting labels are also prepared on cellulosic substrates by screen-printing technique. As expected, UA-SiNCs/SA ink exhibits excellent practicability in anticounterfeiting applications. These findings will trigger the rapid development of RTP SiNCs, envisioning enormous potential in future advanced applications such as high-level anti-counterfeiting, information encryption, and so forth.

Band-Gap Narrowing and Electric Transport Regulation of Hybrid Perovskites via Pressure Engineering.

Lead-free organic-inorganic hybrid perovskites are one class of promising optoelectronic materials that have attracted much attention due to their outstanding stability and environmentally friendly nature. However, the intrinsic band gap far from the Shockley-Queisser limit and the inferior electrical properties largely limit their applicability. Here, a considerable band-gap narrowing from 2.43 to 1.64 eV with the compression rate up to 32.5% is achieved via high-pressure engineering in the lead-free hybrid perovskite MA3Sb2I9. Meanwhile, the electric transport process changes from the initial interaction of both ions and electrons to only the contribution of electrons upon compression. The alteration in electrical characteristics is ascribed to the vibration limitation of organic ions and the enhanced orbital overlap, resulting from the reduction of the Sb-I bond length through pressure-induced phase transitions. This work not only systematically investigates the correlation between the structural and optoelectronic properties of MA3Sb2I9 but also provides a potential pathway for optimizing electrical properties in lead-free hybrid perovskites.

Pressure-Tuning Localized Excitons Toward Enhanced Emission, Photocurrent Enhancement and Piezochromism in Unconventional ACI-Type 2D Hybrid Perovskites.

Simultaneous enhancement of free excitons (FEs) emission and self-trapped excitons (STEs) emission remains greatly challenging because of the radiative pathway competition. Here, a significant fluorescence improvement, associated with the radiative recombination of both FEs and STEs is firstly achieved in an unconventional ACI-type hybrid perovskite, (ACA)(MA)PbI4 (ACA=acetamidinium) crystals with {PbI6} octahedron units, through hydrostatic pressure processing. Note that (ACA)(MA)PbI4 exhibits a 91.5-fold emission enhancement and considerable piezochromism from green to red in a mild pressure interval of 1 atm to 2.5 GPa. The substantial distortion of both individual halide octahedron and the Pb-I-Pb angles between two halide octahedra under high pressure indeed determines the pressure-tuning localized excitons behavior. Upon higher pressure, photocurrent enhancement is also observed, which is attributed to the promoted electronic connectivity in (ACA)(MA)PbI4. The anisotropic compaction reduces the distance between neighboring organic molecules and {PbI6} octahedra, leading to the enhancement of hydrogen bonding interactions. This work not only offers a deep understanding of the structure-optical relationships of ACI-type perovskites, but also presents insights into breaking the limits of luminescent efficiency by pressure-suppressed nonradiative recombination.

Anomalous Pressure-Induced Blue-Shifted Emission of Ionic Copper-Iodine Clusters: The Competitive Effect between Cuprophilic Interactions and Through-Space Interactions.

Developing ionic copper-iodine clusters with multiple emitting is crucial for enriching lighting and display materials with various colors. However, the luminescent properties of traditional ionic copper-iodine clusters are often closely associated with low-energy cluster-centered triplet emission, which will redshift further as the Cu⋅⋅⋅Cu bond length decreases. This article utilizes a pressure-treated strategy to achieve an anomalous pressure-induced blue-shifted luminescence phenomenon in ionic Cu4I6(4-dimethylamino-1-ethylpyridinium)2 crystals for the first time, which is based on dominant through-space charge-transfer (TSCT). Herein, we reveal that the more advantageous through-space interactions in the competition between cuprophilic interactions and through-space interactions can lead to a blue-shifted luminescence. High-pressure angle-dispersive X-ray diffraction and high-pressure infrared experiments show that the enhanced through-space interactions mainly originate from forming new intermolecular C-H⋅⋅⋅I hydrogen bonds and the enhancement of van der Waals interactions between organic cations and anionic clusters. Theoretical calculations and experimental studies of excited-state dynamics confirm that the blue-shifted emission is due to the increased energy gap between the excited triplet and ground states caused by the electron delocalization under stronger through-space interactions. This work deepens previous understanding and provides a new avenue to design and synthetic ionic copper-iodine clusters with high-energy TSCT emission.

Pressure-shortened delayed fluorescence lifetime of solid-state thermally activated delayed fluorescent 4CzIPN: the structure evolution.

The incorporation of mechanochromic luminescence into thermally activated delayed fluorescence (TADF) molecules is a promising strategy for developing multifunctional mechanochromic luminescent materials. Nevertheless, due to the difficulties in systematic design, it is still challenging to controllably exploit the versatility of TADF molecules. In this work, we were surprised to find that the delayed fluorescence lifetime of 1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene crystals was continuously shortened with increasing pressure, which was ascribed to the increasing HOMO/LUMO overlap by planarization of the molecular conformation, as well as the pressure-induced emission enhancement and obvious multicolor emission at high pressure (green to red), owing to the formation of new interactions and the part-planarization of the molecular conformation, respectively. This study not only developed a new function of TADF molecules, but also provided a route to shorten the delayed fluorescence lifetime, which is beneficial for designing TADF-OLEDs with small efficiency roll-off.

Self-Trapped Exciton Emission Enhancement in 3D Cationic Lead Halide Hybrids Via Phase Transition Engineering.

Three-dimensional (3D) cationic lead halide hybrids constructed by organic ions and inorganic networks via coordination bonds are a promising material for solid-state lighting due to their exceptional environmental stability and broad-spectrum emission. Nevertheless, their fluorescence properties are hindered by the limited lattice distortion from extensive connectivity within the inorganic network. Here, a dramatic 100-fold enhancement of self-trapped exciton (STE) emission is achieved in 3D hybrid material [Pb2Br2][O2C(CH2)4CO2] via pressure-triggered phase transition. Notably, pressure-treated material exhibits a 110 nm redshift with 1.5-fold enhancement compared to the initial state after pressure was completely released. The irreversible structural phase transition intensifies the [PbBr3O3] octahedral distortion, which is highly responsible for the optimization of quenched emission. These findings present a promising strategy for improving the optical properties of 3D halide hybrids with relatively high stability and thus facilitate their practical applications by pressure-driven phase transition engineering.

Intense Broadband Emission in the Unconventional 3D Hybrid Metal Halide via High-Pressure Engineering.

Developing hybrid metal halides with self-trapped exciton (STE) emission is a powerful and promising approach to achieve single-component phosphors for wide-color-gamut display and illumination. Nevertheless, it is difficult to generate STEs and broadband emission in the classical and widely used 3D systems, owing to the great structural connectivity of metal-halogen networks. Here, high pressure is implemented to achieve dual emission and dramatical emission enhancement in 3D metal halide of [Pb3 Br4 ][O2 C(CH2 )2 CO2 ]. The pressure-induced new emission is ascribed to the radiation recombination of STEs from the Pb2 Br2 O2 tetrahedra with the promoted distortion through the isostructural phase transition. Furthermore, the wide range of emission chromaticity can be regulated by controlling the distortion order of different polyhedral units upon compression. This work not only constructs the relationship between structure and optical behavior of [Pb3 Br4 ][O2 C(CH2 )2 CO2 ], but also provides new strategies for optimizing broadband emission toward potential applications in solid-state lighting.

Water-borne, durable and multicolor silicon nanoparticles/sodium alginate inks for anticounterfeiting applications.

Recently, water-borne fluorescent inks have attracted extensive attention in anti-counterfeiting applications due to their convenient implementation and eco-friendliness. However, due to poor service durability, the latent authorization information from the inks is easily damaged, and even disappears when encountering water. Moreover, most of the existing fluorescent inks are monochromic, toxic, and allergic to skin, thus are unsuitable for their sustainability during real-life applications. Herein, this work presents environment-friendly, durable, and multicolor fluorescent anti-counterfeiting silicon nanoparticles (SiNPs)/sodium alginate (SA) inks. The multicolor SiNPs are synthesized by a one-pot method with defined morphologies and optical properties. Subsequently, SA is employed as the binder to prepare the fluorescent inks with optimized rheological properties. Practicability results show that the SiNPs/SA inks not only exhibit excellent printability, but also impart authentic information with superior covert performance. More notably, spraying solution of calcium dichloride can further improve fluorescent fastnesses of the SiNPs/SA inks by ionic crosslinking.