Slow Auger Recombination in Ag2Se Colloidal Quantum Dots.

Efficient Auger recombination (AR) presents a significant challenge for the advancement of colloidal quantum dot (QD)-based devices involving multiexcitons. Here, the AR dynamics of near-infrared Ag2Se QDs were studied through transient absorption experiments. As the QD radius increases from 0.9 to 2.5 nm, the biexciton lifetime (τ2) of Ag2Se QDs increases from 35 to 736 ps, which is approximately 10 times longer than that of comparable-sized CdSe and PbSe QDs. A qualitative analysis based on observables indicates that the slow Auger rate is primarily attributed to the low density of the final states. The biexciton lifetime and triexciton lifetime (τ3) of Ag2Se QDs follow R3 and R2.6 dependence, respectively. Moreover, the ratio of τ2/τ3 is ∼2.3-3.2, which is markedly lower than the value expected from statistical scaling (4.5). These findings suggest that environmentally friendly Ag2Se QDs can serve as excellent candidates for low-threshold lasers and third-generation photovoltaics utilizing carrier multiplication.

Toward temperature-insensitive near-infrared optical gain using low-toxicity Ag2Se quantum dots.

With the growing demand for developing lasers with high stability and integration, temperature-insensitive gain materials are highly desirable. Here, temperature-insensitive near-infrared (NIR) optical gain from low-toxicity Ag2Se quantum dots (QDs) is reported. Due to the large energy splitting between the band-edge hole state and the following state (∼430 meV), the thermal depopulation of the band-edge hole state in Ag2Se QDs is significantly suppressed. The long biexciton lifetime (245 ps at 300 K) of the QDs is sufficient to support the establishment of amplified spontaneous emission (ASE). Consequently, the characteristic temperature of the ASE threshold for the Ag2Se QD film is as high as 360 K, and efficient NIR ASE is observed up to 340 K. In addition, when the temperature is lower than 200 K, the ASE peak position is temperature insensitive because acoustic phonons cannot be effectively excited. Our findings reveal that Ag2Se QDs can be utilized as an excellent gain material for environmentally friendly temperature-insensitive NIR lasers.

The fluctuating standard potential of lithium in organic solvents.

The standard potential of a lithium metal electrode versus the standard hydrogen electrode was calculated by constructing the thermodynamic cycle in a hypothetical electrochemical cell with a dual-phase electrolyte. It is demonstrated that the standard potential of the lithium metal electrode can fluctuate over 0.5 V in different organic solvents, and is correlated to the modified donor number by the entropy of fusion of the solvents.

Binary structure and dynamics of the hydrogen bonds in the hydration shells of ions.

Ion-specific effects of cations (Li+, Na+, K+, Mg2+, Ca2+) and anions (F-, Cl-) on the hydrogen bond structure and dynamics of the coordination waters in the hydration shells have been studied using molecular dynamics simulations. Our simulations indicate that the hydrogen bonds between the first and second hydration shell waters show binary structural and dynamic properties. The hydrogen bond with a first shell water as the donor (HD) is strengthened, while those with a first shell water as the acceptor (HA) are weakened. For a hydrated anion, this binary effect reverses, but is less significant. This ion-specific binary effect correlates with the size and the valence of the ion, and is more significant for the strong kosmotropic ions of high charge density.

From a bulk to nanoconfined water chain: bridge water at the pore of the (6,6) carbon nanotube.

Hydrophobic porous materials with nano-pores are critical in many processes such as water desalination and biological membrane transportation. Herein, we performed molecular dynamics (MD) simulations on a prototypical hydrophobic nanochannel consisting of a (6,6) carbon nanotube (CNT) of 4.12 Å in radius and 13.72 Å in length immersed in water. The simulation shows that there are two major filling numbers of water N = 5 and N = 6, with the former being the most stable one. The confined waters form a single-file water chain with two hydrogen bonds per water. An extending water chain is formed for N = 5, with a bridge water near the pore of the CNT linking the water confined inside the CNT and hydration layer around the pore of the CNT. The bridge water can be considered as intermediate water characterized by three hydrogen bonds that distinguish from the confined water and bulk water. On the other hand, the hydration layer is depleted from the pore when N = 6. The analyses of the correlation of the bond order for the adjacent hydrogen bond pair of the hydration layer around the pore of the CNT does not show apparent difference from that of bulk water, though the former is slightly ordered. van Hove analysis of the bridge water shows that it tends to move inside the CNT when N < 5, in order to maintain the chemical equilibrium between the confined water and bulk water. This study highlights the unique structure of water around the hydrophobic pore of a sub-nanometer nanochannel.

Low-threshold near-infrared lasing at room temperature using low-toxicity Ag2Se quantum dots.

The development of colloidal near-infrared quantum dot (QD) lasers has been hindered by the high state degeneracy of lead salt QDs. Here, we show that this challenge can be addressed by utilizing orthorhombic Ag2Se QDs. We demonstrate that the lowest quantized states of Ag2Se QDs display a low, 2-fold degeneracy by employing femtosecond transient absorption (TA) spectroscopy. The optical gain threshold is evaluated to be 156 µJ cm-2, corresponding to ∼1.4 excitons per QD on average. Consequently, the amplified spontaneous emission (ASE) threshold of Ag2Se QD films is as low as 183 µJ cm-2. A large modal gain (∼470 cm-1) of the film is observed by variable stripe length (VSL) measurements. We leverage the low-threshold gain of the QDs to produce microlasers that exhibit single-mode near-infrared emission and a low threshold of 163 µJ cm-2 at room temperature. In addition, the cytotoxicity of Ag2Se QDs is remarkably negligible. Our work represents a significant step toward environmental-friendly near-infrared QD lasers.