Jochen Feldmann

I-III-VI quantum dots are potential candidates for light-emitting and light-harvesting applications due to their heavy-metal–free composition and chemical tunability. Despite their potential, the investigation of intrinsic exciton and excitonic many-body dynamics has often been complicated because of their extensive defect energy landscape. Here, we investigate bright band-gap-emitting AgInS 2 quantum dots of sizes ranging from ∼ 4 to 7 nm using femtosecond pump-probe spectroscopy to link quantum confinement to exciton formation and many-body interactions. The exciton formation time is governed by inter-valence-band hole relaxation. This increases by more than a factor of 4 with decreasing quantum dot size, reflecting size-dependent exciton-phonon scattering efficiency. By temporally correlating hole relaxation with induced absorption dynamics, we identify different exciton-to-biexciton transitions originating from different exciton states. Excitation-fluence-dependent measurements reveal a biexciton decay time that scales with the quantum dot volume. Smaller quantum dots show fast decay of <100 ps, primarily governed by exciton-exciton annihilation. In larger quantum dots, the biexciton lifetime exceeds 400 ps, indicating reduced annihilation efficiency. Complementary streak-camera photoluminescence experiments provide direct spectroscopic evidence that these long-lived biexcitons are partially emissive. Collectively, we report an in-depth ultrafast-optical study yielding fundamental insights into the complex landscape of exciton formation and biexciton physics, which advances the understanding of intrinsic optical processes in AgInS 2 quantum dots among I-III-VI materials.

Lead-halide hybrid perovskites (RNH₃PbX₃, X = halide, e.g., Cl, Br, I; R = organic moiety) show promise for next-generation optoelectronic devices due to their simple synthesis routes, strong light absorption, and high photoluminescence quantum yield. However, postsynthetic halide exchange in lead-halide perovskites poses a challenge for the functionality of many perovskite devices. For example, in all-perovskite heterostructures, halide diffusion results in the formation of undesired mixed alloys rather than sharp interfaces required for many optoelectronic applications. To address this issue, we incorporated lysine molecules, one of the 20 common amino acids, into a hybrid perovskite MAPbBr₃ (MA = CH₃NH₃) host and investigated their impact on the host's ability to undergo postsynthetic halide exchange. We immersed lysine-incorporated MAPbBr₃ crystals in solutions containing Cl^- or I^- for varying durations and analyzed subsequent halide exchange-related changes using ion chromatography, high-resolution powder X-ray diffraction, and photoluminescence spectroscopy. Our findings unanimously indicate that incorporated lysine significantly impedes postsynthetic Cl^- and I^- diffusion into bulk MAPbBr₃. Our new bioinspired approach opens a route toward mitigating postsynthetic halide exchange in lead-halide hybrid perovskites and improving the suitability of perovskite devices for optoelectronic applications.

Optically excited electronic excitations are coupled to the soft and polar halide perovskite lattice, generating coherent phonons after subpicosecond interband laser-excitation. In Ag-based halide double perovskites, Ag-vacancies can bind free excitons, resulting in a pronounced bound exciton resonance. Here, we report the detection of three modulation frequencies corresponding to coherent phonons in Ag-based double perovskite nanocrystals at distinct spectral positions at the bound exciton resonance. Two of them are found in oscillatory spectral shifts of the bound exciton resonance and are identified as Cs- and Br-related bulk phonons. Surprisingly, a third frequency is observed as an intensity modulation. We argue that this amplitude oscillation is a consequence of an optically generated vibronic wave packet localized at a Ag-vacancy. Consequently, the localized coherent phonon modulates the giant oscillator strength of the bound exciton. This optically induced and spatially localized lattice shaking could potentially be useful for initiating photochemical reactions with atomic precision.

Photocatalytic water splitting is a promising approach to generating sustainable hydrogen. However, the transport of photoelectrons to the catalyst sites, usually within ps‐to‐ns timescales, is much faster than proton delivery (∼μs), which limits the activity. Therefore, the acceleration of abstraction of protons from water molecules towards the catalytic sites to keep up with the electron transfer rate can significantly promote hydrogen production. The photobasic effect that is the increase in proton affinity upon excitation offers means to achieve this objective. Herein, we design photobasic carbon dots and identify that internal pyridinic N sites are intrinsically photobasic. This is supported by steady‐state and ultrafast spectroscopic measurements that demonstrate proton abstraction within a few picoseconds of excitation. Furthermore, we show that in water, they form a unique four‐level lasing scheme with optical gain and stimulated emission. The latter competes with photocatalysis, revealing a rather unique mechanism for efficiency loss, such that the stimulated emission can act as a toggle for photocatalytic activity. This provides additional means of controlling the photocatalytic process and helps the rational design of photocatalytic materials.

Photocatalytic water splitting is a promising approach to generating sustainable hydrogen. However, the transport of photoelectrons to the catalyst sites, usually within ps‐to‐ns timescales, is much faster than proton delivery (∼μs), which limits the activity. Therefore, the acceleration of abstraction of protons from water molecules towards the catalytic sites to keep up with the electron transfer rate can significantly promote hydrogen production. The photobasic effect that is the increase in proton affinity upon excitation offers means to achieve this objective. Herein, we design photobasic carbon dots and identify that internal pyridinic N sites are intrinsically photobasic. This is supported by steady‐state and ultrafast spectroscopic measurements that demonstrate proton abstraction within a few picoseconds of excitation. Furthermore, we show that in water, they form a unique four‐level lasing scheme with optical gain and stimulated emission. The latter competes with photocatalysis, revealing a rather unique mechanism for efficiency loss, such that the stimulated emission can act as a toggle for photocatalytic activity. This provides additional means of controlling the photocatalytic process and helps the rational design of photocatalytic materials.

Incorporation of organic molecules into the crystal lattice of biominerals is one of Nature's main strategies to modify the structure, morphology, and specific physical properties of the mineral host. Inspired by this biostrategy, it is shown that several semiconductors, whose band gaps are in the ultraviolet or visible absorption spectrum, can incorporate individual amino acids (AAs) into their crystalline structures. Interestingly, such incorporation is accompanied by an increase in the optical band gap of semiconductor hosts, resulting from an internal quantum confinement effect. In this work, this bioinspired route of band gap tuning is applied for the first time to a semiconductor with a near‐infrared (NIR) band gap. Indeed individual AAs are found to become incorporated into the crystalline structure of lead (II) sulfide (PbS). It is shown that this incorporation induces an expansion of the PbS unit cell as well as changes in the morphology. Moreover, an unprecedented increase of up to 40–50% in the optical band gap is observed in the case of cysteine and lysine incorporation.

SPIE Digital Library Proceedings

It usually requires high temperature and high pressure to reform methanol with water to hydrogen with high turnover frequency (TOF). Here we show that hydrogen can be produced from alkaline methanol on a light‐triggered multi‐layer system with a very high hydrogen evolution rate up to ca. 1 μmol s⁻¹ under the illumination of a standard Pt‐decorated carbon nitride. The system can achieve a remarkable TOF up to 1.8×10⁶ moles of hydrogen per mole of Pt per hour under mild conditions. The total turnover number (TTN) of 470 000 measured over 38 hours is among the highest reported. The system does not lead to any CO_x emissions, hence it could feed clean hydrogen to fuel cells. In contrast to a slurry system, the proposed multi‐layer system avoids particle aggregation and effectively uses light and Pt active sites. The performance is also attributed to the light‐triggered reforming of alkaline methanol. This notable performance is a promising step toward practical light‐driven hydrogen generation.