arXiv subjects

Huotian Zhang

Publications and source records attributed to Huotian Zhang.

8 recordsLinked to original sources

arXiv2026

Vitrification-Devitrification Enables Tunable Photonic and Gas Sorption Properties of Zeolitic Imidazolate Frameworks

Zeolitic imidazolate framework (ZIF) glasses represent an emerging family of melt-quenched glasses, which exhibit immense potential for applications in gas separation, energy storage, and optics. However, their intrinsic porosity remains elusive due to the inherent challenges in resolving their disordered atomistic structures. Here, we systematically investigate the porosity of ZIF-4 and ZIF-62 crystals and their corresponding glasses. CO2 sorption at 195 K enables quantitative assessment of microporosity in both crystalline and glassy states, allowing the accessible micropore volume of the ZIF glasses to be determined. Moreover, establishing a direct relationship between photonic properties and structural porosity in Zn-based ZIF glasses remains challenging. Here we demonstrate striking broadband blue-light emission from ZIF-4 glass annealed under optimized conditions. A pronounced red shift is observed when increasing the annealing temperature above the glass transition temperature. By correlating the evolution of photoluminescence with structural porosity, we reveal the interplay between the photonic and gas sorption properties of ZIF glasses. These findings provide new insights into the structure-property relationships of ZIF glasses and offer a pathway toward the rational design of multifunctional MOF glasses.

cond-mat.mtrl-sci↗

arXiv2025

Towards stable metal inorganic-organic complex glasses

Metal inorganic-organic complex (MIOC) glasses have emerged as a new family of melt-quenched glasses. However, the vitrification of MIOC is challenging since most of the crystalline MIOC precursors decompose before melting. The decomposition problem severely narrows the compositional range of MIOC glass formation. Here, we report a novel approach for preparing the MIOC glasses that combines slow-solvent-removal with subsequent quenching to avoid gel thermal decomposition and crystallization. Specifically, the new approach utilizes an aprotic solvent (acetone) to kinetically prevent the ordering of the metal-ligand complex molecules in solution, thereby suppressing crystallization and forming a gel. The subsequent gradual drying process leads to the removal of the solvent to enhance the connections between molecules through hydrogen bonds, thus causing the formation of a hydrogen-bonded network. The increased network connectivity lowers the mobility of the molecules, thereby avoiding gel crystallization. Consequently, a disordered network is frozen-in during quenching of the dried gel from 130 °C to room temperature, and finally MIOC glass forms. Structural analyses reveal that hydrogen bonds are responsible for connecting the tetrahedral units. The as-prepared MIOC glass exhibits some fascinating behaviors, e.g., Tg increasing with rapid room-temperature relaxation, CO2 uptake, and red-shift of photoluminescence. This work not only presents a novel strategy for fabricating large-sized, stable, functional MIOC glasses, but also uncovers the critical role of hydrogen bonds in MIOC glass formation.

cond-mat.mtrl-sci↗

arXiv2025

Fabrication of hydrogen-bonded metal inorganic-organic complex glasses by ligand-tuning approach

Metal inorganic-organic complex (MIOC) crystals are a new category of hybrid glass formers. However, the glass-forming compositions of MIOC crystals are limited due to lack of both a general design principle for such compositions and a deep understanding of the structure and formation mechanism for MIOC glasses. This work reports a general approach for synthesizing glass-forming MIOC crystals. In detail, the principle of this approach is based on the creation of hydrogen-bonded structural network by substituting acid anions for imidazole or benzimidazole ligands in the tetrahedral units of zeolitic imidazolate framework crystals. By tuning the metal centers, anions, and organic ligands of MIOCs, supramolecular unit structures can be designed to construct supramolecular networks and thereby enable property modulation. Furthermore, mixed-ligand synthesis yielded a mixed-crystal system in which the glass-transition temperature (Tg) can be linearly tuned from 282 K to 360 K through gradual substitution of benzimidazole for imidazole. Interestingly, upon vitrification, MIOCs were observed to undergo reorganization of hydrogen-bonded networks, with retention of tetrahedral units, short-range disorder, and the freezing of multiple conformations. This work offers a new strategy to systematically expand the glass-forming compositional range of MIOCs and to develop functional MIOC glasses.

cond-mat.mtrl-sci↗

arXiv2025

Zeolitic imidazolate framework glasses emit white light

Zeolitic imidazolate framework (ZIF) glasses represent a newly emerged class of melt-quenched glasses, characterized by their intrinsic nanoporous structure, good processability, and multifunctionalities such as gas separation and energy storage. However, creating photonic functionalities in Zn-based ZIF glasses remains elusive. Here we show a remarkable broadband white light-emitting behavior in a Zn-based ZIF glass, which can be enhanced by annealing. Furthermore, we discovered a sharp red shift upon increasing annealing temperature above the critical temperature of 1.07Tg, where Tg is the glass transition temperature, for a short duration of 30 min. Finally, we achieved a high absolute internal photoluminescence quantum yield of 12.2% upon annealing of ZIF glass at 1.13Tg. Based on the optimally annealed ZIF glass, we fabricated a white light-emitting diode (LED) with the luminous efficacy of 4.2 lm/W and high operational stability, retaining 74.1% of its initial luminous efficacy after 180 min of continuous operation. These results not only demonstrate the feasibility of utilizing ZIF glasses in LED applications but also mark a significant advancement in the development of durable, efficient, and multifunctional photonic materials.

physics.optics↗

arXiv2025

Understanding the fill-factor limit of organic solar cells

Although the power conversion efficiencies of organic solar cells (OSCs) have surpassed 20%, they still lag behind commercial inorganic solar cells and emerging perovskite solar cells. To bridge this efficiency gap, improving the fill factor (FF) is critical, provided other photovoltaic parameters are not compromised. However, the fundamental understanding of the FF in OSCs remains incomplete. In this work, we systematically investigate a wide range of OSCs with the FF values spanning 0.27 to 0.80, and analyse the effect of free charge generation and recombination on the FF in OSCs. To explain our observations, we developed an analytical model that quantitatively correlates the applied electric field with the energetics of excited states in donor-acceptor blends. By combining device characterisation, spectroscopy, and theoretical modelling, we reveal that the Stark effect and the field-dependent charge transfer significantly impact the FF in state-of-the-art OSCs with low voltage losses. Our findings highlight that suppressing geminate decay by increasing exciton lifetime is a promising strategy for boosting the FF and achieving future efficiency gains in OSCs.

cond-mat.mtrl-sci↗

arXiv2023

Understanding the Role of Triplet-triplet Annihilation in Non-fullerene Acceptor Organic Solar Cells

Non-fullerene acceptors (NFAs) have enabled power conversion efficiencies exceeding 19% in organic solar cells (OSCs). However, the open-circuit voltage of OSCs remains low relative to their optical gap due to excessive non-radiative recombination, and this now limits performance. Here, we consider an important aspect of OSC design, namely management of the triplet exciton population formed after non-geminate charge recombination. By comparing the blends PM6:Y11 and PM6:Y6, we show that the greater crystallinity of the NFA domains in PM6:Y11 leads to a higher rate of triplet-triplet annihilation (TTA). We attribute this to the four times larger ground state dipole moment of Y11 versus Y6, which improves the long range NFA out-of-plane ordering. Since TTA converts a fraction of the non-emissive triplet states into bright singlet states, it has the potential to reduce non-radiative voltage losses. Through a kinetic analysis of the recombination processes under 1-Sun illumination, we provide a framework for determining the conditions under which TTA may improve OSC performance. If these could be satisfied, TTA has the potential to reduce non-radiative voltage losses by up to several tens of mV and could thus improve OSC performance.

physics.app-ph↗

arXiv2021

Slow Relaxation of Photogenerated Charge Carriers Boosts Open-Circuit Voltage of Organic Solar Cells

Among the parameters determining the efficiency of an organic solar cell, the open-circuit voltage ($V_\text{OC}$) is the one with most room for improvement. Existing models for the description of $V_\text{OC}$ assume that photogenerated charge carriers are thermalized. Here, we demonstrate that quasi-equilibrium concepts cannot fully describe $V_\text{OC}$ of disordered organic devices. For two representative donor:acceptor blends it is shown that $V_\text{OC}$ is actually 0.1-0.2 V higher than it would be if the system was in thermodynamic equilibrium. Extensive numerical modeling reveals that the excess energy is mainly due to incomplete relaxation in the disorder-broadened density of states. These findings indicate that organic solar cells work as nonequilibrium devices, in which part of the photon excess energy is harvested in the form of an enhanced $V_\text{OC}$.

physics.app-ph↗

arXiv2021

Experimentally Validated Hopping-Transport Model for Energetically Disordered Organic Semiconductors

Charge transport in disordered organic semiconductors occurs by hopping of charge carriers between localized sites that are randomly distributed in a strongly energy dependent density of states. Extracting disorder and hopping parameters from experimental data like temperature dependent current-voltage characteristics typically relies on parametrized mobility functionals that are integrated in a drift-diffusion solver. Surprisingly, the functional based on the extended Gaussian disorder model (eGDM) has been extremely successful at this, despite it being based on the assumption of nearest neighbor hopping (nnH) on a regular lattice. We here propose a variable range hopping (VRH) model that has been integrated in a freeware drift-diffusion solver. The mobility model has been calibrated using kinetic Monte Carlo calculations and shows good agreement with the Monte Carlo calculations over the experimentally relevant part of the parameter space. The model is applied to temperature-dependent space charge limited current (SCLC) measurements of different systems. In contrast to the eGDM, the VRH model provides a consistent description of both p-type and n-type devices. We find a critical ratio of aNN/$α$ (mean inter-site distance / localization radius) of ~3 below which hopping to non-nearest neighbors becomes important around room temperature and the eGDM cannot be used for parameter extraction. Typical (Gaussian) disorder values in the range 45-120 meV are found, without any clear correlation with photovoltaic performance when the same active layer is used in an organic solar cell.

cond-mat.mtrl-sci↗