0D Cs3Cu2X5 (X = I,Br, and Cl) Nanocrystals: Colloidal Syntheses and Optical Properties

0D lead‐free metal halide nanocrystals (NCs) are an emerging class of materials with intriguing optical properties. Herein, colloidal synthetic routes are presented for the production of 0D Cs₃Cu₂X₅ (X = I, Br, and Cl) NCs with orthorhombic structure and well‐defined morphologies. All these Cs₃Cu₂X₅ NCs exhibit broadband blue‐green photoluminescence (PL) emissions in the range of 445–527 nm with large Stokes shifts, which are attributed to their intrinsic self‐trapped exciton (STE) emission characteristics. The high PL quantum yield of 48.7% is obtained from Cs₃Cu₂Cl₅ NCs, while Cs₃Cu₂I₅ NCs exhibit considerable air stability over 45 days. Intriguingly, as X is changed from I to Br and Cl, Cs₃Cu₂X₅ NCs exhibit a continuous redshift of emission peaks, which is contrary to the blueshift in CsPbX₃ perovskite NCs.     

New Twists of 3D Chiral Metamaterials

Rationally designed artificial materials, called metamaterials, allow for tailoring effective material properties beyond (“meta”) the properties of their bulk ingredient materials. This statement is especially true for chiral metamaterials, as unlocking certain degrees of freedom necessarily requires broken centrosymmetry. While the field of chiral electromagnetic/optical metamaterials has become rather mature, the field of elastic/mechanical metamaterials is just emerging and wide open. This research news reviews recent theoretical and experimental progress concerning 3D chiral mechanical and optical metamaterials, with special emphasis on work performed at KIT.     

Ligand-Assisted Self-Assembly of 3D Perovskite Nanocrystals into Chiral Inorganic Quasi-2D Perovskites (n = 3) with Ligand-Ratio-Dependent Chirality Inversion

Chiral inorganic quasi-2D perovskites are prepared by self-assembling 3D perovskites in solution for the first time. The quasi-2D perovskite synthesized is a pure-phase perovskite with <n> = 3 and is periodically arranged, which is a big breakthrough in quasi-2D inorganic perovskites.  With the individual chiral CsPbBr₃ nanocrystals (NCs) assemble into quasi-2D perovskite, the g-factor significantly improved (≈5 × 10⁻³). In addition, the chiroptical activity of quasi-2D perovskites is explored to be improved with the lateral size increasing. In the first stage of assembly, chiral optical activity is increased due to the lateral size-dependent optical activity, while the changes in the later stages are attributable to the chiral morphology. Interestingly, chirality inversion is found to be correlated to the number of ligands. It is believed that different conformers of chiral ligands caused by steric hindrance of the original ligand oleylamine result in opposite circular dichroism (CD) polarities. The chirality inversion phenomenon is universal, regardless of the choice of ligands. This work opens up a new path for the synthesis of quasi-2D perovskites and provides more opportunities for the modulation of chiral optical activity.     

High‐Speed Colloidal Quantum Dot Photodiodes via Accelerating Charge Separation at Metal–Oxide Interface

With ever‐growing technological demands in the imaging sensor industry for autonomous driving and augmented reality, developing sensors that can satisfy not only image resolution but also the response speed becomes more challenging. Herein, the focus is on developing a high‐speed photosensor capable of obtaining high‐resolution, high‐speed imaging with colloidal quantum dots (QDs) as the photosensitive material. In detail, high‐speed QD photodiodes are demonstrated with rising and falling times of τ_r = 28.8 ± 8.34 ns and τ_f = 40 ± 9.81 ns, respectively, realized by fast separation of electron–hole pairs due to the action of internal electric field at the QD interface, mainly by the interaction between metal oxide and the QD's ligands. Such energy transfer relations are analyzed and interpreted with time‐resolved photoluminescence measurements, providing physical understanding of the device and working principles.     

Colloidal Nanosurfactants for 3D Conformal Printing of 2D van der Waals Materials

Printing techniques using nanomaterials have emerged as a versatile tool for fast prototyping and potentially large-scale manufacturing of functional devices. Surfactants play a significant role in many printing processes due to their ability to reduce interfacial tension between ink solvents and nanoparticles and thus improve ink colloidal stability. Here, a colloidal graphene quantum dot (GQD)-based nanosurfactant is reported to stabilize various types of 2D materials in aqueous inks. In particular, a graphene ink with superior colloidal stability is demonstrated by GQD nanosurfactants via the π–π stacking interaction, leading to the printing of multiple high-resolution patterns on various substrates using a single printing pass. It is found that nanosurfactants can significantly improve the mechanical stability of the printed graphene films compared with those of conventional molecular surfactant, as evidenced by 100 taping, 100 scratching, and 1000 bending cycles. Additionally, the printed composite film exhibits improved photoconductance using UV light with 400 nm wavelength, arising from excitation across the nanosurfactant bandgap. Taking advantage of the 3D conformal aerosol jet printing technique, a series of UV sensors of heterogeneous structures are directly printed on 2D flat and 3D spherical substrates, demonstrating the potential of manufacturing geometrically versatile devices based on nanosurfactant inks.     

Direct Imprinting of Quasi-3D Nanophotonic Structures into Colloidal Quantum-Dot Devices

Three-dimensional (3D) subwavelength nanostructures have emerged and triggered tremendous excitement because of their advantages over the two-dimensional (2D) counterparts in fields of plasmonics, photonic crystals, and metamaterials. However, the fabrication and integration of 3D nanophotonic structures with colloidal quantum dots (CQDs) faces several technological obstacles, as conventional lithographic and etching techniques may affect the surface chemistry of colloidal nanomaterials. Here, the direct fabrication of functional quasi-3D nanophotonic structures into CQD films is demonstrated by one-step imprinting with well-controlled precision in both vertical and lateral directions. To showcase the potential of this technique, diffraction gratings, bilayer wire-grid polarizers, and resonant metal mesh long-pass filters are imprinted on CQD films without degrading the optical and electrical properties of CQD. Furthermore, a dual-diode CQD detector into an unprecedented mid-wave infrared two-channel polarization detector is functionalized by embedding an imprinted bilayer wire-grid polarizer within the CQDs. The results show that this approach offers a feasible pathway to combine quasi-3D nanostructures with colloidal materials-based optoelectronics and access a new level of light manipulation.     

Theoretical Prediction of Chiral 3D Hybrid Organic–Inorganic Perovskites

Hybrid organic–inorganic perovskites (HOIPs), in particular 3D HOIPs, have demonstrated remarkable properties, including ultralong charge‐carrier diffusion lengths, high dielectric constants, low trap densities, tunable absorption and emission wavelengths, strong spin–orbit coupling, and large Rashba splitting. These superior properties have generated intensive research interest in HOIPs for high‐performance optoelectronics and spintronics. Here, 3D hybrid organic–inorganic perovskites that implant chirality through introducing the chiral methylammonium cation are demonstrated. Based on structural optimization, phonon spectra, formation energy, and ab initio molecular dynamics simulations, it is found that the chirality of the chiral cations can be successfully transferred to the framework of 3D HOIPs, and the resulting 3D chiral HOIPs are both kinetically and thermodynamically stable. Combining chirality with the impressive optical, electrical, and spintronic properties of 3D perovskites, 3D chiral perovskites is of great interest in the fields of piezoelectricity, pyroelectricity, ferroelectricity, topological quantum engineering, circularly polarized optoelectronics, and spintronics.     

单分散SiO_2胶体光子晶体的自组装制备与表征(英文)

使用Stber法化学合成了粒径在200-350nm之间的单分散SiO2,采用垂直沉积技术自组装制备了胶体晶体薄膜。通过扫描电镜与分光光度计对样品的微观结构与透过光谱进行了表征,结果表明,组成胶体晶体的SiO2微球呈面心立方结构,膜层的厚度可以通过胶体溶液的浓度加以控制,胶体膜层透射光谱中出现的峰值位置取决于SiO2微球的大小,并且与布拉格定律理论计算的结果相一致,透射光谱中光学阻带的深度可以通过改变胶体悬浮液中SiO2颗粒的体积分数来调控。     

Programmable Bidirectional Folding of Metallic Thin Films for 3D Chiral Optical Antennas

3D structures with characteristic lengths ranging from nanometer to micrometer scale often exhibit extraordinary optical properties, and have been becoming an extensively explored field for building new generation nanophotonic devices. Albeit a few methods have been developed for fabricating 3D optical structures, constructing 3D structures with nanometer accuracy, diversified materials, and perfect morphology is an extremely challenging task. This study presents a general 3D nanofabrication technique, the focused ion beam stress induced deformation process, which allows a programmable and accurate bidirectional folding (?70°–+90°) of various metal and dielectric thin films. Using this method, 3D helical optical antennas with different handedness, improved surface smoothness, and tunable geometries are fabricated, and the strong optical rotation effects of single helical antennas are demonstrated.     

Thermochromism from Ultrathin Colloidal Sb2Se3 Nanowires Undergoing Reversible Growth and Dissolution in an Amine–Thiol Mixture

Liquid‐based thermochromics can be incorporated into an arbitrarily shaped container and provide a visual map of the temperature changes within its volume. However, photochemical degradation, narrow temperature range of operation, and the need for stringent encapsulation processes are challenges that can limit their widespread use. Here, a unique solution‐based thermochromic comprising ultrathin colloidal Sb₂Se₃ nanowires in an amine–thiol mixture is introduced. The nanowires undergo reversible growth and dissolution with repeated cycles of heating and cooling between 20 and 160 °C, exhibiting intense and contrasting color changes during these processes. Furthermore, the transition temperature in which a change in color first appears can be continuously tuned over a range larger than 100 °C by introducing controlled amounts of Sn²⁺. The colloidal nanowire dispersion in the amine–thiol mixture retains its thermochromic properties over hundreds of temperature cycles, continuous heating at 80 °C over months, and shelf life of up to 2 years in an open container under ambient conditions. To illustrate its utility as a robust liquid thermochromic, the nanowire solution is coated onto standard filter paper and its uses as a rewritable surface by thermal scribing, as well as an inexpensive means of visualizing the temperature distribution of an anisotropically heated block are demonstrated.     

Exploration and Exploitation of Water in Colloidal Crystals

Water on solid surfaces is ubiquitously found in nature, in most cases due to mere adsorption from ambient moisture. Because porous structures have large surfaces, water may significantly affect their characteristics. This is particularly obvious in systems formed by separate particles, whose interactions are strongly influenced by small amounts of liquid. Water/solid phenomena, like adsorption, condensation, capillary forces, or interparticle cohesion, have typically been studied at relatively large scales down to the microscale, like in wet granular media. However, much less is known about how water is confined and acts at the nanoscale, for example, in the interstices of divided systems, something of utmost importance in many areas of materials science nowadays. With novel approaches, in‐depth investigations as to where and how water is placed in the nanometer‐sized pores of self‐assembled colloidal crystals have been made, which are employed as a well‐defined, versatile model system with useful optical properties. In this Progress Report, knowledge gained in the last few years about water distribution in such nanoconfinements is gathered, along with how it can be controlled and the consequences it brings about to extract new or enhance existing material functionalities. New methods developed and new capabilities of standard techniques are described, and the water interplay with the optical, chemical, and mechanical properties of the ensemble are discussed. Some lines for applicability are also highlighted and aspects to be addressed in the near future are critically summarized.     

染料包覆胶态银纳米粒子掺杂的有机复合膜的制备与光吸收特性

为避免传统的湿化学法制备纳米掺杂复合材料中热处理给材料性能带来的负面影响,提出了一种简易可行的工艺方法:通过胶体化学法制备出稳定的胶态银纳米粒子分散系,以它为纳米粒子来源,使有机染料罗丹名6G(R6G)分子包覆到银纳米胶粒表面,将该胶体分散系均匀掺杂到明胶溶液中,制备出染料包覆胶态银纳米粒子掺杂的有机复合膜.本工作成功地制备出无机/有机活性基元掺杂的三元系复合膜,实现了染料分子对金属纳米粒子完全意义上包覆的设想和对活性基元的室温包埋工艺.电镜(TEM)观测了复合膜的显微结构,对复合膜的UV-Vis吸收光谱进行了测量.给出了一种包覆掺杂的结构模型,并用该模型成功地解释了实验结果.     

3D Printing of Customized Li‐Ion Batteries with Thick Electrodes

The growing demand for rechargeable lithium‐ion batteries (LIBs) with higher capacity in customized geometries underscores the need for new battery materials, architectures, and assembly strategies. Here, the design, fabrication, and electrochemical performance of fully 3D printed LIBs composed of thick semisolid electrodes that exhibit high areal capacity are reported. Specifically, semisolid cathode and anode inks, as well as UV curable packaging and separator inks for direct writing of LIBs in arbitrary geometries are created. These fully 3D printed and packaged LIBs, which are encased between two glassy carbon current collectors, deliver an areal capacity of 4.45 mAh cm^?2 at a current density of 0.14 mA cm^?2, which is equivalent to 17.3 Ah L^?1. The ability to produce high‐performance LIBs in customized form factors opens new avenues for integrating batteries directly within 3D printed objects.