Jianbo Jin

Nature Materials, Published online: 16 September 2021; doi:10.1038/s41563-021-01097-x

This Review provides an outlook on current understanding of the role of strain on the performance and stability of perovskite solar cells, as well as on tools to characterize strain in halide perovskite films and on strain management strategies.

A pivotal role in directing the growth of colloidal metal nanocrystals into diverse but well‐controlled shapes is played by surface capping agents. This article offers a comprehensive review of capping agents as well as their use in engineering the surface structures and catalytic properties of metal nanocrystals.

Abstract

Surface capping agents have been extensively used to control the evolution of seeds into nanocrystals with diverse but well‐controlled shapes. Here we offer a comprehensive review of these agents, with a focus on the mechanistic understanding of their roles in guiding the shape evolution of metal nanocrystals. We begin with a brief introduction to the early history of capping agents in electroplating and bulk crystal growth, followed by discussion of how they affect the thermodynamics and kinetics involved in a synthesis of metal nanocrystals. We then present representative examples to highlight the various capping agents, including their binding selectivity, molecular‐level interaction with a metal surface, and impacts on the growth of metal nanocrystals. We also showcase progress in leveraging capping agents to generate nanocrystals with complex structures and/or enhance their catalytic properties. Finally, we discuss various strategies for the exchange or removal of capping agents, together with perspectives on future directions.

In recent years there have been great strides in artificial intelligence (AI), with games often serving as challenge problems, benchmarks, and milestones for progress. Poker has served for decades as such a challenge problem. Past successes in such benchmarks, including poker, have been limited to two-player games. However, poker in particular is traditionally played with more than two players. Multiplayer games present fundamental additional issues beyond those in two-player games, and multiplayer poker is a recognized AI milestone. In this paper we present Pluribus, an AI that we show is stronger than top human professionals in six-player no-limit Texas hold’em poker, the most popular form of poker played by humans.

A facile low‐energy‐cost one‐pot scalable preparation strategy is developed to achieve homogeneously dispersed organic–inorganic perovskites nanoparticles in a freestanding gel with superior stability and high color purity even in water. The modular material design allows for a broad range of mechanical properties tunable from high elasticity stretchable gel in LEDs to rigid arbitrary 2D/3D structures printed by fast 3D‐printing technology.

Abstract

Metal‐halide perovskites have become appealing materials for optoelectronic devices. While the fast advancing stretchable/wearable devices require stability, flexibility and scalability, current perovskites suffer from ambient‐environmental instability and incompatible mechanical properties. Recently perovskite−polymer composites have shown improved in‐air stability with the protection of polymers. However, their stability remains unsatisfactory in water or high‐humidity environment. These methods also suffer from limited processability with low yield (2D film or beads) and high fabrication cost (high temperature, air/moisture‐free conditions), thereby limiting their device integration and broader applications. Herein, by combining facile photo‐polymerization with room‐temperature in‐situ perovskite reprecipitation at low energy cost, a one‐step scalable method is developed to produce freestanding highly‐stable luminescent organogels, within which CH₃NH₃PbBr₃ nanoparticles are homogeneously distributed. The perovskite‐organogels present a record‐high stability at different pH and temperatures, maintaining their high quantum yields for > 110 days immersing in water. This paradigm is universally applicable to broad choices of polymers, hence casting these emerging luminescent materials to a wide range of mechanical properties tunable from rigid to elastic. With intrinsically ultra‐stretchable photoluminescent organogels, flexible phosphorous layers were demonstrated with > 950% elongation. Rigid perovskite gels, on the other hand, permitted the deployment of 3D‐printing technology to fabricate arbitrary 2D/3D luminescent architectures.

One-dimensional (1D) nanomaterials with highly anisotropic optoelectronic properties are key components in energy harvesting, flexible electronics, and biomedical imaging devices. 3D patterning methods that precisely assemble nanowires with locally controlled composition and orientation would enable new optoelectronic device designs. As an exemplar, we have created and 3D-printed nanocomposite inks composed of brightly emitting colloidal cesium lead halide perovskite (CsPbX₃, X = Cl, Br, and I) nanowires suspended in a polystyrene-polyisoprene-polystyrene block copolymer matrix. The nanowire alignment is defined by the programmed print path, resulting in optical nanocomposites that exhibit highly polarized absorption and emission properties. Several devices have been produced to highlight the versatility of this method, including optical storage, encryption, sensing, and full-color displays.

Formation and rupture of nanofilaments are directly observed by in situ current–voltage/transmission electron microscopy to investigate the resistive‐switching mechanism in a model oxide system of polycrystalline SrTiO₃ thin film. High‐resolution transmission electron microscopy, electron‐energy‐loss spectroscopy, and in situ current–voltage measurements reveal the filament‐phase SrTi₁₁O₂₀ and its neighboring structure, which fundamentally establishes the thermodynamic origin and mechanism.

Abstract

Three central themes in the study of the phenomenon of resistive switching are the nature of the conducting phase, why it forms, and how it forms. In this study, the answers to all three questions are provided by performing switching experiments in situ in a transmission electron microscope on thin films of the model system polycrystalline SrTiO₃. On the basis of high‐resolution transmission electron microscopy, electron‐energy‐loss spectroscopy and in situ current–voltage measurements, the conducting phase is identified to be SrTi₁₁O₂₀. This phase is only observed at specific grain boundaries, and a Ruddlesden–Popper phase, Sr₃Ti₂O₇, is typically observed adjacent to the conducting phase. These results allow not only the proposal that filament formation in this system has a thermodynamic origin—it is driven by electrochemical polarization and the local oxygen activity in the film decreasing below a critical value—but also the deduction of a phase diagram for strongly reduced SrTiO₃. Furthermore, why many conducting filaments are nucleated at one electrode but only one filament wins the race to the opposite electrode is also explained. The work thus provides detailed insights into the origin and mechanisms of filament generation and rupture.

Defined nanostructures: Block copolymer coated nanoparticles can be assembled into linear arrays and superlattices with 2‐, 3‐, and 6‐fold rotational symmetry. The type of superlattice is determined by the nanoparticle/domain size ratio and the block copolymer grafting density. This general and versatile method can be applied for a variety of metal, semiconducting, and magnetic nanoparticles.

Abstract

The defined assembly of nanoparticles (NPs) in polymer matrices is an important prerequisite for next‐generation functional materials. A promising approach to control NP positions in polymer matrices at the nanometer scale is the use of block copolymers. It allows the selective deposition of NPs in nanodomains, but the final defined and ordered positioning of the NPs within the domains has not been possible. This can now be achieved by coating NPs with block copolymers. The self‐assembly of block copolymer‐coated NPs directly leads to ordered microdomains containing ordered NP arrays with exactly one NP per unit cell. By variation of the grafting density, the inter‐nanoparticle distance can be controlled from direct NP surface contact to surface separations of several nanometers, determined by the thickness of the polymer shell. The method can be applied to a wide variety of block copolymers and NPs and is thus suitable for a broad range of applications.

Lucky twins: Based on a theoretical analysis of graphene chemical vapor deposition (CVD) growth on a liquid Cu surface, 30 types of twinned graphene polycrystals are predicted and most of them are observed experimentally.

Abstract

Liquid metals have been widely used as substrates to grow graphene and other 2D materials. On a homogeneous and isotropic liquid surface, a polycrystalline 2D material is formed by coalescence of many randomly nucleated single‐crystal islands, and as a result, the domains in a polycrystal are expected to be randomly aligned. Here, we report the unexpected finding that only 30°‐twinned graphene polycrystals are grown on a liquid Cu surface. Atomic simulations confirm that the unique domain alignment in graphene polycrystals is due to the free rotation of graphene islands on the liquid Cu surface and the highly stable 30°‐grain boundaries in graphene. In‐depth analysis predicts 30 types of possible 30°‐twinned graphene polycrystals and 27 of them are observed. The revealed formation mechanism of graphene polycrystals on a liquid Cu surface deepens our fundamental understanding on polycrystal growth and could serve as a guideline for the controlled synthesis of 2D materials.

A general ligand symmetry‐breaking strategy is introduced to design and fabricate 2D Janus gold nanocrystal superlattice sheets with a nanocube on one side yet with a nanostar on the opposite side. Such asymmetric structures display distinct morphology‐dependent surface wettabilities, optical properties, and surface‐enhanced Raman scattering effects between the two sides, providing a novel way to design and tune the material properties of 2D superlattices.

Abstract

2D freestanding nanocrystal superlattices represent a new class of advanced metamaterials in that they can integrate mechanical flexibility with novel optical, electrical, plasmonic, and magnetic properties into one multifunctional system. The freestanding 2D superlattices reported to date are typically constructed from symmetrical constituent building blocks, which have identical structural and functional properties on both sides. Here, a general ligand symmetry‐breaking strategy is reported to grow 2D Janus gold nanocrystal superlattice sheets with nanocube morphology on one side yet with nanostar on the opposite side. Such asymmetric metallic structures lead to distinct wetting and optical properties as well as surface‐enhanced Raman scattering (SERS) effects. In particular, the SERS enhancement of the nanocube side is about 20‐fold of that of the nanostar side, likely due to the combined “hot spot + lightening‐rod” effects. This is nearly 700‐fold of SERS enhancement as compared with the symmetric nanocube superlattices without Janus structures.

Crystal clear? The ambiguity related to the single‐crystal nature of elastically and plastically deformable crystals as well as the correct use of the terms “single crystal/crystalline” and “polycrystal/crystalline” are clarified in this Minireview with selected examples of recently reported bending molecular crystals.

Abstract

The mention of the word “crystal” invokes images of minerals, gems, and rocks, all of which are inevitably solid, hard, and durable entities with well‐defined smooth faces and straight edges. With the discovery in the first half of the 20th century that many molecular crystals are soft and can be deformed in a similar way as rubber or plastic, this perception is changing, and both the concept and formal definition of what a crystal is may require reinterpretation. The seemingly naïve question posed in the title of this Minireview does not have a simple answer. Here, we discuss how the effects of the elastic and plastic deformation of molecular crystals on the diffraction signature give primary evidence of their degree of crystallinity. In most cases, the definition of a crystal holds for both elastically and plastically deformed crystals and, unless there is significant or complete physical separation of the crystal during the deformation, they can safely be considered (deformed) single crystals with a high concentration of defects.

The development of lead‐free perovskites has attracted increasing attention. The design rules for lead‐free perovskite materials with diverse structures are presented. The structure–property relationships and optical‐, electric‐, and magnetic‐related applications of these lead‐free perovskites are summarized. Based on these structure–property relationships, strategies for multifunctional perovskite design are proposed.

Abstract

Lead halide perovskites have emerged as promising semiconducting materials for different applications owing to their superior optoelectronic properties. Although the community holds different views toward the toxic lead in these high‐performance perovskites, it is certainly preferred to replace lead with nontoxic, or at least less‐toxic, elements while maintaining the superior properties. Here, the design rules for lead‐free perovskite materials with structural dimensions from 3D to 0D are presented. Recent progress in lead‐free halide perovskites is reviewed, and the relationships between the structures and fundamental properties are summarized, including optical, electric, and magnetic‐related properties. 3D perovskites, especially A₂B⁺B³⁺X₆‐type double perovskites, demonstrate very promising optoelectronic prospects, while low‐dimensional perovskites show rich structural diversity, resulting in abundant properties for optical, electric, magnetic, and multifunctional applications. Furthermore, based on these structure–property relationships, strategies for multifunctional perovskite design are proposed. The challenges and future directions of lead‐free perovskite applications are also highlighted, with emphasis on materials development and device fabrication. The research on lead‐free halide perovskites at Linköping University has benefited from inspirational discussions with Prof. Olle Inganäs.

The conjugated polyelectrolytes (CPEs) with K⁺ and tetramethylammonium (TMA⁺) are introduced as a multifunctional passivating and hole‐transporting layer for perovskite light‐emitting diodes. TMA⁺ improves significant growth of perovskites with suppressed interfacial defects, resulting in dramatically enhanced emitting properties and device performance. The lower formation energy of Pb_i‐TMA than that of Pb_i‐K suggests that passivation by TMA⁺ ions is more favorable than K⁺ ions.

Abstract

Metal halide perovskites (MHPs) have attracted significant attention as light‐emitting materials owing to their high color purities and tunabilities. A key issue in perovskite light‐emitting diodes (PeLEDs) is the fabrication of an optimal charge transport layer (CTL), which has desirable energy levels for efficient charge injection while blocking opposite charges and enabling perovskite layer growth with reduced interfacial defects. Herein, two poly(fluorene‐phenylene)‐based anionic conjugated polyelectrolytes (CPEs) with different counterions (K⁺ and tetramethylammonium (TMA⁺)) are presented as multifunctional passivating and hole‐transporting layers (HTLs). The crystal growth of MHPs grown on different HTLs is investigated through X‐ray photoelectron spectroscopy, X‐ray diffraction, and density functional theory calculation. The CPE bearing the TMA⁺ counterions remarkably improves the growth of perovskites with suppressed interfacial defects, leading to significantly enhanced emission properties and device performance. The luminescent properties are further enhanced via aging and electrical stress application with effective rearrangement of the counterions on the interfacial defects in the perovskites. Finally, efficient formamidinium lead tribromide‐based quasi‐2D PeLEDs with an external quantum efficiency of 10.2% are fabricated. Using CPEs with varying counterions as a CTL can serve as an effective method for controlling the interfacial defects and improving perovskite‐based optoelectronic device properties.

Stable inorganic perovskite CsPbI₃ thin films and solar cells are obtained by low temperature vacuum deposition without the need for high‐temperature annealing steps. Intentional compositional gradients on the samples allow combinatorial evaluation of structure‐property relationships using high‐throughput experimentation techniques, indicating that the perovskite phase is stable for Cs‐rich conditions. Solar cells with efficiency > 12% are demonstrated.

Abstract

The structural phases and optoelectronic properties of coevaporated CsPbI₃ thin films with a wide range of [CsI]/[PbI₂] compositional ratios are investigated using high throughput experimentation and gradient samples. It is found that for CsI‐rich growth conditions, CsPbI₃ can be synthesized directly at low temperature into the distorted perovskite γ‐CsPbI₃ phase without detectable secondary phases. In contrast, PbI₂‐rich growth conditions are found to lead to the non‐perovskite δ‐phase. Photoluminescence spectroscopy and optical‐pump THz‐probe mapping show carrier lifetimes larger than 75 ns and charge carrier (sum) mobilities larger than 60 cm² V⁻¹ s⁻¹ for the γ‐phase, indicating their suitability for high efficiency solar cells. The dependence of the carrier mobilities and luminescence peak energy on the Cs‐content in the films indicates the presence of Schottky defect pairs, which may cause the stabilization of the γ‐phase. Building on these results, p–i–n type solar cells with a maximum efficiency exceeding 12% and high shelf stability of more than 1200 h are demonstrated, which in the future could still be significantly improved, judging on their bulk optoelectronic properties.