Disorder-tuned conductivity in amorphous monolayer carbon.

Correlating atomic configurations-specifically, degree of disorder (DOD)-of an amorphous solid with properties is a long-standing riddle in materials science and condensed matter physics, owing to difficulties in determining precise atomic positions in 3D structures1-5. To this end, 2D systems provide insight to the puzzle by allowing straightforward imaging of all atoms6,7. Direct imaging of amorphous monolayer carbon (AMC) grown by laser-assisted depositions has resolved atomic configurations, supporting the modern crystallite view of vitreous solids over random network theory8. Nevertheless, a causal link between atomic-scale structures and macroscopic properties remains elusive. Here we report facile tuning of DOD and electrical conductivity in AMC films by varying growth temperatures. Specifically, the pyrolysis threshold temperature is the key to growing variable-range-hopping conductive AMC with medium-range order (MRO), whereas increasing the temperature by 25 °C results in AMC losing MRO and becoming electrically insulating, with an increase in sheet resistance of 109 times. Beyond visualizing highly distorted nanocrystallites embedded in a continuous random network, atomic-resolution electron microscopy shows the absence/presence of MRO and temperature-dependent densities of nanocrystallites, two order parameters proposed to fully describe DOD. Numerical calculations establish the conductivity diagram as a function of these two parameters, directly linking microstructures to electrical properties. Our work represents an important step towards understanding the structure-property relationship of amorphous materials at the fundamental level and paves the way to electronic devices using 2D amorphous materials.

Author Correction: The Apostasia genome and the evolution of orchids.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Polymer Semiconductors: Synthesis, Processing, and Applications.

Polymer semiconductors composed of a carbon-based π conjugated backbone have been studied for several decades as active layers of multifarious organic electronic devices. They combine the advantages of the electrical conductivity of metals and semiconductors and the mechanical behavior of plastics, which are going to become one of the futures of modulable electronic materials. The performance of conjugated materials depends both on their chemical structures and the multilevel microstructures in solid states. Despite the great efforts that have been made, they are still far from producing a clear picture among intrinsic molecular structures, microstructures, and device performances. This review summarizes the development of polymer semiconductors in recent decades from the aspects of material design and the related synthetic strategies, multilevel microstructures, processing technologies, and functional applications. The multilevel microstructures of polymer semiconductors are especially emphasized, which plays a decisive role in determining the device performance. The discussion shows the panorama of polymer semiconductors research and sets up a bridge across chemical structures, microstructures, and finally devices performances. Finally, this review discusses the grand challenges and future opportunities for the research and development of polymer semiconductors.

The Saururus chinensis genome provides insights into the evolution of pollination strategies and herbaceousness in magnoliids.

Saururus chinensis, an herbaceous magnoliid without perianth, represents a clade of early-diverging angiosperms that have gone through woodiness-herbaceousness transition and pollination obstacles: the characteristic white leaves underneath inflorescence during flowering time are considered a substitute for perianth to attract insect pollinators. Here, using the newly sequenced S. chinensis genome, we revisited the phylogenetic position of magnoliids within mesangiosperms, and recovered a sister relationship for magnoliids and Chloranthales. By considering differentially expressed genes, we identified candidate genes that are involved in the morphogenesis of the white leaves in S. chinensis. Among those genes, we verified - in a transgenic experiment with Arabidopsis - that increasing the expression of the "pseudo-etiolation in light" gene (ScPEL) can inhibit the biosynthesis of chlorophyll. ScPEL is thus likely responsible for the switches between green and white leaves, suggesting that changes in gene expression may underlie the evolution of pollination strategies. Despite being an herbaceous plant, S. chinensis still has vascular cambium and maintains the potential for secondary growth as a woody plant, because the necessary machinery, i.e., the entire gene set involved in lignin biosynthesis, is well preserved. However, similar expression levels of two key genes (CCR and CAD) between the stem and other tissues in the lignin biosynthesis pathway are possibly associated with the herbaceous nature of S. chinensis. In conclusion, the S. chinensis genome provides valuable insights into the adaptive evolution of pollination in Saururaceae and reveals a possible mechanism for the evolution of herbaceousness in magnoliids.

Achieving Ideal and Environmentally Stable n-Type Charge Transport in Polymer Field-Effect Transistors.

Realizing ideal charge transport in field-effect transistors (FETs) of conjugated polymers is crucial for evaluating device performance, such as carrier mobility and practical applications of conjugated polymers. However, the current FETs using conjugated polymers as the active layers generally show certain non-ideal transport characteristics and poor stability. Here, ideal charge transport of n-type polymer FETs is achieved on flexible polyimide substrates by using an organic-inorganic hybrid double-layer dielectric. Deposited conjugated polymer films show highly ordered structures and low disorder, which are supported by grazing-incidence wide-angle X-ray scattering, near-edge X-ray absorption fine structure, and molecular dynamics simulations. Furthermore, the organic-inorganic hybrid double-layer dielectric provides low interfacial defects, leading to excellent charge transport in FETs with high electron mobility (1.49 ± 0.46 cm2 V-1 s-1) and ideal reliability factors (102 ± 7%). Fabricated polymer FETs show a self-encapsulation effect, resulting in high stability of the FET charge transport. The polymer FETs still work with high mobility above 1 cm2 V-1 s-1 after storage in air for more than 300 days. Compared with state-of-the-art conjugated polymer FETs, this work simultaneously achieves ideal charge transport and environmental stability in n-type polymer FETs, facilitating rapid device optimization of high-performance polymer electronics.

Assessing the Role of BN-Embedding Position in B2N2-Perylenes.

Incorporating heteroatoms can effectively modulate the molecular optoelectronic properties. However, the fundamental understanding of BN doping effects in BN-embedded polycyclic aromatic hydrocarbons (PAHs) is underexplored, lacking rational guidelines to modulate the electronic structures through BN units for advanced materials. Herein, a concise synthesis of novel B2N2-perylenes with BN doped at the bay area is achieved to systematically explore the doping effect of BN position on the photophysical properties of PAHs. The shift of BN position in B2N2-perylenes alters the π electron conjugation, aromaticity and molecular rigidness significantly, achieving substantially higher electron transition abilities than those with BN doped in the nodal plane. It is further clarified that BN position dominates the photophysical properties over BN orientation. The revealed guideline here may apply generally to novel BN-PAHs, and aid the advancement of BN-PAHs with highly-emissive performance.

Buffer Chain Model for Understanding Crystallization Competition in Conjugated Polymers.

It remains challenging to comprehensively understand the packing models of conjugated polymers, in which side chains play extremely critical roles. The side chains are typically flexible and non-conductive and are widely used to improve the polymer solubility in organic solutions. Herein, a buffer chain model is proposed to describe link between conjugated backbone and side chains for understanding the relationship of crystallization competition of conductive conjugated backbones and non-conductive side chains. A longer buffer chain is beneficial for alleviating such crystallization competition and further promoting the spontaneous packing of conjugated backbones, resulting in enhanced charge transport properties. Our results provide a novel concept for designing conjugated polymers towards ordered organization and enhanced electronic properties and highlight the importance of balancing the competitive interactions between different parts of conjugated polymers.

Azonia-Naphthalene: A Cationic Hydrophilic Building Block for Stable N-Type Organic Mixed Ionic-Electronic Conductors.

Conjugated polymers that can efficiently transport both ionic and electronic charges have broad applications in next-generation optoelectronic, bioelectronic, and energy storage devices. To date, almost all the conjugated polymers have hydrophobic backbones, which impedes efficient ion diffusion/transport in aqueous media. Here, we design and synthesize a novel hydrophilic polymer building block, 4a-azonia-naphthalene (AN), drawing inspiration from biological systems. Because of the strong electron-withdrawing ability of AN, the AN-based polymers show typical n-type charge transport behaviors. We find that cationic aromatics exhibit strong cation-π interactions, leading to smaller π-π stacking distance, interesting ion diffusion behavior, and good morphology stability. Additionally, AN enhances the hydrophilicity and ionic-electronic coupling of the polymer, which can help to improve ion diffusion/injection speed, and operational stability of organic electrochemical transistors (OECTs). The integration of cationic building blocks will undoubtedly enrich the material library for high-performance n-type conjugated polymers.

Origin and diversification of a Himalayan orchid genus Pleione.

Pleione is an orchid endemically distributed in high mountain areas across the Hengduan Mountains (HDM), Himalayas, Southeast Asia and South of China. The unique flower shapes, rich colors and immense medicinal importance of Pleione are valuable ornamental and economic resources. However, the phylogenetic relationships and evolutionary history of the genus have not yet been comprehensively resolved. Here, the evolutionary history of Pleione was investigated using single-copy gene single nucleotide polymorphisms and chloroplast genome datasets. The data revealed that Pleione could be divided into five clades. Discordance in topology between the two phylogenetic trees and network and D-statistic analyses indicated the occurrence of reticulate evolution in the genus. The evolution could be attributed to introgression and incomplete lineage sorting. Ancestral area reconstruction suggested that Pleione was originated from the HDM. Uplifting of the HDM drove rapid diversification by creating conditions favoring rapid speciation. This coincided with two periods of consolidation of the Asian monsoon climate, which caused the first rapid diversification of Pleione from 8.87 to 7.83 Mya, and a second rapid diversification started at around 4.05 Mya to Pleistocene. The interaction between Pleione and climate changes, especially the monsoons, led to the current distribution pattern and shaped the dormancy characteristic of the different clades. In addition to revealing the evolutionary relationship of Pleione with orogeny and climate changes, the findings of this study provide insights into the speciation and diversification mechanisms of plants in the East Asian flora.

The Apostasia genome and the evolution of orchids.

Constituting approximately 10% of flowering plant species, orchids (Orchidaceae) display unique flower morphologies, possess an extraordinary diversity in lifestyle, and have successfully colonized almost every habitat on Earth. Here we report the draft genome sequence of Apostasia shenzhenica, a representative of one of two genera that form a sister lineage to the rest of the Orchidaceae, providing a reference for inferring the genome content and structure of the most recent common ancestor of all extant orchids and improving our understanding of their origins and evolution. In addition, we present transcriptome data for representatives of Vanilloideae, Cypripedioideae and Orchidoideae, and novel third-generation genome data for two species of Epidendroideae, covering all five orchid subfamilies. A. shenzhenica shows clear evidence of a whole-genome duplication, which is shared by all orchids and occurred shortly before their divergence. Comparisons between A. shenzhenica and other orchids and angiosperms also permitted the reconstruction of an ancestral orchid gene toolkit. We identify new gene families, gene family expansions and contractions, and changes within MADS-box gene classes, which control a diverse suite of developmental processes, during orchid evolution. This study sheds new light on the genetic mechanisms underpinning key orchid innovations, including the development of the labellum and gynostemium, pollinia, and seeds without endosperm, as well as the evolution of epiphytism; reveals relationships between the Orchidaceae subfamilies; and helps clarify the evolutionary history of orchids within the angiosperms.

Resilience of infertile families undergoing in vitro fertilization: An application of the double ABC-X model.

BACKGROUND: Family resilience plays a crucial role in protecting the mental health and family stability of infertile patients. However, information associated with infertile families resilience is scarce. The double ABC-X model provides a roadmap for this, helps organize knowledge, and lays the foundation for knowledge development. AIMS: To describe the current situation of family resilience of infertile women, and to test the predictive theoretical model of family resilience based on infertility stigma, individual resilience, coping style, and posttraumatic growth. DESIGN: A cross-sectional study. METHODS: A convenience sample of 372 infertile women undergoing in vitro fertilization were recruited between April and August 2020. The Chinese-Family Resilience Assessment Scale, Infertility Stigma Scale, Simplified Coping Style Questionnaire, Chinese version of Connor-Davidson Resilience Scale, and Chinese version of Post Traumatic Growth Inventory were used to measure family resilience, infertility stigma, individual resilience, coping style, and posttraumatic growth. Structural equation models were used to analyze the relationship among these variables. RESULTS: The results showed that family resilience was related to infertility stigma, positive coping, and individual resilience. Moreover, the path analysis indicated that positive coping and individual resilience mediated the effects of infertility stigma on family resilience. CONCLUSIONS: A high level of stigma among infertile women should be identified. Interventions for targeting positive coping and individual resilience might ultimately increase their family resilience.

"Spine Surgery" of Perylene Diimides with Covalent B-N Bonds toward Electron-Deficient BN-Embedded Polycyclic Aromatic Hydrocarbons.

BN-embedded polycyclic aromatic hydrocarbons (PAHs) with unique optoelectronic properties are underdeveloped relative to their carbonaceous counterparts due to the lack of suitable and facile synthetic methods. Moreover, the dearth of electron-deficient BN-embedded PAHs further hinders their application in organic electronics. Here we present the first facile synthesis of novel perylene diimide derivatives (B2N2-PDIs) featuring n-type B-N covalent bonds. The structures of these compounds are fully confirmed through the detailed characterizations with NMR, MS, and X-ray crystallography. Further investigation shows that the introduction of BN units significantly modifies the photophysical and electronic properties of these B2N2-PDIs and is further understood with the aid of theoretical calculations. Compared with the parent perylene diimides (PDIs), B2N2-PDIs exhibit deeper highest occupied molecular orbital energy levels, new absorption peaks in the high-energy region, hypsochromic shift of absorption and emission maxima, and decrement of photoluminescent quantum yields. Single-crystal field-effect transistors based on B2N2-PDIs showcase an electron mobility up to 0.35 cm2 V-1 s-1, demonstrating their potential application in optoelectronic materials.

Achieving Efficient n-Doping of Conjugated Polymers by Molecular Dopants.

ConspectusMolecular doping is one of the most central propositions in the field of organic electronics. Unlike classical inorganic semiconductors doped by atomic substitution, organic conjugated materials react with molecular dopants, and then intermolecular charge transfer is involved within. Therefore, the complex noncovalent interactions between two components often cause the molecular dopant to destroy the orderly stacking of the host organic materials and reduce the original properties of the material, such as carrier mobility, which here we call the "doping dilemma." Recently, many studies focus on improving p-doping efficiency and electrical conductivity of doped conjugated polymers; however, the development of n-type molecular doping currently lags far behind that of its p-counterpart. It is well-known that both efficient p- and n-type molecular doping are indispensable in various organic electronic devices, including light-emitting diodes, photovoltaics, field-effect transistors, and thermoelectrics. It is thus an urgent requirement to achieve efficient n-doping in conjugated polymers.In this Account, we give a brief overview of our efforts to improve the n-doping efficiency in conjugated polymers with several strategies from the aspects of the polymer/dopant molecular design and the exploration of the n-type molecular doping mechanism and charge transport mechanism in n-doped organic materials. For the conjugated polymer engineering, we first demonstrate that increasing the electron affinity of the host polymer through halogen substitution can boost the n-doping efficiency. Still, the rigid coplanar backbones of conjugated polymers play a crucial role in the polaron delocalization and final electrical performance. In addition, we emphasize the importance of morphology control in the doped polymers to address the "doping dilemma." For n-dopants designing, we summarize some basic guidelines from molecular sizes and shapes, the interaction between dopants (or dopant cations) and polymers, and the effects of dopants on morphology to design high-efficacy n-type molecular dopants. We propose that the polymers and the dopants need to be treated as a whole system; while enhancing the ionization efficiency, more attention should be paid to the carrierization (free-carrier generation) efficiency of these binary systems. In the end, we adopt the n-type polymer thermoelectric material as an example to discuss the grand challenges encountered in practical applications of n-doped conjugated polymers. The air stability and micrometer-thick thermo-leg processing of n-doped polymers are highlighted for thermoelectric applications. It is our hope that this Account showcases a blueprint for rational approaches and a deep understanding toward the design and development of efficient n-doping in conjugated polymers, bringing n-doped organic materials into the next era.

Controlling Solution-State Aggregation and Solid-State Microstructures of Conjugated Polymers by Tuning Backbone Conformation.

Molecular ordering of conjugated polymers both in solution-state aggregates and in solid-state microstructures is a determining factor of the charge transport properties in optoelectronic devices. However, the effect of backbone conformation in conjugated polymers on assembly structures is still unclear. Herein, to understand such backbone conformation effect, three novel chlorinated benzodifurandionge-based oligo(p-phenylene vinylene) (BDOPV) polymers are systematically developed. These BDOPV-based polymers exhibit significantly twisted backbone conformation (near 90° interunit torsion angle) between conjugated units, which can prevent polymer chains from forming ordered assembly structures by increasing conformational energy penalty in closely packed chains. A higher rotational barrier of the torsion angle would further prevent polymer chains from assembling, finally resulting in nonaggregated chains in solution and highly disordered solid-state packing structures. This work will deepen the understanding of the relationship between polymer backbone conformation and assembly structures, contributing to the exploration of the structure-property relationship of polymers.

Regulation of High Miscibility for Efficient Charge-Transport in n-Doped Conjugated Polymers.

Strong interchain interactions of conjugated polymers usually result in poor miscibility with molecular dopants, limiting the doping efficiency because of uncontrolled phase separation. We have developed a strategy to achieve efficient charge-transport and high doping miscibility in n-doped conjugated polymers. We solve the miscibility issue through disorder side-chains containing dopants better. Systemic structural characterization reveals a farther side-chain branching point will lead to higher disorders, which provides appropriate sites to accommodate extrinsic molecular dopants without harming original chain packings and charge-transport channels. Therefore, better sustainability of solid-state microstructure is obtained, yielding a stable conductivity even when overloading massive dopants. This work highlights the importance of realizing high host-dopant miscibility in molecular doping of conjugated polymers.

BN-Anthracene for High-Mobility Organic Optoelectronic Materials through Periphery Engineering.

Despite the remarkable synthetic accomplishments in creating diverse polycyclic aromatic hydrocarbons with B-N bonds (BN-PAHs), their optoelectronic applications have been less exploited. Herein, we report the achievement of high-mobility organic semiconductors based on existing BN-PAHs through a "periphery engineering" strategy. Tetraphenyl- and diphenyl-substituted BN-anthracenes (TPBNA and DPBNA, respectively) are designed and synthesized. DPBNA exhibits the highest hole mobility of 1.3 cm2  V-1 s-1 in organic field-effect transistors, significantly outperforming TPBNA and all the reported BN-PAHs. Remarkably, this is the first BN-PAH with mobility over 1 cm2  V-1 s-1 , which is a benchmark value for practical applications as compared with amorphous silicon. Furthermore, high-performance phototransistors based on DPBNA are also demonstrated, implying the high potential of BN-PAHs for optoelectronic applications when the "periphery engineering" strategy is implemented.

Multi-level aggregation of conjugated small molecules and polymers: from morphology control to physical insights.

Aggregation of molecules is a multi-molecular phenomenon occurring when two or more molecules behave differently from discrete molecules due to their intermolecular interactions. Moving beyond single molecules, aggregation usually demonstrates evolutive or wholly emerging new functionalities relative to the molecular components. Conjugated small molecules and polymers interact with each other, resulting in complex solution-state aggregates and solid-state microstructures. Optoelectronic properties of conjugated small molecules and polymers are sensitively determined by their aggregation states across a broad range of spatial scales. This review focused on the aggregation ranging from molecular structure, intermolecular interactions, solution-state assemblies, and solid-state microstructures of conjugated small molecules and polymers. We addressed the importance of such aggregation in filling the gaps from the molecular level to device functions and highlighted the multi-scale structures and properties at different scales. From the view of multi-level aggregation behaviors, we divided the whole process from the molecule to devices into several parts: molecular design, solvation, solution-state aggregation, crystal engineering, and solid-state microstructures. We summarized the progress and challenges of relationships between optoelectronic properties and multi-level aggregation. We believe aggregation science will become an interdisciplinary research field and serves as a general platform to develop future materials with the desired functions.

Efficient n-Doping of Polymeric Semiconductors through Controlling the Dynamics of Solution-State Polymer Aggregates.

Doping of polymeric semiconductors limits the miscibility between polymers and dopants. Although significant efforts have been devoted to enhancing miscibility through chemical modification, the electrical conductivities of n-doped polymeric semiconductors are usually below 10 S cm-1 . We report a different approach to overcome the miscibility issue by modulating the solution-state aggregates of conjugated polymers. We found that the solution-state aggregates of conjugated polymers not only changed with solvent and temperature but also changed with solution aging time. Modulating the solution-state polymer aggregates can directly influence their solid-state microstructures and miscibility with dopants. As a result, both high doping efficiency and high charge-carrier mobility were simultaneously obtained. The n-doped electrical conductivity of P(PzDPP-CT2) can be tuned up to 32.1 S cm-1 . This method can also be used to improve the doping efficiency of other polymer systems (e.g. N2200) with different aggregation tendencies and behaviors.

A Stable Triplet-Ground-State Conjugated Diradical Based on a Diindenopyrazine Skeleton.

High-spin conjugated radicals have great potential in magnetic materials and organic spintronics. However, to obtain high-spin conjugated radicals is still quite challenging due to their poor stability. We report the successful synthesis and isolation of a stable triplet conjugated diradical, 10,12-diaryldiindeno[1,2-b:2',1'-e]pyrazine (m-DIP). With the m-xylylene analogue skeleton containing electron-deficient sp2 -nitrogen atoms, m-DIP displays significant aromatic character within its pyrazine ring and its spin density mainly delocalizes on the meta-pyrazine unit, making it a triplet ground state conjugated diradical. Our work provides an effective "spin density tuning" strategy for stable high-spin conjugated radicals.

Thermally Activated n-Doping of Organic Semiconductors Achieved by N-Heterocyclic Carbene Based Dopant.

Molecular doping plays an important role in the modification of carrier density of organic semiconductors thus enhancing their optoelectronic performance. However, efficient n-doping remains challenging, especially owing to the lack of strongly reducing and air-stable n-dopants. Herein, an N-heterocyclic carbene (NHC) precursor, DMImC, is developed as a thermally activated n-dopant with the excellent stability in air. Its thermolysis in situ regenerates free NHC and subsequently dopes typical organic semiconductors. In sequentially doped FBDPPV films, DMImC does not disturb the π-π packing of the polymer and achieves good miscibility with the polymer. As a result, a high electrical conductivity of up to 8.4 S cm-1 is obtained. Additionally, the thermally activated doping and the excellent air stability permit DMImC to be noninteractively co-processed with polymers in air. Our results reveal that DMImC can be served as an efficient n-dopant suitable for various organic semiconductors.