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Solution-state self-assemblies of block copolymers to form nanostructures are tremendously attractive for their tailorable morphologies and functionalities. While incorporating moieties with strong ordering effects may introduce highly orientational control over the molecular packing and dictate assembly behaviors, subtle and delicate driving forces can yield slower kinetics to reveal manifold metastable morphologies. Herein, we report the unusually convoluted self-assembly behaviors of a liquid crystalline block copolymer bearing triphenylene discotic mesogens. They undergo unusual multiple morphological transitions spontaneously, driven by their intrinsic subtle liquid crystalline ordering effect. Meanwhile, liquid crystalline orderedness can also be built very quickly by doping the mesogens with small-molecule dopants, and the morphological transitions are dramatically accelerated and various exotic micelles are produced. Surprisingly, with high doping levels, the self-assembly mechanism of this block copolymer is completely changed from intramolecular chain shuffling and rearrangement to nucleation-growth mode, based on which self-seeding experiments can be conducted to produce highly uniform fibrils.
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The fabrication of uniform cylindrical nanoobjects from soft materials has attracted tremendous research attention from both fundamental research and practical application points of view but has also posed outstanding challenges in terms of their preparation. Herein, we report a one-step method to assemble cylindrical micelles (CMs) with highly controllable lengths from a single liquid crystalline block copolymer by an in situ nucleation-growth strategy. By adjusting the assembly conditions, the lengths of the CMs are controlled from hundreds of nanometers to micrometers. Several influencing factors are systematically investigated to comprehensively understand the process. Particularly, the solvent quality is found determinative in either enhancing or suppressing the nucleation process to produce shorter and longer CMs, respectively. Taking advantage of this strategy, the lengths of CMs can be nicely controlled over a wide concentration range of four orders of magnitude. Lastly, CMs are produced on decent scales and applied as additives to dramatically toughen glassy plastic matrix, revealing an unprecedented length-dependent toughening effect.
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The self-assembly morphologies of subunits are largely governed by thermodynamics, which plays a less important role in dimensional control. Particularly for one-dimensional assemblies from block copolymers (BCPs), the negligible energy difference between short and long ones imposes great challenges in length control. Herein, we report that by incorporating additional polymers to induce in situ nucleation and trigger the subsequent growth, controllable supramolecular polymerization driven by mesogenic ordering effect could be realized from liquid crystalline BCPs. The length of the resultant fibrillar supramolecular polymers (SP) is controlled by tuning the ratio between nucleating and growing components. Depending on the choice of BCPs, the SPs can be homopolymer-like, heterogeneous triblock, and even pentablock copolymer-like. More interestingly, with insoluble BCP as a nucleating component, amphiphilic SPs are fabricated, which can undergo spontaneous hierarchical assembly.
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Porous organic polymers (POPs) have aroused great and wide attention from the materials community, while the identification of their precise structures is still very challenging. The well-defined structures are of great importance in understanding the relationship between the structure and function of the polymer materials, though they are sometimes ignored and do not receive enough attention. In this letter, an efficient 15N labeling technique and 15N solid-state NMR (15N-SSNMR) were combined to obtain strong evidence for the presence of the azo bond and keto-hydrazone structure in the solid state. Thus, the structure of tris(ß-hydroxyl-azo)-benzene in previously proposed hydroxylazobenzene polymers was revised to tris(ß-keto-hydrazo)-cyclohexane in TKH-POPs for the first time. In contrast, similar tautomerization did not occur in the azo coupling polymerization of 1,3,5-triaminobenzene and diazonium salts, i.e., tris(ß-amino-azo)-benzene remained in Azo-POPs. This work will open up a window to develop innovative porous organic polymers more efficiently with the aid of 15N-SSNMR.
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[This corrects the article DOI: 10.1021/acsomega.9b04026.].
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The efficient super-continuum (SC) generation on a surface via a high-order photo-electron interaction is a great challenge for integrated optics because the surficial nonlinear optical efficiency is usually limited by finite light-matter interaction length and electric field intensity. Nowadays, epsilon-near-zero (ENZ) materials, showing infinite enhanced electronic field in theory, provide a kind of new platform to obtain a giant nonlinear response on the surface. Here, under the irradiation of a multiwavelength laser, an exotic and efficient SC generation from 406 to 1100 nm on the ENZ aluminum-doped zinc oxide surface was experimentally demonstrated by diversified nonlinear processes, including second harmonic generation, third harmonic generation, four wavelength mixing, and cascading stimulated Raman scattering. Particularly, an unprecedented nonlinear conversion efficiency of 3.94% W-1, 16 orders of magnitude higher than the common surface case (about 10-16% W-1), was presented.
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Two-dimensional (2D) materials have exotic intrinsic electronic band structures and are considered as revolutionary foundations for novel nanodevices. Band engineering of 2D materials may pave a new avenue to overcome numerous challenges in modern technologies, such as room temperature (RT) photodetection of light with photon energy below their band gaps. Here, we reported the pioneering RT MoS2-based photodetection in the terahertz (THz) region via introducing Mo4+ and S2- vacancies for rational band gap engineering. Both the generation and transport of extra carriers, driven by THz electromagnetic radiations, were regulated by the vacancy concentration as well as the resistivity of MoS2 samples. Utilizing the balance between the carrier concentration fluctuation and carrier-scattering probability, a high RT photoresponsivity of 10 mA/W at 2.52 THz was realized in an Mo-vacancy-rich MoS2.19 sample. This work overcomes the challenge in the excessive dark current of RT THz detection and offers a convenient way for further optoelectronic and photonic devices based on band gap-engineered 2D materials.
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Gapless surface states (SSs) are features of topological semimetals and are extensively observed. Nowadays, the emerging question is whether the SSs possess exotic and applicable properties. Here, associated with the symmetrical selection rule for nonlinear optical materials, the surface nonlinear optics on a centrosymmetric Dirac nodal-line semimetal ZrSiS crystal is studied and it is found that the SSs bring record nonlinear susceptibilities. The unprecedented conversion efficiencies for second and third harmonic generations are 0.11 and 0.43, respectively, more than ten orders of magnitude larger than the typical surface second harmonic generation. This work discovers a new route toward studying the SSs for applications in nonlinear photonics.
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Photodetection using semiconductors is critical for capture, identification, and processing of optical information. Nowadays, broadband photodetection is limited by the underdeveloped mid-IR photodetection at room temperature (RT), primarily as a result of the large dark currents unavoidably generated by the Fermi-Dirac distribution in narrow-bandgap semiconductors, which constrains the development of some modern technologies and systems. Here, an electronic-structure strategy is proposed for designing ultrabroadband covering mid- and even far-IR photodetection materials operating at RT and a layered MoS2 is manifested with an engineered bandgap of 0.13 eV and modulated electronic state density. The sample is designed by introducing defect energy levels into layered MoS2 and its RT photodetection is demonstrated for wavelengths from 445 nm to 9.5 µm with an electronic state density-dependent peak photoresponsivity of 21.8 mA W-1 in the mid-IR region, the highest value among all known photodetectors. This material should be a promising candidate for modern optoelectronic devices and offers inspiration for the design of other optoelectronic materials.
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Mid- and even long-infrared photodetection is highly desired for various modern optoelectronic devices, and photodetectors that operate at room temperature (RT) remain challenging and are being extensively sought. Recently, the Weyl semimetal has attracted much interest, and its Lorentz invariance can be broken to have tilted chiral Weyl cones around the Fermi level, which indicates that the photocurrent can be generated by the incident photons at arbitrarily long wavelengths. Furthermore, the atypical linear dispersion bands in Weyl cones result in high carrier mobility and quadratic energy dependence of the density of states, which can enhance the efficiency of the photocurrent and suppress thermal carriers, in addition to its favorable large absorption coefficient. In this study, a Weyl semimetal TaAs photodetecting prototype is reported, which operates at RT with an outstanding response that ranges from the visible to the long-infrared range. This study indicates that the Weyl semimetal TaAs should boost the development of modern optoelectronics and photonics.