基于扭转悬链线结构的高效手性吸波器

近年来,超构表面(metasurface)作为一种人工二维结构由于其超薄的几何结构以及灵活的电磁调控能力受到了学界的广泛关注,如何进一步提高超构表面器件的性能成为了该领域的研究热点。悬链线电磁学(catenary electromagnetics)作为一类新兴的超构表面设计原理为设计高效率超构表面器件提供了新的思路和方法。本文提出了一种基于扭转悬链线结构的超构表面,其能够实现对不同旋向入射的圆偏振电磁波的高效选择性吸收。仿真结果表明所设计的器件在工作波长处对左旋圆偏振电磁波吸收率接近于1,而右旋圆偏振入射时吸收率小于22%,其对应的二向色性大于78%。同时,文章分析了产生高效率手性吸收的物理机制并且提出了一种基于该类结构的信息加密方法。该工作在手性成像与手性探测等领域具有一定的应用前景。     

淀粉苯基氨基甲酸酯类手性固定相的制备及用于HPLC手性体分离性能的研究

合成了含有3,5-二甲基和3,5-二氯取代基团的混合型淀粉(苯基氨基甲酸酯)衍生物(CSP-2),并作为手性体分离材料涂敷在氨丙基化多孔硅胶表面,制得新型高效液相色谱(HPLC)用手性固定相;通过1H核磁共振(1H NMR)和红外光谱(IR)表征衍生物结构;以正己烷-异丙醇(9∶1,v/v)为流动相,对多种手性对映体进行了拆分;结果表明,CSP-2综合了单一取代基团淀粉(苯基氨基甲酸酯)衍生物的手性拆分性能,具有优越的手性分离能力,同时固定相的稳定性大大增强。     

超材料宽带圆偏振器的研究进展

超材料因其独特的性质可以作为选择圆偏振光的器件,即圆偏振器。随着偏振分辨成像系统的重要性日益增强,圆偏振器已被用于增强对比度、圆偏振显微镜以及生物分子的检测,如氨基酸、DNA和具有固有手性结构的葡萄糖,尤其是在可见光波长下工作的圆偏振器已经引起了人们广泛的关注,已被用作控制复杂显示系统中光的偏振态的关键光学元件。然而通过传统方法获取圆偏振器有很大的局限性,如体积庞大、工作带宽窄等,极大地限制了它们的发展。近几年来,超材料中螺旋结构和堆叠结构的提出,促进了宽带圆偏振器的发展。本文简述了超材料中螺旋结构和堆叠结构形成宽带圆偏振器的偏振原理,详述了两种结构作为宽带圆偏振器的数值模拟和实验研究进展。     

新型有机电致荧光材料研究进展

有机发光二极管因独特的优势被看作新一代的照明及平面显示技术,引起了研究人员的广泛关注。传统的荧光材料仅能利用单重态激子发光,因而效率并不理想。近年来,能够利用三重态激子能量发光的新型荧光材料的研究实现了新的突破。按照三重态激子到单重态激子的转化机理,荧光材料可以分为三重态-三重态湮灭、热致延迟荧光和局域电荷转移杂化激发态三种特殊类型。本文围绕着这几种类型的荧光材料展开了探讨,介绍了有机电致荧光器件的概况以及不同类型荧光材料的发光机理,并从分子设计的角度说明了高性能发光器件的设计思路。     

螺旋结构手性材料的结构参数过旋波性的影响

手性材料具有旋波性。本工作首次研究了螺旋结构手性掺杂体的几何结构参数对旋波性的影响。螺旋结构手性体的结构参数由螺旋体的螺径、线径和环数来表示。利用普通的微波圆波导测量系统,在８．５￣１１．５ＧＨＺ频段内测量了电磁波通过不同螺肇结构手性材料后的偏转角。结果表明：螺旋体的几何结构参数对偏转角有较大影响,随着螺肇体结构参数的变化,有Ｃｏｔｔｏｎ效应出现。这些实验结果为手性材料的设计提供了实验依据。     

TMEP作为缓冲层增加有机发光器件的效率的研究

在有机发光器件中的发光层和阴极之间插入了稳定性好、有良好电子传输能力的苝酸四甲酯(TMEP)新型缓冲层,改善了有机电致发光器件的亮度和发光效率.在电流密度为200mA/cm2时,有缓冲层的器件B效率为0.82cd/A,没有缓冲层的器件A效率为0.14cd/A.     

HPLC用苯基氨基甲酸酯类手性固定相的制备及分离性能

合成了同时含有3,5-二甲基和3,5-二氯取代基团的纤维素(苯基氨基甲酸酯)衍生物(CSP-1),作为手性体分离材料涂敷在氨丙基化硅胶表面,制得新型高效液相色谱(HPLC)用手性固定相;利用1H核磁共振(1H-NMR)和红外光谱(IR)表征了衍生物结构;以正己烷-异丙醇(体积比9∶1)为流动相,对多种手性对映体进行了拆分。结果表明,CSP-1具有很好的手性体分离能力,综合了单一取代基团纤维素(苯基氨基甲酸酯)衍生物的手性拆分性能。     

高效单发光层绿色有机发光二极管的制备与性能研究

为了提升绿色有机发光二极管的效率,设计了阶梯能级结构的器件,使得载流子在器件中更有效传输,进而有效减缓了器件效率的衰减。选择热致延迟荧光材料(4s,6s)-2,4,5,6-四(9-氢咔唑-9-基)间苯二腈(4CzIPN)作为发光材料,并将其掺杂到能级匹配的主体材料1,3-二(咔唑-9-基)苯(mCP)中构成发光层,制备了一系列单发光层的绿色有机发光二极管。在发光材料的掺杂浓度为2%(wt,质量分数),发光层的厚度为20nm条件下,制得的器件性能最佳,其启亮电压为3.4V,其最大亮度、电流效率、功率效率和外量子效率分别为20706cd/m~2、50.49cd/A、41.96lm/W和16.7%。在亮度为1000cd/m~2条件下,其电流效率和外量子效率仍然高达34.06cd/A和11.6%。器件显示主峰位于504nm的4CzIPN特征发射,随着掺杂浓度的提升,越来越多的电子和空穴被4CzIPN分子所俘获,导致主体材料mCP的特征发射峰逐渐减弱。     

具有非对称性结构的咔唑修饰硼氮窄发射热活化延迟荧光材料的合成和性质研究

构建高性能的绿光、红光窄发射多重共振热活化延迟荧光材料是当前发光材料研究的热点和难点。通过在硼氮骨架的间位上引入咔唑给体基团，构建了兼具多重共振荧光特征和分子内电荷转移态的荧光材料mBNCz,咔唑基团的引入提高了分子的HOMO能级，分子的荧光发射峰发生显著红移。同时，化合物具备窄的荧光发射光谱、良好的热稳定性、高的荧光量子产率和显著的热活化延迟荧光特征，在发光显示材料中具有较高的应用潜力。     

有机半导体照明(有机照明)研究进展

采用有机发光二极管(OLEDs)的有机半导体照明(有机照明)是绿色环保、健康安全的新型面光源,有望在固态照明领域得到广泛的应用。有机照明的发展是随着有机发光材料的不断进步而进步的。有机发光材料从最初的荧光材料发展到磷光材料以及最近提出的热活化延迟荧光材料,其性能在不断地提升。基于这些材料的白光OLEDs的性能也在不断提升。最早的白光器件基于荧光小分子材料,但是由于只能利用单线态激子发光,效率很低。随后磷光材料的引入使得白光器件的效率大幅度提升,但是由于蓝色磷光材料本身的稳定性问题,全磷光白光器件的寿命较短。为了结合荧光和磷光的优点,人们提出了荧光/磷光杂化的白光器件,这是目前最有前景的一类白光器件结构。目前针对有机照明的研究,已从早期只关注效率突破阶段,进入到综合提高效率和寿命阶段。从荧光白光、磷光白光以及荧光/磷光混合白光3个方面对有机照明的研究状况、发展趋势进行了介绍。     

Control of Circularly Polarized Electroluminescence in Induced Twist Structure of Conjugate Polymer

An extremely high degree of circularly polarized photoluminescence (CPPL) and electroluminescence (CPEL) (dissymmetry factor values: |g_PL| = 0.72 and |g_EL| = 1.13) are generated from twisted stacking of achiral conjugated polymer induced by nonemitting chiral dopant of high helical twisting power for the first time. Using a theoretical analysis incorporating the Stokes parameter, the twisting angle and birefringence of the aligned conjugated polymer, and the degree of linear polarization in the emitted light are found to make a roughly equal contribution to the degree of CPEL as to the degree of CPPL. Moreover, it is also found that the location of the recombination zone within the emitting layer is a crucial parameter for determining the difference in the dissymmetry factor between CPEL and CPPL. This result is applied to an organic light‐emitting display to improve the luminous efficiency by 60%.     

Photon Upconverted Circularly Polarized Luminescence via Triplet–Triplet Annihilation

Circularly polarized luminescent materials are of increasing attention due to their potential applications in advanced optical technologies, such as chiroptical devices and optical sensing. Recently, in all reported circularly polarized luminescent materials, high‐energy excitation results in low‐energy or downconverted circularly polarized luminescence (CPL) emission. Although photon upconversion—i.e., the conversion of low‐energy light into higher‐energy emission, with a wide variety of applications—has been widely reported, the integration of photon upconversion and CPL in one chiral system to achieve higher‐energy CPL emission has never been reported. Herein, a brief review is provided of recent achievements in photon‐upconverted CPL via the triplet–triplet annihilation mechanism, focusing on the amplified dissymmetry factor g_lum through energy transfer process and dual upconverted and downconverted CPL emission through chirality and energy transfer process.     

Chiral Octahydro‐Binaphthol Compound‐Based Thermally Activated Delayed Fluorescence Materials for Circularly Polarized Electroluminescence with Superior EQE of 32.6% and Extremely Low Efficiency Roll‐Off

Circularly polarized organic light‐emitting diodes (CP‐OLEDs) are particularly favorable for the direct generation of CP light, and they demonstrate a promising application in 3D display. However, up to now, such CP devices have suffered from low brightness, insufficient efficiency, and serious efficiency roll‐off. In this study, a pair of octahydro‐binaphthol ( OBN )‐based chiral emitting enantiomers, (R/S)‐OBN‐Cz , are developed by ingeniously merging a chiral source and a luminophore skeleton. These chirality–acceptor–donor (C–A–D)‐type and rod‐like compounds concurrently generate thermally activated delayed fluorescence with a small ΔE_ST of 0.037 eV, as well as a high photoluminescence quantum yield of 92% and intense circularly polarized photoluminescence with dissymmetry factors (|g_PL|) of ≈2.0 × 10^?3 in thin films. The CP‐OLEDs based on (R/S)‐OBN‐Cz enantiomers not only display obvious circularly polarized electroluminescence signals with a |g_EL| of ≈2.0 × 10^?3, but also exhibit superior efficiencies with maximum external quantum efficiency (EQE_max) up to 32.6% and extremely low efficiency roll‐off with an EQE of 30.6% at 5000 cd m^?2, which are the best performances among the reported CP devices to date.     

Enantiomeric MOF Crystals Using Helical Channels as Palettes with Bright White Circularly Polarized Luminescence

The host–guest chemistry of metal–organic frameworks (MOFs) has enabled the derivation of numerous new functionalities. However, intrinsically chiral MOFs (CMOFs) with helical channels have not been used to realize crystalline circularly polarized luminescence (CPL) materials. Herein, enantiomeric pairs of MOF crystals are reported, where achiral fluorophores adhere to the inner surface of helical channels via biology-like H-bonds and hence inherit the helicity of the host MOFs, eventually amplifying the luminescence dissymmetry factor (g_lum) of the host l /d -CMOF (±1.50 × 10⁻³) to a maximum of ±0.0115 for the composite l /d -CMOF⊃fluorophores. l /d -CMOF⊃fluorophores in pairs generate bright color-tunable CPL and almost ideal white CPL (0.33, 0.32) with a record-high photoluminescence quantum yield of ≈30%, which are further assembled into a white circularly polarized light-emitting diode. The present strategy opens a new avenue for propagating the chirality of MOFs to realize universal chiroptical materials.     

聚苯醚/钙镧钛微波复合基板

微波复合基板兼具树脂基体的高韧性和陶瓷填料优异的介电和热学性能, 是航空航天、电子对抗、5G通讯等领域的关键材料。本工作采用螺杆造粒与注塑成型相结合的新技术制备了聚苯醚(简写为PPO)为基体、钙镧钛(Ca_0.7La_0.2TiO₃, 简写为CLT)陶瓷为填料的新型微波复合基板, 并对基板的显微结构、微波介电性能、热学性能和力学性能进行表征。结果表明, 采用这种新技术制备的微波复合基板组成均匀且结构致密。随着CLT陶瓷的体积分数从0增大至50%, 基板的介电常数从2.65提高到12.81, 介电损耗从3.5×10 ^-3降低至2.0×10 ^-3 (@10GHz); 同时热膨胀系数从7.64×10 ^-5 ℃ ^-1显著降低至1.49×10 ^-5 ℃ ^-1, 热导率从0.19 W·m ^-1·K ^-1提高至0.55 W·m ^-1·K ^-1; 此外抗弯强度从97.9 MPa提高至128.7 MPa。填充体积分数40%CLT陶瓷的复合基板综合性能优异: ε_r=10.27, tanδ=2.0×10 ^-3(@10GHz), α=2.91×10 ^-5 ℃ ^-1, λ=0.47 W·m ^-1·K ^-1, σ_s=128.7 MPa, 在航空航天、电子对抗、5G通讯等领域具有良好的应用前景。     

Full‐Color Tunable Circularly Polarized Luminescent Nanoassemblies of Achiral AIEgens in Confined Chiral Nanotubes

Circularly polarized luminescent (CPL) materials are currently attracting great interest. While a chiral building is usually necessary in order to obtain CPL materials, here, this study proposes a general approach for fabricating 1D circularly polarized luminescent nanoassemblies from achiral aromatic molecules or aggregation‐induced emissive compounds (AIEgens). It is found that a C₃ symmetric chiral gelator can individually form hexagonal nanotube structures and encapsulate the guest molecules. When achiral AIEgens are encapsulated into the confined nanotubes via organogelation, the AIEgens will emit circularly polarized luminescence. Further, the direction of the CPL could be controlled by the supramolecular chirality of the nanotube. Remarkably, the approach is universal and various kinds of the AIEgens can be doped to show such property, providing a full‐color‐tunable circularly polarized luminescence.     

Tailoring Chiroptical Activity of Iron Disulfide Quantum Dot Hydrogels with Circularly Polarized Light

Chiral inorganic nanomaterials have recently attracted significant attention because of their many important applications, such as in asymmetric catalysis and chiral sensing. Here, chiral iron disulfide quantum dots (FeS₂ QDs) are synthesized via chirality transfer using l/d ‐cysteine (Cys) as chiral ligands. The chiral FeS₂ QDs are coassembled with two gelators to produce a cogel (l ‐ or d ‐[Gel+FeS₂]) with a g‐factor value of ±0.06. Interestingly, the cogels display intense circularly polarized luminescence. More significantly, the degree of twisting (twist pitch) and the diameter of the cogels can be markedly regulated by illumination with circularly polarized light (CPL) in the ranges of 120–213 and 37–65 nm, respectively, which is caused by the CPL‐induced electron transfer. This research opens the way for the design of chiroptical devices with a wide range of functions and applications.     

应变速率对一种无铼单晶高温合金低周疲劳性能的影响

研究了一种无铼镍基单晶高温合金在1223 K、不同应变速率(5×10^-4s^-1、1×10^-3s^-1、5×10^-3s^-1、1×10^-2s^-1)条件下的低周疲劳行为。结果表明:在四种应变速率条件下,合金均表现出循环稳定。随着应变速率的增加,合金的疲劳寿命逐渐增加,且其半寿命稳定滞后回线环内面积逐渐减少,表明低应变速率合金更容易积累蠕变塑性变形。疲劳裂纹源均萌生于试样表面,随着应变速率的增加,疲劳过程中产生的塑性变形越来越少,疲劳裂纹扩展区的面积逐渐增大。低应变速率时,较大的塑性变形导致合金取向发生明显的偏转,诱发多滑移系开动进而形成位错网;反之,高应变速率时,合金没有产生明显的塑性变形,只有单一方向的位错塞积形成位错束。     

Fe/Al异质金属接头界面组织演变、生长动力学及力学性能

采用真空扩散连接方法研究Fe/Al异质金属接头界面组织演变规律、金属间化合物(intermetallic compound,IMC)生长动力学及力学性能。结果表明：焊接温度为550 ℃时,接头界面无IMC生成,当焊接温度超过575 ℃时,界面由Fe₂Al₅及少量FeAl₃ IMC构成,且随焊接温度升高IMC层迅速长大。在120 min保温时间条件下,接头剪切强度随焊接温度的升高先增加后降低,当焊接温度为575 ℃时,接头剪切强度达到最大值37 MPa。在550~625 ℃范围内,基于热力学分析得出Fe₂Al₅的吉布斯自由能ΔG_Fe-Al最低,而FeAl₃的ΔG_Fe-Al次之,在接头界面处IMC生成顺序为Fe₂Al₅→FeAl₃。Fe/Al接头界面IMC的生长随焊接温度呈抛物线规律,其生长激活能为282.6 kJ·mol^-1。在575,600,625 ℃条件下,界面IMC的生长速率分别为1.13×10^-14,3.59×10^-14,1.21×10^-13 m²·s^-1。     

纳米级Li4Ti5O12负极材料的制备及其输运特性

以酞酸丁酯和乙酸锂为前驱体,通过溶胶凝胶法成功制备了纳米钛酸锂Li_4Ti_5O₁₂(LTO)负极材料。采用X射线衍射分析、扫描电镜(SEM)和透射电镜(TEM)分别对材料的物相与形貌进行了表征分析,并研究了煅烧条件和包覆改性对LTO输运特性的影响。研究表明,煅烧温度为800℃,时间为10 h条件下制备的样品的输运特性最佳,离子电导率为8.8×10^-8 S/cm,电子电导率为8.53×10^-10 S/cm。均匀的碳包覆层可以有效地改善样品的输运特性,LTO/C复合活性材料的离子与电子电导率分别达到4.35×10^-7 S/cm和9.63×10^-8 S/cm。电化学性能测试表明,碳包覆后的活性材料在0.1 C倍率下首次放电容量可达172.4 mAh/g;在5 C高倍率下循环充放电50次后,容量保持率可达94.4%,表现出较好的电化学性能。