硅烯量子点的等离激元激发

基于含时密度泛函理论, 研究了硅烯量子点的等离激元激发. 沿量子点所在的平面方向, 体系中有两个主要的等离激元共振带. 一个等离激元共振带位于2.0 eV附近, 另一个等离激元共振带位于7.0 eV附近. 由于离域化的π电子参与了两个等离激元共振带的激发, 沿激发方向随着矩形硅烯量子点边长的增加, 体系的两个等离激元共振带都发生红移. 硅烯量子点的等离激元激发还依赖于边界的构型. 此外, 由于六角形硅烯量子点的对称性较高,沿量子点所在平面的不同方向激发时, 体系的等离激元共振模式相同.     

硅烯量子点二聚物的等离激元激发

基于含时密度泛函理论,研究了随着间距改变时硅烯量子点二聚物的等离激元激发特性。沿垂直于硅烯所在平面方向激发时,在一定间距范围内,硅烯量子点二聚物中形成了长程电荷转移激发模式。参与长程电荷转移激发的π电子主要在两个量子点之间运动。该等离激元模式随着间隙的减小发生蓝移。此外,在不同间距时,体系中还有两个等离激元共振带,分别位于7和15 eV附近。沿平行于硅烯所在平面方向激发时,由于两个量子点之间的耦合,在低能     

表面等离激元金属纳米粒子的多元化结构及应用

目前, 单一的金属纳米粒子结构已经难以满足多学科交叉发展的需求. 因此, 将多种金属纳米粒子(如不同尺寸、 形状、 组分等)集成在同一基底表面, 能够充分发挥不同金属纳米粒子的性质和优势, 极具研究价值和应用价值. 本文介绍了多元化表面等离激元纳米粒子结构的构筑方法, 以及其在信息编码、 光电器件、 能源催化等领域的应用. 最后, 提出了当前在多元化结构制备中存在的挑战, 并展望了利用多元化结构实现性能提升的前景.     

大面积多元化表面等离激元金纳米粒子结构的制备

具有显著表面等离激元共振效应的贵金属纳米粒子因其独特的光电学性质在许多领域表现出了潜在的应用价值。结合纳米压印技术与自组装技术发展了一种高效的多元化纳米粒子结构的制备方法,并制备了一种由不同尺寸金纳米粒子构成的周期性表面等离激元纳米粒子结构。实验结果证明此种方法在大批量制备和结构多元化的控制方面具有独特的优势。利用不同的表面等离激元纳米粒子结构对不同荧光分子增强效果的差异,设计了2种具有明显明暗差异的荧光条码,展示了多重的荧光增强响应。     

等离激元表面晶格共振研究进展

当金属纳米粒子排列成有序阵列结构时,沿阵列平面内传播的衍射波与单粒子局域等离激元共振耦合,将导致等离激元共振急剧窄化,光谱宽度降至2 nm以下.与共振宽度在80 nm以上的常规单粒子共振相比,这种具有高品质因子的衍射耦合等离激元共振称为等离激元表面晶格共振.近年来,关于表面晶格共振研究已成为纳米光子学领域的研究热点,在发光、激光、光伏、通讯、存储以及传感等领域显示出巨大的应用前景.本文主要综述等离激元表面晶格共振的基本原理和性质,包括共振宽度、共振品质、电场增强,探讨了表面晶格共振的测试方法、影响因素以及纳米光学应用.     

可调控且稳定的SrMoO4等离激元共振用于增强的可见光驱动的氮还原

光催化固氮是最具潜力的人工光合过程之一,也是有望取代工业Haber-Bosch方法实现氨的绿色合成的清洁能源技术之一.由于氮气分子还原为氨需要较高的还原电位,导致大部分常规的半导体材料的导带能级不能满足固氮反应的热力学要求.同时,固氮光催化剂普遍存在光响应波段窄、表面催化活性低、太阳光向氨的转化效率低等问题.缺陷工程是目前制备高效固氮光催化剂的最有效的途径之一.在催化剂中引入缺陷可以带来两个方面的好处:(1)促进氮气分子在缺陷位点上的化学吸附和活化,从而降低反应能垒;(2)拓宽催化剂的太阳光响应波段,提高对太阳光的利用效率.等离激元效应来自于自由载流子的集体振荡,广泛存在于金属纳米结构中.尽管金属等离激元纳米材料在光催化中也有广泛的应用,可以通过等离激元增强的光吸收和散射、热载流子传输以及等离激元共振能量传递等机理提高太阳能转化效率,但其能量转化效率仍有限,多用于弥补半导体材料的弱点.研究发现,一些半导体纳米材料在可见光和近红外光范围表现出优异的等离激元共振吸收.相比等离激元金属纳米材料,这些半导体的等离激元共振效应的调控手段更加丰富.等离激元半导体材料普遍具有较高的缺陷浓度、非常宽的光响应波段,因而是理想的固氮光催化剂.本文利用具有还原性的气氛处理溶剂热法制备的SrMoO4,通过引入高浓度的氧空位,实现了可调控的稳定的等离激元共振吸收.制备的SrMoO4在可见光和近红外光范围具有强的等离激元吸收,其共振吸收峰的中心位置可从520调到815 nm,显著拓宽了SrMoO4的光响应波段,而样品的本征吸收边仍然位于310 nm.研究发现,氢气还原没有改变Sr的氧化态,而是将Mo6+还原成Mo5+.紫外光电子能谱分析结果表明,高温氢气处理没有改变SrMoO4样品的导带和价带能级.电子顺磁共振研究结果表明,氢气处理在SrMoO4中形成了大量的氧空位.Mott-Schottky测试结果发现,氢气处理后的样品的载流子浓度高达～2.0×1020 cm-3.具有等离激元效应的SrMoO4表现出优异的可见光固氮性能,相比不具有等离激元效应的SrMoO4,在入射光波长大于420 nm的可见光照射下,在氢气气氛中处理10 min,3,6和8h的SrMoO4样品的氨的产率分别为41.2,36.3,24.5和20.8 μg gcat-1 h-1.其增强光催化活性主要来源于更宽的太阳光吸收波段、等离激元激发产生的热载流子和丰富的缺陷活性位点.一方面,SrMoO4具有较高的导带能级,本征激发形成的导带电子能在热力学上将氮气分子还原为氨;另一方面,等离激元激发产生的热载流子具有较高的能量,能够越过固液界面的肖特基能垒,将吸附在催化剂表面缺陷处的氮气分子还原为氨.但是,尽管缺陷在光催化固氮中展现出多方面的优点,其在半导体中的浓度仍需进一步的优化.     

等离激元纳米贴片天线耦合MEH-PPV超薄膜的高亮快速发射（英文）

作为一类潜在的纳米光源,共轭聚合物薄膜的荧光寿命通常在1～10 ns的范围内,这阻碍了其在高速光子器件中的应用。本文实现了等离激元纳米贴片天线(NPA)耦合聚[2-甲氧基-5-(2-乙基己氧基)-1,4-苯基乙烯基](MEH-PPV)薄膜的高亮、快速发射,其中11 nm厚的聚(二烯丙基二甲基氯化铵)/聚苯乙烯磺酸钠(PDDA/PSS)_n多层自组装膜用作介质层来调节等离激元微腔的损耗特性。实验结果表明,MEH-PPV超薄膜的发射强度增强了1.9倍,而辐射速率增加了7.2倍。以上结果为开发基于MEH-PPV聚合物薄膜的高速光子源提供了理论依据。     

不同氮掺杂石墨烯氧还原反应活性的密度泛函理论研究

N掺杂石墨烯作为一种具有较高活性和稳定性的氧还原反应(ORR)催化剂,受到人们的广泛关注。然而不同的N掺杂类型对氧还原活性的影响一直存在争议。本文通过密度泛函理论分别对石墨型和吡啶型两种N掺杂石墨烯的ORR活性进行比较研究。能带结构分析表明,石墨氮掺杂石墨烯(GNG)的导电性随掺N量的增加而降低;吡啶氮掺杂石墨烯(PNG)的导电性则随掺N量的增加先提高后降低。当N掺杂浓度达到4.2%(原子分数)时,PNG具有最优导电性。且当N掺杂浓度大于1.4%时,PNG的导电率总是高于GNG。氧还原自由能阶梯曲线发现O₂的质子化是整个氧还原过程的潜在控制步骤。在同等氮掺杂浓度下,O₂的质子化自由能能变在GNG上低于在PNG上,意味着若在同等电子传输能力的情况下,GNG具有比PNG更优异的催化活性。进一步分析发现：当N掺杂浓度在低于2.8%时,GNG和PNG导电性差异小,其催化ORR活性由O₂质子化反应难易程度决定,GNG的催化活性优于PNG;当N掺杂浓度高于2.8%时,氮掺杂石墨烯的电子传输性能(导电性)成为决定催化剂ORR活性的主要因素,因此PNG表现出较GNG更高的活性。     

铜族金属与完整及氮掺杂石墨烯的相互作用

基于广义梯度密度泛函理论和周期平板模型,研究了铜族金属单原子和双原子簇与完整及氮掺杂石墨烯的结合情况.结果表明,氮掺杂后石墨烯的电子结构特性由半金属性变为金属性;铜族金属在完整及石墨型氮掺杂石墨烯上的吸附较弱,结合能约为0.5eV,而在吡啶型氮掺杂和吡咯型氮掺杂石墨烯上有较强的化学吸附,结合能一般大于1eV;吡咯型氮掺杂后的构型不稳定,金属原子及簇与包含该结构的石墨烯衬底作用时会使其向吡啶型氮掺杂转变,并最终得到基于吡啶型氮掺杂的稳定吸附构型.Mulliken电荷布居分析显示,吸附在吡啶型氮掺杂石墨烯上的金属单原子与金属双原子簇带电性质相反.态密度及轨道分析表明,Cu与吡啶型氮掺杂石墨烯空位处留有悬挂键的三个原子成键,而Au与其中两个C原子成键.     

等离激元激励表面增强拉曼光谱检测技术与仪器

本文总结了近年来基于传播型表面等离激元（Propagafingsurfaceplasmons,PSPs）参与的表面增强拉曼（Surface—enhancedRamanscattering,SERS）技术和仪器方面的研究进展．内容主要包括3部分：（1）基于PSPs激励拉曼散射的装置和技术,包括在消逝场下激发PSPs共振增强拉曼的原理与装置、与表面等离子体共振（Surfaceplasmonresonance,SPR）传感技术的联用及新型结构的长程等离激元激励拉曼技术的研究进展;（2）通过引入局域型表面等离激元（Localizedsurfaceplasmons,LSPs）进一步增强SERS,进而实现PSPs-LSPs共同增强拉曼的超灵敏检测技术,包括在消逝场激发的PSPs基础上,增加纳米粒子实现的PSPs与LSPs共同增强拉曼的原理、装置,以及用该方法进行生物体系的免疫识别检测,此外,还在微纳周期结构上实现了PSPs与LSPs共同激励拉曼;（3）基于PSPs耦合的定向SERS技术,包括在消逝场结构和周期结构上实现SERS定向耦合发射以达到高激发和高收集效率的新技术．     

Characteristic Spectral Patterns in the Carbon‐13 Nuclear Magnetic Resonance Spectra of Hexagonal and Crenellated Graphene Fragments

Nuclear magnetic resonance (NMR) spectroscopy is an important molecular characterisation method that may aid the synthesis and production of graphenes, especially the molecular‐scale graphene nanoislands that have gathered significant attention due to their potential electronic and optical applications. Herein, carbon‐13 NMR chemical shifts were calculated using density functional theory methods for finite, increasing‐size fragments of graphene, hydrogenated graphene (graphane) and fluorinated graphene (fluorographene). Both concentric hexagon‐shaped (zigzag boundary) and crenellated (armchair) fragments were investigated to gain information on the effect of different types of flake boundaries. Convergence trends of the ¹³C chemical shift with respect to increasing fragment size and the boundary effects were found and rationalised in terms of low‐lying electronically excited states. The results predict characteristic behaviour in the ¹³C NMR spectra. Particular attention was paid to the features of the signals arising from the central carbon atoms of the fragments, for graphene and crenellated graphene on the one hand and graphane and fluorographene on the other hand, to aid the interpretation of the overall spectral characteristics. In graphene, the central nuclei become more shielded as the system size increases whereas the opposite behaviour is observed for graphane and fluorographene. The ¹³C signals from some of the perimeter nuclei of the crenellated fragments obtain smaller and larger chemical shift values than central nuclei for graphene and graphane/fluorographene, respectively. The diameter of the graphenic quantum dots with zigzag boundary correlates well with the predicted carbon‐13 chemical shift range, thus enabling estimation of the size of the system by NMR spectroscopy. The results provide data of predictive quality for future NMR analysis of the graphene nanoflake materials.     

Reactivity of Graphene and Hexagonal Boron Nitride In‐Plane Heterostructures with Oxygen: A DFT Study

A density‐functional study has been undertaken to investigate the chemical properties of in‐plane heterostructures of graphene and hexagonal boron nitride. The interactions of armchair and zigzag linking edges with oxygen are looked at in detail. The results of the calculations indicate that the linking edges are highly reactive to oxygen atoms and predict that oxygen molecules can accordingly be adsorbed dissociatively. Furthermore, because oxygen atoms cooperatively interact with the heterostructures, the process can lead to opening of the linking edges, thus splitting the two materials.     

石墨烯条带的电子结构与性质:电场及长度效应

在密度泛函理论(DFT)和含时密度泛函理论(TDDFT)的基础上对宽度上含有8个zigzag链的石墨烯条带(8-ZGNR)的基态和激发态的性质进行了理论研究,着重考察了条带长度及电场的影响.B3LYP杂化泛函的计算结果显示:在基态上,8-ZGNR的最低能量态并不具有磁性,随着长度的增加,才会显示出反铁磁的性质.静电场的加入使8-ZGNR显示出反铁磁性和半金属性.在激发态上,诱导电子会随着外激光脉冲的变化而发生移动和变化,但是相比而言,α自旋电子更容易被激发而产生较明显的诱导电子密度,而β自旋电子则更容易脱离外激光场的控制而产生非绝热现象.     

ZrN6-Doped Graphene for Ammonia Synthesis: A Density Functional Theory Study

Considering the pivotal role of ammonia in the modern chemical industry, designing effective catalysts for the N₂-to-NH₃ conversion stimulates great research enthusiasms. In this work, by means of density functional theory calculations, we systematically investigated the electrocatalysis of six-coordinated transition metal atom anchored graphene for nitrogen fixation. The free energy analysis shows that the ZrN₆ configuration has a good activity toward ammonia synthesis under overpotential of 0.51 V. According to the electron transfer analysis, ZrN₆ site plays a bridging role in charge transfer between the functional graphene and the reactant. Furthermore, the presence of N₆ coordination increases the electron accumulation on the NNH_x intermediates, which weakens the intermolecular N−N bond, reducing the thermodynamic barrier of protonation process. This work provides a basic understanding of the interaction between transition metal and the adjacent coordination in tuning the reactivity.     

Formation and Photoinduced Electron Transfer in Porphyrin- and Phthalocyanine-Bearing N-Doped Graphene Hybrids Synthesized by Click Chemistry

Graphene doped with heteroatoms such as nitrogen, boron, and phosphorous by replacing some of the skeletal carbon atoms is emerging as an important class of two-dimensional materials as it offers the much-needed bandgap for optoelectronic applications and provides better access for chemical functionalization at the heteroatom sites. Covalent grafting of photosensitizers onto such doped graphenes makes them extremely useful for light-induced applications. Herein, we report the covalent functionalization of N-doped graphene (NG) with two well-known electron donor photosensitizers, namely, zinc porphyrin (ZnP) and zinc phthalocyanine (ZnPc), using the simple click chemistry approach. Covalent attachment of ZnP and ZnPc at the N-sites of NG in NG−ZnP and NG−ZnPc hybrids was confirmed by using a range of spectroscopic, thermogravimetric and imaging techniques. Ground- and excited-state interactions in NG−ZnP and NG−ZnPc were monitored by using spectral and electrochemical techniques. Efficient quenching of photosensitizer fluorescence in these hybrids was observed, and the relatively easier oxidations of ZnP and ZnPc supported excited-state charge-separation events. Photoinduced charge separation in NG−ZnP and NG−ZnPc hybrids was confirmed by using the ultrafast pump-probe technique. The measured rate constants were of the order of 10¹⁰ s,⁻¹ thus indicating ultrafast electron transfer phenomena.     

Regulating the Electronic Structure of Freestanding Graphene on SiC by Ge/Sn Intercalation: A Theoretical Study

The intrinsic n-type of epitaxial graphene on SiC substrate limits its applications in microelectronic devices, and it is thus vital to modulate and achieve p-type and charge-neutral graphene. The main groups of metal intercalations, such as Ge and Sn, are found to be excellent candidates to achieve this goal based on the first-principle calculation results. They can modulate the conduction type of graphene via intercalation coverages and bring out interesting magnetic properties to the entire intercalation structures without inducing magnetism to graphene, which is superior to the transition metal intercalations, such as Fe and Mn. It is found that the Ge intercalation leads to ambipolar doping of graphene, and the p-type graphene can only be obtained when forming the Ge adatom between Ge layer and graphene. Charge-neutral graphene can be achieved under high Sn intercalation coverage (7/8 bilayer) owing to the significantly increased distance between graphene and deformed Sn intercalation. These findings would open up an avenue for developing novel graphene-based spintronic and electric devices on SiC substrate.