有序金纳米颗粒阵列的制备及光吸收特性研究

采用纳米球刻蚀技术中漂移法在玻璃基片上制备较大 面积不同直径的聚苯乙烯小球掩模板, 采用磁控溅射技术在掩模板上沉积不同厚度的金薄膜, 去除聚苯乙烯小球后, 通过扫描电子显微镜观察到周期排列的三角状金纳米颗粒点阵. 通过紫外-可见分光光度计测试所制备样品的光吸收特性, 发现表面等离子体共振峰随粒径增大发生红移, 随金纳米颗粒高度增加发生蓝移. 基于Mie理论, 利用Matlab软件编程对不同粒径的金阵列光吸收特性进行理论模拟, 并与实验结果进行对比. 关键词： 纳米球刻蚀 金纳米颗粒阵列 表面等离子体共振     

场发射冷阴极微栅孔阵列制备技术

实现了一种采用聚苯乙烯纳米球自组装技术和微机械制造技术加工的场发射阴极用亚微米栅极微孔阵列。设计了一套完整的工艺实验方案,首先采用微球自组装技术获得了亚微米级金属网孔掩膜,然后通过反应离子刻蚀技术获得了亚微米栅极孔阵列,从而实现了集成度高、分布均匀的周期性亚微米孔洞阵列的制备,微孔集成度达到108cm-2。实验研究了氧气刻蚀聚苯乙烯微球的规律。采用金属掩膜,四氟化碳干法刻蚀二氧化硅,获得了深度为500 nm的微孔。实验结果证明该工艺方案是一种获得大面积、均匀分布、集成度高的场发射冷阴极栅孔阵列的有效方法。     

磁控溅射制备微球表面金属Mo涂层的研究

利用磁控溅射制备了各种工艺参数不同的微球表面金属Mo涂层样品,并通过白光干涉仪和扫描电子显微镜对样品的表面及剖面进行了系统的测试分析。分别探究了溅射工作气压和沉积制备时间对微球表面Mo涂层表面形貌以及结晶质量的影响规律。结果表明通过优化工艺参数可制备微球直径约为800μm、涂层厚度为3.5μm到14.1μm、厚度均匀性良好的微球表面Mo涂层。Mo涂层中的晶粒呈现出柱状结构致密堆积在一起,且随涂层的厚度增加晶粒间空隙增大。     

基于直接胶体晶体刻蚀技术的高度有序纳米硅阵列的尺寸及形貌控制

以自组装单层胶体小球阵列为掩模，采用直接胶体晶体刻蚀技术在硅表面制备二维有序尺寸可控的纳米结构.在样品制备过程中，首先通过自组装法在硅表面制备了直径200nm的单层聚苯乙烯(PS)胶体小球的二维有序阵列；然后对样品直接进行反应离子刻蚀(RIE)，以氧气为气源，利用氧等离子体对聚苯乙烯小球和对硅的选择性刻蚀作用，通过改变刻蚀时间，制备出不同尺寸的PS胶体小球的有序单层阵列；接着以此二维PS胶体单层膜为掩模，以四氟化碳为气源对样品进行刻蚀；最后去除胶体球后得到二维有序的硅柱阵列.SEM和AFM的测量结果表明：改变氧等离子体对胶体球的刻蚀时间和四氟化碳对硅的刻蚀时间，可以控制硅柱的尺寸以及形貌，而硅柱阵列的周期取决于原始胶体球的直径. 关键词： 胶体晶体刻蚀 纳米硅柱阵列     

氧化钨二维微米球腔阵列对聚苯胺电致变色的影响

采用气/液界面自组装方法制备规整排列的聚苯乙烯微球二维单层结构,以此为模板,采用电化学沉积法在电极表面构筑了有序的氧化钨微球腔阵列,进一步在氧化钨球腔内电化学沉积聚苯胺,采用吸收光谱研究了电极表面球腔阵列结构对聚苯胺电致变色行为的影响.     

利用表面微结构提高波长上转换红外探测器效率

波长上转换红外探测器具有实现大面阵焦平面的优势, 但光提取效率是制约器件整体效率的关键因素之一. 本文主要研究利用表面微结构来提高波长上转换红外探测器的效率. 首先通过仿真计算研究了表面微结构参数对光提取效率的影响, 然后基于优化设计的参数, 采用聚苯乙烯纳米球掩膜刻蚀的方法制作了具有圆台型表面微结构的波长上转换红外探测器. 测试结果表明, 具有表面微结构的器件的光提取效率比无表面微结构的器件提高了130%. 本文制作表面微结构的方法可以实现波长上转换红外探测器件整体效率的提高.     

激光刻蚀类球状微米金刚石聚晶薄膜对场致电子发射稳定性的影响

在覆盖金属钛层的陶瓷上,通过微波等离子体化学气相沉积(MPCVD)法制备出类球状微米金刚石聚晶薄膜,并通过激光刻蚀金刚石聚晶薄膜的表面.利用扫描电子显微镜、拉曼光谱,X射线衍射分析了刻蚀前后的结构和表面形貌,测试了刻蚀前后薄膜的场致电子发射特性,发现激光的刻蚀对金刚石聚晶薄膜场致电子发射的稳定性有一定的提高,并对其制备过程及发射机理进行了研究.     

电极间距对ZnO基MSM紫外光电探测器性能的影响

利用金属有机物化学气相沉积法在蓝宝石衬底上制备了ZnO薄膜。利用Au电极,在ZnO薄膜上制备电极间距不同的金属-半导体-金属结构紫外光电探测器。发现随着电极间距从150μm降至5μm,探测器响应度呈现出从15 mA/W到75 mA/W的明显提高。同时,随着电极间距的减小,器件的I-V曲线线形发生了显著改变。这被归结为电极间距变化改变了器件耗尽区宽度和电极间电阻造成的结果。     

基于周期性电极的窄条单纵模674nm半导体激光器

报道了中心波长在674 nm的周期性电极窄条形单纵模半导体激光器。其制作工艺简单,仅使用i线光刻技术和普通的刻蚀技术制作的周期性沟槽与周期性电极结构即保证了器件工作在增益耦合机制下,进而实现单纵模激光输出。当注入电流为85 mA、测试温度18℃时,激光器的输出功率为2.603 mW。当注入电流为60 mA时,在不同测试温度下,器件均保持单纵模工作。当室温为16℃时,测得器件的光谱线宽可达到2.42 pm,边模抑制比为47 dB。由于该器件制作成本低,性能优良,可广泛应用于实际生产中。     

室温合成非晶三硫化钼析氢催化剂的性能调制以及其在串联制氢器件中的应用

高催化活性、低成本、良好工艺兼容性以及高稳定性的析氢催化剂是实现一体化光电化学水解制氢器件的关键, 然而传统的贵金属催化剂由于储量稀缺、成本高昂而严重限制了光电化学水解制氢器件的产业化进程. 本文在室温下通过湿法化学合成法制备了高催化活性、成本低廉以及工艺兼容性好的非金属非晶三硫化钼析氢催化剂, 并研究了不同催化剂滴涂量对其催化活性以及串联制氢器件制氢性能的影响. 结果表明, 存在最优化非晶三硫化钼催化剂滴涂量以获得最佳催化活性(10 mA/cm²电流密度对应电势达260 mV vs. RHE(可逆氢电极), 塔菲尔斜率达68 mV/dec), 其粗糙表面以及多孔结构可获得更大的电化学接触面积以促进析氢反应. 进一步将其作为光阴极应用于串联制氢器件, 可有效降低过电势损失和提高光生电流密度输出, 与光阳极结合有望提高制氢效率.     

Pillar effects in MoS2 catalysts supported on Al and Zr pillared clays in a hydrotreatment reaction: A preliminary study

Molybdenum (Mo) supported on aluminum-pillared clay (Al-PILC) and zirconium-pillared clay (Zr-PILC) with contents of 0.6, 1.4 and 2.8 atoms of Mo/nm² were prepared and tested in the hydrogenation (HYD) of naphthalene (NP). It was found that the molybdenum sulfide (MoS₂) catalysts supported on Zr- pillared clays were more active than the samples supported on Al-pillared clays and catalysts supported on alumina. The catalysts were characterized by X-ray diffraction (XRD), thermogravimetric analysis, nitrogen adsorption and transmission electron microscopy (TEM). Characterization analysis clearly pointed out to a close interaction of MoS₂ with ZrO₂ in the pillared clays. Therefore, the highest hydrogenation activities can be related to the presence of an interaction of MoS₂ with ZrO₂, probably with a different electronic interaction between the active phase and the support, than that reported for the MoS₂/Al₂O₃ system.     

碳纳米管/二硒化钼有机玻璃的非线性吸收、非线性散射和光限幅特性

MoSe₂的禁带宽度较窄（1.1–1.5 eV）,且具有可调谐的激子光电效应,这样使其在光致发光、光电晶体管、太阳能电池和光学非线性等方面具有潜在的应用价值.然而,纯的MoSe₂的光生电子空穴复合率较高,限制了其在某些光学领域中的应用.通过设计MoSe₂的复合材料,可以降低材料的光生电子空穴复合率,从而扩展其应用领域.首先,通过热溶剂法合成CNT/MoSe₂复合材料;然后,通过浇铸法将其分散在甲基丙烯酸甲酯（MMA）中制备成有机玻璃,其中MMA会聚合成聚甲基丙烯酸甲酯（PMMA）,并利用改进的Z-扫描技术首次对CNT/MoSe₂/PMMA有机玻璃的非线性吸收、非线性散射和光限幅特性进行了研究.研究表明,随着输入能量的变化,通过调节输入能量,CNT/MoSe₂/PMMA有机玻璃表现出饱和吸收（SA）和从SA到反饱和吸收的转变.结合材料特性及应用条件要求,可以得到CNT/MoSe₂/PMMA有机玻璃在光学设备,如光学限制器和锁模/调Q激光器等方向具有较好的应用前景.     

六角星形MoSe_2双层纳米片的制备及其光致发光性能

采用化学气相沉积法,以三氧化钼作为钼源,硒粉作为硒源,在H_2/Ar气氛下生长出硒化钼纳米片.扫描电镜、X射线衍射表征结果表明,MoSe_2产物呈六角星状,横向尺寸约10μm,具有很好的晶体质量和结构.拉曼光谱表征其结构,确定其为双层纳米片.研究表明,高温反应时间对双层纳米片的生长具有重要的影响.通过对双层纳米片的生长机理的探究,推测其经历了3个生长过程:在高温下,Mo源和Se源被气化成气态分子并发生硒化反应形成晶核;晶核呈三角形外延生长;当反应时间持续增加,在空间位阻效应的影响下,晶体以中心原子岛为核,外延耦合生长出第二层三角形,最终形成六角星状双层纳米片.光致发光光谱结果表明,六角星状MoSe_2双层纳米片在1.53 eV处具有直接带隙和1.78 eV处具有间接带隙,其较宽范围的激发光谱响应预测其在光电探测器件领域具有潜在的应用前景.     

层状二硫化钼研究进展

近年来,层状二硫化钼由于其特殊的类石墨烯结构和独特的物理化学性质已成为国内外研究的热点.本文综述了层状二硫化钼的物理结构、价带结构和光学性质;介绍了制备方法,包括生长制备和剥离制备.生长制备的原料包括四硫代钼酸铵((NH4)_2MoS_4)、钼(Mo)和三氧化钼(MoO_3)等.剥离制备包括微机械剥离、液相超声法、锂离子插层法和电化学锂离子插层法等.归纳了层状二硫化钼在场效应晶体管、传感器和存储方面的应用,展望了层状二硫化钼的研究前景.     

Interface engineering of transition metal dichalcogenide/GaN heterostructures: Modified broadband for photoelectronic performance

The GaN-based heterostructures are widely used in optoelectronic devices, but the complex surface reconstructions and lattice mismatch greatly limit the applications. The stacking of two-dimensional transition metal dichalcogenide (TMD = MoS₂, MoSSe and MoSe₂) monolayers on reconstructed GaN surface not only effectively overcomes the larger mismatch, but also brings about novel electronic and optical properties. By adopting the reconstructed GaN (0001) surface with adatoms (N-ter GaN and Ga-ter GaN), the influences of complicated surface conditions on the electronic properties of heterostructures have been investigated. The passivated N-ter and Ga-ter GaN surfaces push the mid-gap states to the valence bands, giving rise to small bandgaps in heterostructures. The charge transfer between Ga-ter GaN surface and TMD monolayers occurs much easier than that across the TMD/N-ter GaN interfaces, which induces stronger interfacial interaction and larger valence band offset (VBO). The band alignment can be switched between type-I and type-II by assembling different TMD monolayers, that is, MoS₂/N-ter GaN and MoS₂/Ga-ter GaN are type-II, and the others are type-I. The absorption of visible light is enhanced in all considered TMD/reconstructed GaN heterostructures. Additionally, MoSe₂/Ga-ter GaN and MoSSe/N-ter GaN have larger conductor band offset (CBO) of 1.32 eV and 1.29 eV, respectively, extending the range from deep ultraviolet to infrared regime. Our results revel that the TMD/reconstructed GaN heterostructures may be used for high-performance broadband photoelectronic devices.     

电化学析氢反应中单层MoSe2氢吸附机理第一性原理研究

基于密度泛函理论的第一性原理方法,本文计算了单层2H相MoSe₂纳米材料表面及两种边缘（Mo原子边缘、Se原子边缘）不同活性位点、不同氢原子吸附率下的氢吸附吉布斯自由能（Gibbs free energy,用△G_H⁰表示）,并且将对应的微观结构进行了系统分析比较,得出△G_H⁰最接近于0 eV的吸附位点及相应的吸附率.同时,结合差分电荷密度和电负性理论,分析了单层MoSe₂两种边缘氢吸附的电荷转移及成键特性,进一步解释了不同吸附位点呈现的结构与能量趋势.最后,通过基于密度泛函理论的第一性原理分子动力学模拟,研究了高温热运动对两种边缘氢吸附的影响,获得了氢原子发生脱附的临界温度及对应的微观动态过程.该理论研究从原子尺度揭示了单层2H相MoSe₂纳米材料边缘不同位点在不同温度下对氢原子吸附和脱附的微观机理,证实了Mo原子边缘的畸变和重构行为,加深了对实验中单层2H相MoSe₂边缘在不同温度下氢吸附机理的理解,为实验中通过控制MoSe₂边缘设计廉价高效的析氢催化剂提供理论参考.     

Mechanical properties of lateral transition metal dichalcogenide heterostructures

Transition metal dichalcogenide(TMD)monolayers attract great attention due to their specific structural,electronic and mechanical properties.The formation of their lateral heterostructures allows a new degree of flexibility in engineering electronic and optoelectronic dervices.However,the mechanical properties of the lateral heterostructures are rarely investigated.In this study,a comparative investigation on the mechanical characteristics of 1H,IT'and 1H/1T'heterostructure phases of different TMD monolayers including molybdenum disulfide(M0S₂)molybdenum diselenide(MoSe₂),Tungsten disulfide(WS₂),and Tungsten diselenide(WSe₂)was conducted by means of density functional theory(DFT)calculations.Our results indicate that the impact of the lateral heterostructures has a relatively weak mechanical strength for all the TMD monolayers.The significant correlation bet ween the mechanical properties of the TMD monolayers and their structural phases can be used to tune their stiffness of the materials.Our findings,therefore,suggest a novel strategy to manipulate the mechanical characteristics of TMDs by engineering their structural phases for their practical applications.     

Chemical effects of Ne bombardment on the MoS2(0001) surface studied by high-resolution photoelectron spectroscopy

The effect of 1 keV Ne⁺ bombardment on the clean MoS₂(0001)-1 × 1 surface with fluences between 4 × 10¹⁴ and 4 × 10¹⁶ Ne⁺/cm² was studied using high-resolution photoelectron spectroscopy excited with synchrotron radiation. Spectra of the Mo 3d and S 2p core levels were measured with photon energies that ensured that the kinetic energy of the photoelectrons was the same, resulting in the same depth being probed for both core levels. For lower fluences (i.e., 2 × 10¹⁵ Ne⁺/cm²), S vacancy defect formation occurs in the MoS₂ lattice, with the concurrent formation of a small amount (< 10%) of dispersed elemental molybdenum [Mo(0)]. For fluences greater than l × 10¹⁶ Ne⁺/cm², the Mo(0) is the predominant species in the surface region, while the remaining species consist of amorphous MoS_2−x and polysulfide species. Valence band spectra taken with photon energies of 152 and 225 eV were consistent with the core level results. The movement of the valence band maximum toward the Fermi level indicated the formation of a metallic surface region. Annealing the sample to temperatures up to 1000 K resulted in the formation of metallic Mo coexisting, in approximately equal amounts, with reformed MoS₂ in a surface with no long-range order as determined by LEED. Finally, a qualitative depth distribution of the chemical species present after Ne⁺ bombardment was determined by varying the photon energies used for the core level spectra. The results indicate that the preferential sputtering of sulfur over molybdenum occurs predominantly through a mechanism involving chemical bonding effects, specifically, through the preferential emission of polysulfide ions over other species in the bombarded region.     

Role of graphene in improving catalytic behaviors of AuNPs/MoS2/Gr/Ni-F structure in hydrogen evolution reaction

The efficient production of hydrogen through electrocatalytic decomposition of water has broad prospects in modern energy equipment. However, the catalytic efficiency and durability of hydrogen evolution catalyst are still very deficient, which need to be further explored. Here in this work, we prove that introducing a graphene layer (Gr) between the molybdenum disulfide and nickel foam (Ni-F) substrate can greatly improve the catalytic performance of the hybrid. Owing to the excitation of local surface plasmon resonance (LSPR) of gold nanoparticles (NPs), the electrocatalytic hydrogen releasing activity of the MoS₂/Gr/Ni-F heterostructure is greatly improved. This results in a significant increase in the current density of AuNPs/MoS₂/Gr/Ni-F composite material under light irradiation and in the dark at 0.2 V (versus reversible hydrogen electrode (RHE)), which is much better than in MoS₂/Gr/Ni-F composite materials. The enhancement of hydrogen release can be attributed to the injection of hot electrons into MoS₂/Gr/Ni-F by AuNPs, which will improve the electron density of MoS₂/Gr/Ni-F, promote the reduction of H₂O, and further reduce the activation energy of the electrocatalyst hydrogen evolution reaction (HER). We also prove that the introduction of graphene can improve its stability in acidic catalytic environments. This work provides a new way of designing efficient water splitting system.