钙钛矿CsPbX3(X=Cl,Br,I)与五环石墨烯范德瓦耳斯异质结的界面相互作用和光电性能的第一性原理研究

异质结工程是一种提高半导体材料光电性能的有效方法.本文构建了全无机钙钛矿CsPbX₃(X=Cl,Br,I)和二维五环石墨烯penta-graphene(PG)的新型范德瓦耳斯(vdW)异质结,利用第一性原理研究了CsPbX₃-PG异质结不同界面接触的稳定性,进而计算了稳定性较好的Pb-X接触界面异质结的电子结构和光电性能.研究结果表明,CsPbX₃-PG(X=Cl,Br,I)异质结具有II型能带排列特征,能级差距由Cl向I逐渐缩小,具有良好的光生载流子分离能力和电荷输运性质.此外,研究发现CsPbX₃-PG异质结能有效拓宽材料的光吸收谱范围,并能显著提高其光吸收能力,尤其是CsPbI₃具有最优的光吸收性能.经理论估算,CsPbX₃-PG的光电功率转换效率(PCE)可高达21%.这些结果表明,全无机金属卤化物钙钛矿CsPbX₃-PG异质结可以有效地提高半导体材料的光电性能,预期在光电转换器件中具有重要的应用潜力.     

场助InGaAsP/InP异质结半导体光电阴极的研究

本文通过对InGaAsP/InP场助异质结半导体光电阴极的材料生长、场助肖特基结的制备及阴极激活等工艺的系统研究,研制出具有较高光谱响应的半导体光电阴极,生长出优于文献报道的晶格失配率标准的材料,得到相当80年代国际水平理想因子值的场助肖特基结,用实验数据介绍提高量子效率数量级的方法和条件.研究结果表明场助异质半导体光电阴极是在红外波段很有潜力的光电发射体.     

半导体量子点和碳点基零维/二维异质结光催化剂构筑及应用

半导体量子点因其具有精准的尺寸调控、独特的光电特性、丰富的表面活性位点等优势,在光催化剂设计和机理研究中获得了广泛关注。与传统半导体量子点主要作为光吸收单元不同,新兴的碳点更是在增加光吸收、促进电荷分离和增加表面反应位点等光催化不同环节均展现出优异的应用潜力。然而,量子点光催化剂由于小尺寸带来电荷复合严重、易团聚、稳定性差等问题而限制了其光催化性能。解决这些问题的主要途径之一是将零维(0D)量子点负载到超薄的二维(2D)纳米片上,形成0D/2D纳米复合材料,使量子点更加分散和稳定,且2D纳米材料促进的加速电荷转移能够抑制光生电荷的复合,从而可以有效地改善量子点基光催化剂的催化活性和稳定性。本文系统阐述了半导体量子点和碳点基0D/2D异质结光催化剂的构筑及应用,着重讨论了不同类型0D/2D异质结的光催化作用机理及面临的挑战,最后对其未来发展进行了分析和展望。     

电场对graphene/InSe范德瓦耳斯异质结肖特基势垒的调控

半导体与金属接触是制作纳电子和光电子器件时非常重要的问题,接触类型对器件的功能实现和性能影响很大.为了制备高性能多功能化器件,就必须对界面处的势垒高度和接触类型进行调控.采用基于密度泛函理论的第一性原理计算研究了外电场作用下graphene/In Se范德瓦耳斯异质结的电子结构.计算结果表明异质结中的graphene和In Se保留了各自的本征电子性质,在界面处形成了欧姆接触.外电场可以有效调控graphene/In Se异质结中的肖特基势垒,不但可以调控肖特基势垒的高度,而且可以调控界面接触类型.外电场还可以有效调控graphene和In Se界面电荷转移的数量和方向.     

WSe2/GeS 异质结的增强光致发光

二维半导体材料为纳米尺度的光学性质研究提供了良好的支持. 当将其构筑成异质结时, 界面间的相互作用可以改变原光电性质或产生新的性质, 是二维材料光电子器件功能控制的重要手段. 利用机械剥离法制备WSe2/GeS 异质结, 通过发光光谱研究异质结层间激子的光学性质. 结果表明:p 型 GeS 与弱 n 型 WSe2 构筑成异质结时会产生新的层间激子. 与 GeS 和 WSe2 的荧光发射强度相比, 异质结的层间激子发光强度显著增加. 此研究为设计具有先进光电性能的二维半导体器件提供了思路.     

光电协同增强的场效应对LaAlO_3/SrTiO_3界面中持续光电导的调控

LaAlO_3/SrTiO_3异质结界面体系具有新奇的二维自由电子气现象、暂态光电导效应、持续光电导效应等丰富的光电性质,是近年来科学界研究的热点之一.本文研究了场效应对LaAlO_3/SrTiO_3界面光电导效应的调控,发现光电协同增强的场效应可以使得LaAlO_3/SrTiO_3界面产生显著的持续光电导效应,进一步研究发现:在光电协同效应的影响下,随着负的背栅门电压的增加,持续光电导的数值增大,在-70 V附近达到极值;随着负的背栅门电压处理时间的增加,持续光电导的数值单调增加.LaAlO_3/SrTiO_3异质结中这种场增强的持续光电导效应可为多参数可调的光电子记忆器件的研发提供参考依据.     

基于聚合物共混的有机场效应晶体管光电性能研究

采用聚合物共混的方法制备了体异质结薄膜,将其作为光敏半导体层制备了有机场效应光晶体管.利用原子力显微镜表征了共混薄膜的分相情况,探究了器件提高激子解离效率的机理,并对比了聚合物共混前后有机场效应晶体管的光电性能变化和相分离情况.结果表明：制备的聚合物共混光晶体管在微弱光线条件下(0.038 mW/cm²,808 nm)具有较高的光敏性(为10⁶).通过共混聚合物半导体材料制备体异质结薄膜可以有效地提高激子解离的效率,通过双层绝缘层能进一步降低光晶体管的暗电流,从而提高器件的光敏性.     

CuPc/MoS2范德瓦耳斯异质结荧光特性

在众多二维材料中,过渡金属硫族化合物由于其具有独特的光电特性深受广大研究者喜爱.近年来,由二维过渡金属硫族化合物材料与有机半导体结合构建的范德瓦耳斯异质结受到极大的关注.这种异质结可以利用两者的优势对光电特性等性能进行调控,为许多基础物理和功能器件的构建提供了研究思路.本文构建了酞菁铜/二硫化钼(CuPc/MoS₂)范德瓦耳斯异质结,并对其荧光特性进行了表征和分析.与单层MoS₂相比较发现,引入有机半导体CuPc后,异质结当中发生了明显的荧光淬灭现象.通过荧光分析,该现象可以用引入CuPc后异质结中负三激子与中性激子之比增加来解释.此外,通过第一性原理计算分析发现,引入CuPc会在MoS₂的禁带中引入中间带隙态,使得CuPc与MoS₂之间产生非辐射复合,这同样会导致荧光淬灭的发生.CuPc/MoS₂异质结的荧光淬灭现象可以为同类型范德瓦耳斯异质结的光电特性调控研究提供参考和思路.     

C/SiC纳米管异质结电子结构的第一性原理研究

采用基于密度泛函理论的第一性原理计算,对扶手椅型(4,4)和(6,6)及锯齿型(8,0)和(10,0)C/SiC纳米管异质结的电子结构进行了研究.结果表明两类异质结结构都表现为半导体特性.扶手椅型纳米管异质结形成了Ⅰ型异质结,电子和空穴都限制在碳纳米管部分.锯齿型纳米管异质结中价带顶主要分布在碳纳米管部分及C/SiC界面处,而导带底均匀分布在整个纳米管异质结上.这两种异质结结构在未来纳米器件中具有潜在的应用价值. 关键词： C/SiC纳米管异质结 第一性原理 电子结构     

利用脉冲激光沉积外延制备CsSnBr3/Si异质结高性能光电探测器

钙钛矿半导体具有光吸收系数高、载流子扩散长度大和荧光量子效率高等优异物理特性,已在光电探测器、太阳能电池等领域展现出重要的应用潜力.但卤化铅钙钛矿的环境毒性和稳定性大大限制了该类器件的应用范围.因此,寻找低毒、稳定的非铅钙钛矿半导体尤为重要.利用锡元素替代铅元素并生长高质量的锡基钙钛矿薄膜是实现其光电器件应用的可行方案.本文采用脉冲激光沉积方法,在N型单晶硅(100)衬底上外延生长了一层(100)取向的CsSnBr₃钙钛矿薄膜.霍尔效应及电学测试结果表明,基于CsSnBr₃/Si半导体异质结在暗态下具有明显的异质PN结电流整流特征,在光照下具有显著的光响应行为,并具有可自驱动、高开关比(10⁴)以及毫秒量级响应/恢复时间等优良光电探测器件性能.本文研究结果表明利用脉冲激光沉积方法在制备新型钙钛矿薄膜异质结、实现快速灵敏的光电探测方面具有重要应用前景.     

Fabrication of carbon nanotube-threephase organic photodetectors with high responsivity and wide spectrum and the underlying mechanisms

In this work, we incorporated single-walled carbon nanotubes (SWCNTs) into organic three-phase heterojunction active layer detectors, and systematically experimentally investigated the influences of single walled carbon nanotubes (SWCNTs) on the photoabsorption and photoelectric properties of the organic three-phase heterojunction detectors. Under -1 V bias voltage, the average photoresponsivity of three primary colors detector is 475 mA/W, about 2–3 times higher than that of similar devices that without SWCNTs. The average external quantum efficiency (EQE) increases to 111%. The results show that the incorporation of single-walled carbon nanotubes in the three-phase bulk heterojunction active layer maintains the original spectral morphology, while increases a higher degree of aggregation and crystallinity of the organic conjugated polymer, and further enhances a larger capacity of light absorption, regardless of the number of active layer's mixed phases. Under -1 V bias voltage, the average photoresponsivity of three primary colors detector is 475 mA/W, about 2–3 times higher than that of similar devices. The average external quantum efficiency (EQE) can be increased to 111%. In terms of carrier transport, SWCNT can increase the exciton dissociation area, dissociation rate of the film, and provide a fast transport channel for the charge, therefore improve the charge collection of the electrode. In a concentration range of 0.75–1.75 wt% and in high-energy photon excitation, single-walled carbon nanotubes can produce a multiple exciton generation.     

单壁碳纳米管膜及其三聚氰胺甲醛树脂复合材料的光电特性

单壁碳纳米管能够强烈吸收光线,尤其是在近红外区域,并能将光能转换成热能.同时,单壁碳纳米管还具有相当大的将热能转换成电能的能力.通过真空过滤方法,将由化学气相沉积生成的单壁碳纳米管阵列制备成单壁碳纳米管膜.根据研究的需要设计了一个简单的单壁碳纳米管膜光伏性质测试实验装置,并在其两端成功地实现了由红外光转换为电压输出.通过功能化步骤,制备了单壁碳纳米管/三聚氰胺甲醛树脂复合材料膜,实验结果表明该复合材料能产生符号相反的输出电压.这预示着单壁碳纳米管及其三聚氰胺甲醛树脂复合材料在光电领域具有良好的应用前景.     

氮化硼纳米带功能化碳纳米管的热自旋输运性质

热自旋电子学器件结合了自旋电子学和热电子学各自的优点,对人类可持续发展具有重要作用.本文研究了锯齿形BN纳米带(ZBNRs)共价功能化碳纳米管(SWCNT)的电子结构,发现ZBNRs-B-(6,6)SWCNT为磁性半金属,nZBNRs-B-(6,6)SWCNT(n=2—8)为磁性金属;nZBNRs-N-(6,6)SWCNT(n=1—8)为双极化铁磁半导体;4ZBNRs-B-(4,4)SWCNT和4ZBNRs-N-(4,4)SWCNT为磁性半金属,4ZBNRs-B-(m,m)SWCNT(m=5—9)为磁性金属;4ZBNRs-N-(m,m)SWCNT(m=5—9)为双极化铁磁半导体.然后,基于锯齿形BN纳米带共价功能化碳纳米管设计了新型热自旋电子学器件,发现基于ZBNRs-N-(6,6)SWCNT的器件具有热自旋过滤效应;而8ZBNRs-N-(6,6)SWCNT和nZBNRs-B-(6,6)SWCNT(n=1,8)都存在自旋相关塞贝克效应.这些发现表明BN纳米带功能化碳纳米管在热自旋电子学器件方面具有潜在的应用.     

van der Waals gap-inserted light-emitting p–n heterojunction of ZnO nanorods/graphene/p-GaN film

We report on the electroluminescent (EL) and electrical characteristics of graphene-inserted ZnO nanorods (NRs)/p-GaN heterojunction diode. In a comparative study, ZnO NRs/p-GaN and ZnO NRs/graphene/p-GaN heterojunctions exhibit white and yellow EL emissions, respectively, at reverse bias (rb) voltages. The different EL colors are results of different dichromatic EL peak intensity ratios between 2.25 and 2.8 eV light emissions which are originated from ZnO and p-GaN sides, respectively. The 2.25 eV EL is predominant in both the heterojunctions, because of recombination by numerous electrons tunneled from p-GaN to ZnO across the thin barriers of the staggered broken gap with a large band offset in ZnO/p-GaN and the van der Waals (vdW) gap formed by graphene insertion at ZnO NRs/p-GaN. However, as for the 2.8 eV EL intensity, ZnO NRs/graphene/p-GaN hardly shows the EL emission, whereas ZnO NRs/p-GaN exhibits the substantially strong EL peak. We discuss that the significantly reduced 2.8 eV EL emission of ZnO NRs/graphene/p-GaN is a result of decreased depletion layer thickness at p-GaN side where the recombination events occur for 2.8 eV EL before the reverse bias-driven tunneling because the insertion of graphene (or vdW gap barrier) inhibits the carrier diffusion whose amount determines the depletion thickness when forming the heterojunctions. This study opens a way of suppressing (or enhancing) the specific EL wavelength for the dichromatic EL-emitting heterojunctions simply by inserting atom-thick vdW layer.     

Solution processed fabrication of single wall carbon nanotubes thin film by electrohydrodynamic atomization deposition technique and its characterization

An effective method for the fabrication of thin film of single wall carbon nanotubes (SWCNT) using the electro-hydrodynamic atomization (EHDA) deposition technique was demonstrated. In this study, the SWCNT aqueous based dispersion ink was subjected to electrostatic atomization by using an EHDA deposition system. The ink flow visualization under the influence of electric field was performed and the operating EHDA parametric envelope of the ink was explored. Then the deposition of SWCNT through the EHDA process was carried out onto a metallic substrate at a fixed flow rate and corresponding applied voltage thereby achieving thickness ranging from ??70 to 130?nm by making multiple deposition passes. The microscopic inspection of the film was performed and thin film quality was examined by scanning electron microscope analysis. Finally, electrical behavior of the SWCNT film onto a metallic substrate through temperature dependent current-voltage measurements was investigated. The SWCNT film deposited onto the metallic substrate showed electrical conductivity of ??2.98?S/cm.     

Band offsets of epitaxial LaAlO3/TiO2 interface determined by X-ray photoelectron spectroscopy

Room-temperature ferromagnetism in doped anatase TiO₂ has previously been observed, ferromagnetic semiconductor heterostructures based on anatase TiO₂ can thus provide a new opportunity to study spin-dependent transport phenomena at room temperature. An accurate determination of barrier heights or band offsets at the TiO₂-based heterojunctions is of great importance for the spintronics application with semiconductors. X-ray photoelectron spectroscopy with high-energy resolution was used to determine the band offsets of epitaxial LaAlO₃/TiO₂ heterojunction on SrTiO₃(001) substrate fabricated by pulsed laser deposition. Results showed an upward band bending of 0.48(0.03) eV when the film thickness of the overlayer LaAlO₃ above 4 unit cells. The valence band offset obtained is about 0.35(0.16) eV. Assuming bulk band gaps for the LaAlO₃ and TiO₂ epitaxial films, the associated conduction band offset is about 2.95(0.16) eV. These results show that LaAlO₃ can be an ideal tunneling barrier for TiO₂-based heterojunctions.     

Energy band alignment of 2D/3D MoS2/4H-SiC heterostructure modulated by multiple interfacial interactions

The interfacial properties of MoS₂/4H-SiC heterostructures were studied by combining first-principles calculations and X-ray photoelectron spectroscopy. Experimental (theoretical) valence band offsets (VBOs) increase from 1.49 (1.46) to 2.19 (2.36) eV with increasing MoS₂ monolayer (1L) up to 4 layers (4L). A strong interlayer interaction was revealed at 1L MoS₂/SiC interface. Fermi level pinning and totally surface passivation were realized for 4H-SiC (0001) surface. About 0.96e per unit cell transferring forms an electric field from SiC to MoS₂. Then, 1L MoS₂/SiC interface exhibits type I band alignment with the asymmetric conduction band offset (CBO) and VBO. For 2L and 4L MoS₂/SiC, Fermi level was just pinning at the lower MoS₂ 1L. The interaction keeps weak vdW interaction between upper and lower MoS₂ layers. They exhibit the type II band alignments and the enlarged CBOs and VBOs, which is attributed to weak vdW interaction and strong interlayer orbital coupling in the multilayer MoS₂. High efficiency of charge separation will emerge due to the asymmetric band alignment and built-in electric field for all the MoS₂/SiC interfaces. The multiple interfacial interactions provide a new modulated perspective for the next-generation electronics and optoelectronics based on the 2D/3D semiconductors heterojunctions.     

退火对ZnO薄膜晶体结构和ZnO/p-Si异质结光电性质的影响

采用脉冲激光沉积方法在p-Si(100)衬底卜牛长ZnO薄膜,分别在500℃、600℃和700℃下真空退火,采用X射线衍射仪研究了退火对ZnO薄膜品体结构的影响,并测量了ZnO的面电阻和ZnO/p-Si异质结的、I-V特性曲线.研究表明,随着退火温度的升高,ZnO的(002)衍射峰强度逐渐增大,半峰全宽不断减小,同时薄膜内应力减小,ZnO晶粒尺寸变大.表明高温退火有助于ZnO薄膜结晶质量的提高.在没有光照的条件下,异质结的漏电流随退火温度的增加而增大;用650 nm光照射样品时,600℃退火的样品表现出最明显的光电效应,而过高的退火温度会破坏ZnO/p-Si异质结的界面结构,使其光电流变小.所以,要得到性能良好的光电器件,应选取适当的退火温度.     

First-principles study of the switching characteristics of the 15,16-dinitrile DDP/CPD-based optical molecular switch with carbon nanotube electrodes

We have studied the switching characteristics of an optical molecular switch based on the 15,16-dinitrile dihydropyrene/cyclophanediene (DDP/CPD) molecule with two single-walled carbon nanotube (SWCNT) electrodes using first-principles transport calculations. It is shown that the DDP shows an overall higher conductance than the CPD at low bias which is independently of the SWCNT chirality. Meantime, the conductance of the molecular switch can be tuned by the chirality of the SWCNT.     

Photosensitivity of semiconductor-protein systems

Photovoltaic effects have been revealed in a new class of semiconductor/B heterojunctions. Considering various semiconductor materials (Si, GaAs, InSe, CdSiAs₂, ZnGeP₂, and CuGaS₂) and native proteins, we found that it is possible to create photosensitive structures on their basis and managed to prepare them. The photoelectric parameters of the semiconductor/B systems are measured for the first time. It is shows that these structures have a photosensitivity whose level is characteristic of solid-state photoconverters. The spectral dependences of the quantum efficiency of photoconvertion are studied. The window effect for such structures has been established: the long-wavelength boundary of photosensitivity is determined by the energy gap of a semiconductor, whereas the short-wavelength boundary in the vicinity of 3.55 is explained by the quasi-interband transitions in the wide-gap component common for all the heterojunctions—the protein. The conclusion is drawn that the structures of this new class based on crystals of anisotropic semiconductors can be used as broad-band photoconverters of the natural radiation and photoanalyzers of a linearly polarized radiation.