Layered semiconducting electrides in p-block metal oxides

Layered semiconducting electrides in p-block metal oxides

Jiaqi Dai#, Feng Yang, Cong Wang, Fei Pang, Zhihai Cheng, and Wei Ji*

In conventional electrides, excess electrons are localized in crystal voids to serve as anions. Most of these electrides are metallic and the metal cations are primarily from the s-block, d-block, or rare-earth elements. Here, we report a class of p-block metal-based electrides found in bilayer SnO and PbO, which are semiconducting and feature electride states in both the valence band (VB) and conduction band (CB), as referred to 2D “bipolar” electrides. These bilayers are hybrid electrides where excess electrons are localized in the interlayer region and hybridize with the orbitals of Sn atoms in the VB, exhibiting strong covalent-like interactions with neighboring metal atoms. Compared to previously studied hybrid electrides, the higher electronegativity of Sn and Pb enhances these covalent-like interactions, leading to largely enhanced semiconducting bandgap of up to 2.5 eV. Moreover, the CBM primarily arises from the overlap between metal states and interstitial charges, denoting a potential electride and forming a free-electron-like (FEL) state with small effective mass. This state offers high carrier mobilities for both electron and hole in bilayer SnO, suggesting its potential as a promising p-type semiconductor material.

Magnetically-controlled non-volatile charging states in bilayer graphene-CrOCl heterostructures

Magnetically-controlled non-volatile charging states in bilayer graphene-CrOCl heterostructures

Shimin Cao#, Runjie Zheng#, Cong Wang#, Ning Ma, Mantang Chen, Yuanjun Song, Ya Feng, Tingting Hao, Yu Zhang, Kenji Watanabe, Takashi Taniguchi, X.C. Xie, Wei Ji*, Yu Ye*, Zheng Han*, Jian-Hao Chen*

Charge carrier densities in electronic heterostructures are typically responsive to external electric fields or chemical doping but rarely to their magnetization history. Here, we demonstrate that magnetization acts as a non-volatile control parameter for the density of states in bilayer graphene (BLG) interfaced with the antiferromagnetic insulator chromium oxychloride (COC). Using capacitance measurements, we observe a hysteretic behavior in the density of states of BLG on a COC substrate in response to an external magnetic field, which is unrelated to the history of electrostatic gating. First-principles calculations revealed that such hysteresis arises from the magnetic-field-controlled charge transfer between BLG and COC during the antiferromagnetic (AFM) to ferrimagnetic-like (FiM) state phase transition of COC. Our work demonstrates that interfacial charging states can be effectively controlled magnetically, and it also shows that capacitance measurement is a suitable technique for detecting subtle changes not detectable via conventional resistivity measurements. These findings broaden the scope of proximity effects and open new possibilities for nanoelectronics applications.

Exploring Potential for Semiconductor to Quantum Anomalous Hall Insulator Transitions via Substrate-Induced Structural Modifications in Ti3Se4 Monolayers

Exploring Potential for Semiconductor to Quantum Anomalous Hall Insulator Transitions via Substrate-Induced Structural Modifications in Ti3Se4 Monolayers

Zhipeng Song#, Haixia Cheng#, Yun Cao, Qi Zheng, Yurou Guan, Chen Liu, Jierui Huang1 Li Huang, Jiaou Wang, Hui Guo, Guangchao Chen, Chengmin Shen, Shixuan Du, Hongliang Lu*, Wei Ji*, Xiao Lin*, and Hong-Jun Gao

The quantum anomalous Hall (QAH) effect in two-dimensional (2D) topological materials has attracted widespread attention due to its potential for dissipationless chiral edge transport without an external magnetic field, which is highly promising for low-power electronic applications. However, identifying materials that exhibit these properties remains particularly challenging, as only a limited number of such materials are known, raising the intriguing question of whether it is possible to induce the QAH effect in materials with ordinary properties through structural modifications. In this work, we grow an unreported 2D titanium selenide (Ti3Se4) on a Cu(111) substrate using molecular beam epitaxy. Low-energy electron diffraction and scanning tunneling microscopy characterizations reveal a brick-like structure. First-principles calculations and X-ray photoelectron spectroscopy measurements confirm its composition to be Ti3Se4. Our calculations further demonstrate that monolayer Ti3Se4, in its grown form on Cu(111), has the potential to host the QAH effect. Interestingly, when we examine its freestanding form, the monolayer transitions from a QAH insulator candidate into a conventional semiconductor, despite only minor differences in their atomic structures. This transition enlightens us that subtle lattice adjustments can induce a transition from semiconductor to QAH properties in freestanding Ti3Se4. This discovery provides a potential route to engineering practical materials that may exhibit the QAH effect.

Twist-angle dependent pseudo-magnetic fields in monolayer CrCl2/graphene heterostructures

Twist-angle dependent pseudo-magnetic fields in monolayer CrCl2/graphene heterostructures

Zhengbo Cheng#, Nanshu Liu#, Jinghao Deng, Hui Zhang, Zemin Pan, Chao Zhu, Shuangzan Lu, Yusong Bai, Xiaoyu Lin, Wei Ji*, Chendong Zhang*

The generation of pseudo-magnetic fields in strained graphene leads to quantized Landau levels in the absence of an external magnetic field, providing the potential to achieve a zero-magnetic-field analogue of quantum Hall effect. Here, we report the realization of pseudo-magnetic field in epitaxial graphene by building monolayer CrCl2/graphene heterointerface. The CrCl2 crystal structure exhibits spontaneous breaking of three-fold rotational symmetry, yielding anisotropic displacement field at the interface. Using scanning tunneling spectroscopy, we have discovered a sequence of pseudo-Landau levels associated with massless Dirac fermions. A control experiment performed on CrCl2/NbSe2 interface confirms the origin as the pseudo-magnetic field in the graphene layer that strongly interacts with the CrCl2. More interestingly, the strength of the pseudo-magnetic fields can be tuned by the twist angle between the monolayer CrCl2 and graphene, with a variation of up to threefold, depending on the twist angle of 0° to 30°. This work presents a rare 2D heterojunction for exploring PMF-related physics, such as valley Hall effect, with the advantage of easy and flexible implementation.

研究组单分子尺度电子-振动激发合作研究获新突破

研究组单分子尺度电子-振动激发合作研究获新突破

近日,物理学院季威教授研究组联合武汉大学丰敏教授、匹兹堡大学H. Petek教授等研究团队,在扫描隧道电子显微结中设计了利用体相SnSe的半导体隙隔离单层C60导带与衬底耦合的策略,使实验得以观察到近20年久寻未得的单个C60分子最低频电子-振动激发模式,理论计算揭示了C60/SnSe界面电荷转移偶极(一种普遍存在却未引起重视的物理现象)对电子-振动激发模式的选择性增强机理,相关结果于2024年10月23日以“Charge-transfer dipole low-frequency vibronic excitation at single-molecular scale”为题发表在Science Advances 10, eado3470 (2024)上。

电子-振动激发(vibronic excitation)是指分子在吸收或发射能量时,同时发生电子态和振动态的变化,即电子和振动能级同时跃迁,在理解化学反应动力学、分子光谱和电子传输过程中起关键作用。

C60是研究电子-振动激发的原型分子。在以往的研究中,C60分子在其单分子晶体管中表现出Hg1)低频电子-振动激发 [Nature 407, 57-60 (2000)]。而在具有亚分子尺度分辨率的实空间扫描隧道电子显微镜观察中,此前采用的金属衬底与C60分子之间具有很强的相互作用,强烈展宽的分子能级掩盖了这些低能振动信号。为此,科学家在C60分子与金属衬底之间引入了一层超薄绝缘层,有效抑制了衬底和分子间的相互作用,从而成功观察到了一些频率较高的振动模式,如Hg2)、Hg5) 和Hg6)模式[J. Phys. Chem. B 109, 8513-8518 (2005), J. Chem. Phys. 120, 11371-11375 (2004).]。然而,频率最低的Hg(ω1)模式(约33 meV)却始终寻而未得。这主要是因为受到电子隧穿条件的限制,绝缘层厚度有限,可以抑制但无法有效隔离分子和金属衬底之间的相互作用,研究者一筹莫展。

为克服这一挑战,中国人民大学、武汉大学和美国匹兹堡大学的研究团队采用了一种新颖的隔离相互作用策略,即将C60分子支持在SnSe(001)半导体表面上(如上图)。这种结构使分子能级和SnSe能带在界面处形成了II型能带排列,即C60的最低未占据态(LUMO)置于SnSe衬底的能隙中。这有效隔离了C60能级与衬底能带的电子耦合,得以更清晰地观察低频的振动激发模式,尤其是此前难以探测的Hg(ω1)模式。

具体的研究发现,C60分子在SnSe半导体表面上的吸附构型呈现出两种不同的岛状结构,并且C60分子展现出三种不同的STM形貌(如下图)。结合密度泛函理论计算,确定了C60分子的吸附构型。扫描隧道光谱微分电流-电压(dI/dV)谱在SnSe半导体禁带中的LUMO共振处表现出电子-振动激发的特征,且该特征随其能量逐渐偏离SnSe的导带底而不断增强。这表明,通过精心设计分子-半导体界面的II型能带排列,可以选择性地隔离和增强特定的电子-振动态,从而获得清晰的低频电子-振动激发信号。这为在纳米尺度深入理解和灵活控制分子振动动力学提供了一种新颖的基础方法。

进一步研究发现,低频Hg1)振动激发普遍存在于所有C60分子中,与其在表面上的排列方式无关,这挑战了传统认为电子-振动激发受分子取向影响的认识。理论计算表明C60 / SnSe界面处存在由电荷转移导致的界面偶极,显著增强了Hg(ω1)的电子-振动激发(如下图)。该发现具有广泛的意义:它揭示了一种通过设计分子-半导体界面来控制分子电子传输的方法,为更高效的分子电子器件、能源系统和传感技术的开发开辟了可能的新途径。

该研究成果于2024年10月23日以“Charge-transfer dipole low-frequency vibronic excitation at single-molecular scale”为题发表在《Science Advances》期刊上,物理学院官雨柔和武汉大学娄灿灿、崔兴霞博士为论文的共同第一作者。物理学院季威教授、武汉大学丰敏教授与匹兹堡大学Hrvoje Petek教授为该论文的共同通讯作者。该工作的理论计算部分由人民大学官雨柔博士生、周谐宇博士(原物理学院博士生)和季威教授完成,实验部分由合作单位完成,并得到了国家自然科学基金、科技部、教育部等项目的支持。

《Science Advances》是Science家族的一员,是由AAAS(美国科学促进会)出版开放获取综合性科学期刊。该期刊旨在发表各个科学领域的原创性研究成果,并鼓励跨学科合作和交流。根据2022年发布的Journal Citation Reports,《Science Advances》的影响因子为19.6。

文章链接:C. Lou, Y. Guan, X, Cui et al., Charge-transfer dipole low-frequency vibronic excitation at single-molecular scale, Science Advances, DOI: 10.1126/sciadv.ado3470, https://www.science.org/doi/10.1126/sciadv.ado3470