四种功能低维结构在表面上的生长与操控研究

低维结构（包括零维量子点和单原子、一维纳米线以及二维薄膜材料等）的新奇物性为半导体单元微型化和高性能器件多样化的研发提供了广阔的研究平台。一方面，低维结构展现出丰富的量子限域效应、拓扑物态和强关联效应等量子效应，以其为核心将可能制备出具有特殊或优异功能的器件。另一方面，低维结构的物性可以通过生长调控、衬底诱导或者元素掺杂等方式进行有效改良，在精密制造、信息计算、新能源和生物医疗等领域都有广阔的应用前景。尽管低维结构的相关研究已经十分丰富，但仍然存在不少难题悬而未决，比如原子级精度的零维量子点甚至单原子器件的构建、性能优异的纳米线的制备与表征、新型二维材料的原位生长与性能研究等。低维结构一般都依附于表面，在所有表面原位表征分析技术中，扫描隧道显微镜（STM）具有无与伦比的优势。因此，结合STM实验和第一性原理计算，对表面上四种低维结构的生长和操控展开研究，并针对不同维度的四个体系各提供了相应的调控手段，实现了部分人工可控的生长与制备。主要研究内容如下：

基于STM纵向操纵术和脉冲诱导分解术实现了单个磷原子在单晶硅表面的精确植入。硅中植入单个磷原子是实现基于单个磷原子的一种固态量子比特方案的核心步骤。实验和理论证明P4分子以微弱的范德华力吸附在硅表面。通过两步法利用P4分子实现了单个磷原子在硅表面的可控植入。第一步：通过STM纵向操纵术将P4分子在硅表面任意位置“提起”与“放下”，实现了原子级地精准定位。第二步：通过脉冲诱导分解术将在目标位点的P4分子分解成单个磷原子以实现植入。与国际主流的硅磷量子比特制备方案相比，新方法有植入位点精度高、植入数量可控和可操作性强的特点。

基于金衬底对As4分子的分解作用，制备了一种新型的一维砷纳米链结构。制备的扶手椅型砷链与Au(111)表面形成（2×3）超胞结构，并且能在较大衬底温度范围内保持稳定（< 600 K）。理论计算表明一维自由砷链具有半导体性质，其本征能隙为0.5 eV。通过对比其它衬底表面生长砷的实验结果和理论计算，证明只有Au(111)表面适合扶手椅型砷链的形成。通过STM针尖操控实现了砷链在Au(111)表面的翻转，证明了砷链可以从金衬底表面进行剥离。与碳纳米管中制备一维砷链的方案相比，新制备方案具有砷链结构稳定、纯度高和操作简单、可大量制备的优点。

通过低温生长制备出了一种高质量的二维As4分子膜。其中四面体形状的As4分子以正置和倒置交替排列的姿态在Au(111) 和HOPG表面自组装形成结构相同的有序膜。实验和理论证明As4分子膜与HOPG的相互作用明显弱于与金衬底的相互作用。因此，HOPG表面的As4分子膜更多地保留了其本征的半导体物性。As4分子膜在Au(111)表面由于衬底的作用，存在具有19.1°夹角的两种取向。通过充分理解砷在不同衬底上的生长机理，为将来进一步制备出高质量砷烯奠定了基础。

通过钾掺杂实现了对有机分子苉（Picene）薄膜电子结构的调控。苉分子块材通过碱金属掺杂可以转变成有机超导体，但是将其降低到二维是否仍具有超导特性还有争议。首先在Au(111) 表面沉积了苉分子薄膜，然后通过钾原子沉积和退火，实现了钾原子的有效掺杂。随着钾掺杂率的增加，KxPicene（x=0~4）薄膜上依次出现了几种新的有序结构。同时，随着从钾原子转移到苉分子膜的电荷量增加，掺钾苉分子膜的费米能级逐渐向最低未占据分子轨道（LUMO）移动。特别是对于K3.4Picene，其LUMO态跨过费米能级时劈裂成上下两个态，揭示着这种系统存在强的电子关联效应，并且未见超导态的出现。

The novel physical properties of low-dimensional (LD) structures, including zero-dimensional (0D) quantum dots and single atoms, one-dimensional (1D) nanowires and two-dimensional (2D) thin-film materials, etc. provide a broad research platform for the miniaturization of semiconductor elements and the diversification of high-performance devices. On the one hand, LD structures exhibit rich quantum effects, such as quantum confinement effects, topological states, and strong correlation effects, which will lead to the fabrication of devices with special or excellent functions. On the other hand, the physical properties of LD structures can be effectively improved through growth regulation, substrate induction or element doping, etc., and have broad applications in the fields of precision manufacturing, information computing, new energy and biomedicine. Although the relevant research on LD structures has been abundant, there are still many unsolved problems, such as the construction of 0D quantum dots and even single-atom devices at atomic-level precision, the preparation and characterization of nanowires with excellent performance, and the in-situ growth and performance of new 2D materials. LD structures are generally attached to surfaces, and scanning tunneling microscopy (STM) offers unparalleled advantages among all surface in-situ characterization and analysis techniques. Therefore, we combined STM experiments and first-principle calculations to study the growth and manipulation of four LD structures on the surface, and provided corresponding control methods for each of the four systems at different dimensions, realizing partial artificial control, growth and preparation. The main research contents are as follows:

Based on STM vertical manipulation and pulse-induced decomposition, the precise implantation of individual phosphorus atoms on the single-crystal silicon surface is realized. Implanting a single phosphorus atom into silicon is a core step in implementing a solid-state qubit scheme based on a single phosphorus atom. Experiments and theories have proved that the P₄ molecule adsorbs on the surface of the silicon with a weak van der Waals force. We have achieved the controllable implantation of single phosphorus atom on the silicon surface by a two-step method using P₄ molecules. Step 1: The P₄ molecule is "pick-up and "drop-off" at any position on the silicon surface by STM vertical manipulation, achieving atomic-level precise positioning. Step 2: The P₄ molecule is decomposed into single phosphorus atom at the target site by STM pulse-induced decomposition for implantation. Compared with the international mainstream Si:P qubit preparation scheme, our method has the characteristics of high implantation accuracy, controllable implantation quantity and strong operability.

Based on the decomposition of As₄ molecules by gold substrates, a novel 1D arsenic nanochain structure has been fabricated. The armchair arsenic forms a (2×3) supercell structure with the Au(111) surface and remains stable over a wide range of substrate temperature (< 600 K). Theoretical calculations show that the intrinsic 1D arsenic chain has semiconductor properties with an energy gap of 0.5 eV. Comparing the experimental results and theoretical calculations of arsenic grown on other substrates, it is shown that only the Au(111) surface is suitable for the formation of armchair arsenic chains. We have achieved the flip-up of arsenic nanochains on the Au(111) surface through STM tip manipulation, and have proved that arsenic chains can be peeled off from the gold substrate. Compared with the scheme for fabricating 1D arsenic chains in carbon nanotubes, our scheme has the advantages in stable and high-purity arsenic nanochains, simple fabrication and large-scale production.

Based on low temperature growth, a high-quality 2D As₄ molecular film is fabricated. The tetrahedral-shaped As₄ molecules are self-assembled into forming the same ordered structure on the Au(111) and HOPG surfaces in an alternating upright and inverted posture. Experiments and theoretical calculations prove that the interaction between the As₄ molecular film and HOPG is significantly weaker than that with the gold substrate. Therefore, the As₄ molecular film on the HOPG surface retains more of its intrinsic semiconductor properties. As₄ molecular film on the Au(111) surface are two orientations with an angle of 19.1° due to the effects of the Au(111) substrate. By fully understanding the growth mechanism of arsenic on different substrates, the foundation is laid for fabricating high-quality arsenene in the future

By potassium doping, the electronic structure of the organic picene molecular film is regulated controllably. Picene bulk can be transformed into superconductors by alkali metals doping, but it is controversial whether they are remains superconductivity when this system is reduced to 2D. At first, we have achieved the efficient potassium doping into the picene film on the Au(111) surface by depositing and annealing. With the increase of potassium doping ratio, several new ordered structures in the K_xPicene films (x = 0 to 4) appear in turn. At the same time, the Fermi level of the potassium-doped picene molecular film gradually moves towards the lowest unoccupied molecular orbital (LUMO) state as the amount of charge transferred from potassium atoms into the picene molecular film increases. Especially, the LUMO state of K_3.4Picene is split into two states when is crosses the Fermi energy level, revealing that the system has a strong electron correlation effect, and no superconducting state appears.

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