Hybridization of Organic Molecules with Metal Substrates in the Presence of Surface Passivation Layers

表面钝化层存在下有机分子与金属基材的杂化

• 批准号: 327143884
• 负责人: Professor Dr. Torsten Fritz
• 金额: --
• 依托单位: Lehrstuhl für Angewandte Physik / Festkörperphysik
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2017
• 资助国家: 德国
• 起止时间: 2016-12-31 至 2019-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/327143884?language=en
• 关键词: Hybridization; Organic; Molecules; Metal; Substrates

Aromatic molecules adsorbed in a flat-lying manner on metal surfaces tend to couple electronically to the substrate, i.e., a hybridization of metal substrate and molecular states occurs. Controlling the degree of electronic coupling (or decoupling) is highly desirable from both a fundamental and an application-based point of view, as it governs important properties of the interface.Previous research in the literature mainly aims at measuring the bonding strength (feasible, e.g., with TDS), and to characterize the adsorption as (mostly) chemisorbed or (mostly) physisorbed. In contrast, the project proposed here strives for going beyond this existing binary categorization. In fact, we do not want to measure any integral bonding strength, but examine in detail the impact the hybridization has on the individual electronic states of molecular adsorbates, including both occupied and unoccupied states in the investigation. This will be accomplished by the selection of complementary research methods (EELS, IETS, STS ARUPS). While it has long been known theoretically that individual states interact differently with the substrate (see, e.g., the concept of charge back donation), detailed experimental studies are scarce. Of particular interest is the study of the influence of hybridization on electronic transitions, which should take place by means of Differential Reflectance Spectroscopy (DRS): diverse previous work of the applicant have shown that on various substrates differently broadened absorption spectra of the first monolayer of organic molecules are observed, ranging in shape from monomer-like (being similar to solvent spectra) to greatly broadened and even structureless, depending on the type of interaction. A direct comparison of the absorption spectra of one and the same molecule on different surfaces is feasible by the extraction of the complex dielectric function from the primary DRS data.By inclusion of selected model molecules we want to attempt to derive generalized rules for the hybridization of molecular states on metals. Experimentally, we will vary the degree of hybridization by employing different passivation layers. We will focus on graphene and hexagonal boron nitride (h-BN). We will further consider decoupling of aromatic molecular backbones from surfaces by using phenyl spacer groups. Here, we will concentrate on dibenzotetraphenylperiflanthene (DBP) since it has evolved as a promising material for applications in organic photovoltaic devices (OPVDs) and organic light emitting diodes (OLEDs).A further, even more ambitious project goal is to derive a quantitative measure (figure-of-merit) for the degree of hybridization based on our spectral information, especially on an analysis of the spectral shape and the spectral broadening of the optical spectra.

芳香族分子以平坦的方式吸附在金属表面，倾向于以电子方式耦合到衬底上，即金属衬底和分子态的杂化。从基本和基于应用的观点来看，控制电子耦合(或去耦合)的程度都是非常可取的，因为它控制着界面的重要属性。以前的文献研究主要旨在测量键合强度(例如，利用TDS是可行的)，并将吸附表征为(主要)化学吸附或(主要)物理吸附。相比之下，这里提出的项目努力超越这种现有的二进制分类。事实上，我们不想测量任何积分的成键强度，而是详细地研究杂化对分子吸附的各个电子态的影响，包括研究中的占据态和未占据态。这将通过选择互补的研究方法(EELS、IETS、STS ARUPS)来实现。虽然从理论上早就知道各个状态与底物的相互作用是不同的(例如，参见按存储容量使用计费捐赠的概念)，但详细的实验研究还很少。特别令人感兴趣的是杂交对电子跃迁的影响的研究，这应该通过差示反射光谱(DRS)进行：申请人以前的各种工作表明，在不同的底物上观察到有机分子第一单分子层的不同展宽的吸收光谱，从单体形状(类似于溶剂光谱)到极大展宽甚至无结构，取决于相互作用的类型。直接比较同一分子在不同表面上的吸收光谱是可行的，通过从原始DRS数据中提取复介电函数。通过包含选定的模型分子，我们试图推导出金属表面分子态杂化的普遍规则。在实验上，我们将通过采用不同的钝化层来改变杂化程度。我们将重点介绍石墨烯和六方氮化硼(h-BN)。我们将进一步考虑使用苯基间隔基将芳香族分子主链从表面解偶联。在这里，我们将集中讨论二苯并四苯基环菲(DBP)，因为它已经成为一种在有机光伏器件(OPVD)和有机发光二极管(OLED)中应用的有前途的材料。此外，更雄心勃勃的项目目标是根据我们的光谱信息，特别是对光谱形状和光谱展宽的分析，推导出杂化程度的定量测量(优值系数)。

项目成果

The role of initial and final states in molecular spectroscopies.

初始态和最终态在分子光谱中的作用

• DOI: 10.1039/c8cp07318j
• 发表时间: 2019
• 期刊: Physical chemistry chemical physics : PCCP
• 作者: T. Kirchhuebel;O. L. A. Monti;T. Munakata;S. Kera;R. Forker;T. Fritz
• 通讯作者: T. Fritz

Fraternal twins: distinction between PbPc and SnPc by their switching behaviour in a scanning tunnelling microscope

• DOI: 10.1088/1361-648x/aafeae
• 发表时间: 2019-04-03
• 期刊: JOURNAL OF PHYSICS-CONDENSED MATTER
• 影响因子: 2.7
• 作者: Forker, Roman;Gruenewald, Marco;Fritz, Torsten
• 通讯作者: Fritz, Torsten

Role of Initial and Final States in Molecular Spectroscopies: Example of Tetraphenyldibenzoperiflanthene (DBP) on Graphite

初始态和最终态在分子光谱中的作用：石墨上的四苯基二苯并二萘嵌苯 (DBP) 示例

• DOI: 10.1021/acs.jpcc.0c05448
• 发表时间: 2020
• 期刊: Journal of Physical Chemistry C
• 影响因子: 3.7
• 作者: T. Kirchhuebel;S. Kera;T. Munakata;N. Ueno;R. Shiraishi;T. Yamaguchi;K. Yonezawa;T. Ueba;F. Bussolotti;J. Yang;T. Yamada;R. Mori;S. Kunieda;T. Huempfner;M. Gruenewald;R. Forker;T. Fritz
• 通讯作者: T. Fritz

Ordered Superstructures of a Molecular Electron Donor on Au(111).

Au(111) 上分子电子供体的有序超结构

• DOI: 10.1021/acs.langmuir.7b00306
• 发表时间: 2017
• 期刊: Langmuir : the ACS journal of surfaces and colloids
• 作者: A. Mehler;T. Kirchhuebel;N. Néel;F. Sojka;R. Forker;T. Fritz;J. Kröger
• 通讯作者: J. Kröger

Hybridization vs decoupling: influence of an h-BN interlayer on the physical properties of a lander-type molecule on Ni(111)

• DOI: 10.3762/bjnano.11.101
• 发表时间: 2020-08
• 期刊: Beilstein Journal of Nanotechnology
• 影响因子: 3.1
• 作者: M. Schaal;Takumi Aihara;M. Gruenewald;F. Otto;J. Domke;R. Forker;H. Yoshida;T. Fritz