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.

在金属表面上以平坦的方式吸附的芳族分子倾向于以电子方式将底物逐渐融合到底物，即金属底物和分子状态的杂交发生。从基本和基于应用程序的角度来控制电子耦合（或脱耦）的程度是高度理想的，因为它控制着界面的重要特性。文献中的详尽研究主要旨在衡量粘结强度（例如可行的TDS），并以TDS为特征，并表征As andsor Asermed Asemors（或最多）化学。相比之下，这里提出的项目努力超越现有的二元分类。实际上，我们不想衡量任何积分键的强度，而是详细检查杂交对分子吸附物的单个电子状态的影响，包括在研究中包括被占领和无占用状态的影响。这将通过选择补充研究方法（EEL，IET，STS ARUPS）来实现。从理论上讲，长期以来已经知道各个状态与底物的相互作用不同（例如，参见电荷返回捐赠的概念），但详细的实验研究很少。特别感兴趣的是研究杂交对电子过渡的影响的研究，应通过差异反射光谱法（DRS）进行：申请人的先前工作表明，在各种底物上，在各种底物上都可以观察到了较大的有机分子的第一个单体分子的吸收光谱，并且与单域相似，依次相似，依次依次，依次相似，依次依次，依次相似，依次依次，依次依次依次依次，依次依次依次。关于互动的类型。通过从初级DRS数据中提取复杂的介电函数的一个和同一分子在不同表面上的吸收光谱的直接比较是可行的。通过纳入所选模型分子，我们希望尝试为金属上分子状态的杂交得出广义规则。在实验上，我们将通过采用不同的钝化层来改变杂交程度。我们将专注于石墨烯和六角硼硝酸盐（H-BN）。我们将通过使用苯基间隔基组进一步考虑将芳族分子骨架与表面脱钩。在这里，我们将专注于二苯苯基苯基氯烷基（DBP），因为它已作为在有机光伏设备（OPVD）和有机光发射二极管（OLEDS）（OLEDS）（OLEDS）中应用的有前途的材料（OPVD）。光谱的光谱形状和光谱拓宽。

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