Structure of van der Waals bound hybrids of organic semiconductors and transition metal dichalcogenides: the case of acene films on MoS2

Transition metal dichalcogenides (TMDC) are important representatives in the emerging field of two‐dimensional materials. At present their combination with molecular films is discussed as it enables the realization of van der Waals bound organic/inorganic hybrids which are of interest in future device architectures. Here, we discuss the potential use of molybdenum disulfide (MoS₂) as supporting substrate for the growth of well‐defined, crystalline organic adlayers. By this means, hybrid systems between the TMDC surface and organic compounds can be prepared, allowing for the profound investigation of mutual optical and electronic coupling mechanisms. As model system, we choose pentacene and perfluoropentacene as prototypical organic semiconductors and analyze their film formation on MoS₂(001) surfaces. In both cases, we observe smooth, crystalline film growth in lying molecular configuration, hence enabling the preparation of well‐defined hybrid systems. By contrast, on defective MoS₂ surfaces both materials adopt an upright molecular orientation and exhibit distinctly different film morphologies. This emphasizes the importance of highly ordered TMDC surfaces with low defect density for the fabrication of well‐defined hybrid systems.     

Organic functionalization of group IV semiconductor surfaces: principles, examples, applications, and prospects

Organic functionalization is emerging as an important area in the development of new semiconductor-based materials and devices. Direct, covalent attachment of organic layers to a semiconductor interface provides for the incorporation of many new properties, including lubrication, optical response, chemical sensing, or biocompatibility. Methods by which to incorporate organic functionality to the surfaces of semiconductors have seen immense progress in recent years, and in this article several of these approaches are reviewed. Examples are included from both dry and wet processing environments. The focus of the article is on attachment strategies that demonstrate the molecular nature of the semiconductor surface. In many cases, the surfaces mimic the reactivity of their molecular carbon or organosilane counterparts, and examples of functionalization reactions are described in which direct analogies to textbook organic and inorganic chemistry can be applied. This article addresses the expected impact of these functionalization strategies on emerging technologies in nanotechnology, sensing, and bioengineering.     

Patterned nucleation control in vacuum deposition of organic molecules

We report a generally applicable method to pattern organic molecules on mesoscopic scales. In our method, organic molecular beam deposition was conducted on substrate surfaces prepatterned with materials to which the organic molecules have larger binding energies in comparison to the substrate. Fully uniform nucleation control at these predefined locations can be achieved by an appropriate selection of the growth parameters including temperature and deposition rate. The physical mechanisms involved are studied by Monte Carlo simulations and stand in good agreement with the experimental findings.     

Self-assembling and self-limiting monolayer deposition

Effects of spatial ordering of molecules on surfaces are commonly utilized to deposit ultra-thin films with a thickness of a few nm. In this review paper, several methods are discussed, that are distinguished from other thin film deposition processes by exactly these effects that lead to self-assembling and self-limiting layer growth and eventually to coatings with unique and fascinating properties and applications in micro-electronics, optics, chemistry, or biology. Traditional methods for the formation of self-assembled films of ordered organic molecules, such as the Langmuir-Blodgett technique along with thermal atomic layer deposition (ALD) of inorganic molecules are evaluated. The overview is complemented by more recent developments for the deposition of organic or hybrid films by molecular layer deposition. Particular attention is given to plasma assisted techniques, either as a preparative, supplementary step or as inherent part of the deposition as in plasma enhanced ALD or plasma assisted, repeated grafting deposition. The different methods are compared and their film formation mechanisms along with their advantages are presented from the perspective of a plasma scientist. The paper contains lists of established film compounds and a collection of the relevant literature is provided for further reading.     

Effect of Carrier Differences on Spin Polarized Injection into Organic and Inorganic Semiconductors

Spin polarized injection into organic and inorganic semiconductors are studied theoretically from the spin diffusion theory and Ohm＇s law, and the emphases are placed on the effect of the carrier differences on the current spin polarization. The mobility and the spin-flip time of carriers in organic and inorganic semiconductors are different. From the calculation, it is found that current spin polarization at a ferromagnetic/organic interface is higher than that at a ferromagnetic/inorganic interface because of different carriers in them. Effects of the conductivity matching, the spin dependent interracial resistances, and the bulk spin polarization of the ferromagnetic layer on the spin polarized injection are also discussed.     

有机无机肥配施黑土胡敏酸结构光谱学特征

土壤有机质是土壤的重要组成部分,在土壤肥力、环境保护、农业可持续发展等方面都具有重要作用。腐殖质作为土壤有机质的主体,对土壤的一系列性质和形态产生影响,其数量、组成和性质可以反映一定的成土条件和过程,是土壤肥力的重要指标。由于腐殖质分子组成的不确定性,各种方法均存在一定的局限性,优化寻求更为准确可靠的腐殖酸表征方法已成为当前研究的热点。施肥方式改变土壤中胡敏酸的组成与结构,但短期的影响程度难以用常规的测定技术检测出来。利用38年的黑土长期定位试验,通过腐殖质组分HA的分离和纯化,多种光谱分析方法的联合应用,从物质结构的角度分析土壤中单施有机肥和有机无机肥配施对黑土HA有机化合物的分子结构变化的影响。分析显示,M和MNPK施肥处理较CK处理均可提高土壤有机碳和HA含量,增加土壤中HA的总反应热、中温放热值、2920/1720值、脂族C含量、f450/500值,表明单施有机肥和有机无机肥配施后土壤HA芳构化程度降低,脂族含量增加,结合简单化,但M施肥处理增加幅度小于MNPK施肥处理。分析结果表明：多种光谱技术的联合应用,可以相互认证其结果的准确性。同时试验结果也证明有机无机肥配施较单施有机肥,更能提高土壤有机碳和土壤HA的脂族C含量,增加作物产量,培肥地力。     

Luminescence of molecules adsorbed on surfaces of wide gap materials

We report on the photoluminescence spectra of thin films of chain-like π-conjugated molecules on well-defined surfaces of wide gap inorganic materials. The aim is to study the energy transfer processes across the organic/substrate interface which limit the luminescence of molecules in close contact to substrate surfaces. We discuss quaterthiophene (4 T) adsorbed on the c(2×2)-ZnSe(0 0 1) surface and tetracene (Tc) on the surface of a thin epitaxial Al₂O₃ film on Ni₃Al(1 1 1). For thin films vapor-deposited at low substrate temperatures, we observe no luminescence signal for both systems, which indicates the presence of fast luminescence quenching processes at the organic/inorganic interface. After annealing, luminescence spectra corresponding to those of the bulk crystals are obtained. This can be explained by the formation of 3D-crystallites, which effectively separate most molecules from the organic/inorganic interface.     

Electronic,structural and chemical effects of charge-transfer at organic/inorganic interfaces

During the last decade, interest on the growth and self-assembly of organic molecular species on solid surfaces spread over the scientific community, largely motivated by the promise of cheap, flexible and tunable organic electronic and optoelectronic devices. These efforts lead to important advances in our understanding of the nature and strength of the non-bonding intermolecular interactions that control the assembly of the organic building blocks on solid surfaces, which have been recently reviewed in a number of excellent papers. To a large extent, such studies were possible because of a smart choice of model substrate-adsorbate systems where the molecule-substrate interactions were purposefully kept low, so that most of the observed supramolecular structures could be understood simply by considering intermolecular interactions, keeping the role of the surface always relatively small (although not completely negligible). On the other hand, the systems which are more relevant for the development of organic electronic devices include molecular species which are electron donors, acceptors or blends of donors and acceptors. Adsorption of such organic species on solid surfaces is bound to be accompanied by charge-transfer processes between the substrate and the adsorbates, and the physical and chemical properties of the molecules cannot be expected any longer to be the same as in solution phase. In recent years, a number of groups around the world have started tackling the problem of the adsorption, self- assembly and electronic and chemical properties of organic species which interact rather strongly with the surface, and for which charge-transfer must be considered. The picture that is emerging shows that charge transfer can lead to a plethora of new phenomena, from the development of delocalized band-like electron states at molecular overlayers, to the existence of new substrate-mediated intermolecular interactions or the strong modification of the chemical reactivity of the adsorbates. The aim of this review is to start drawing general conclusions and developing new concepts which will help the scientific community to proceed more efficiently towards the understanding of organic/inorganic interfaces in the strong interaction limit, where charge-transfer effects must be taken into consideration.     

Theoretical Study of the Electronic and Optical Properties of a Heterostructure Based on PTCDA Organic Semiconductor and MoSe2

JETP Letters - The structural and physicochemical properties of the MoSe2/PTCDA heterostructure, which consists of two-dimensional inorganic and molecular organic semiconductors, have been studied...     

Exciton effects in disordered semiconductors

Experimental data on optical and photoelectric properties of molecular (polymeric) disordered semiconductors of inorganic and organic nature are analyzed. It is shown that anomalies in optical properties and in the structure of the internal photoeffect quantum-yield spectrum can be understood by assuming the existence of exciton states in disordered semiconductors.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 2, pp. 86–101, February, 1976.The author is grateful to Prof. S. G. Grenishin for his interest in this work.     

Device relevant organic films and interfaces: A surface science approach

Here the morphology, molecular orientation and electronic structure of in situ prepared para-sexiphenyl (6P) and α-sexithiophene (6T) films studied with atomic force microscopy, near edge X-ray absorption fine structure spectroscopy and valence band photoemission are presented. Attention is given to the differences between different organic crystallite orientations and the pitfalls in the interpretation of area averaging surface sensitive techniques that can arise from inhomogeneities in the films, which commonly occur even on single crystal inorganic substrates. The growth of organic-organic heterostructures is then considered for sexithiophene films grown on homogeneous upright (6P(0 0 1)) and lying (6P(2 0 3)) crystalline films. In both cases, the orientation of the substrate molecules is imposed on the molecules of the second species and thick films of upright-on-upright or lying-on-lying could be produced. The organic substrates are thus shown to be excellent templates for further organic film growth that do not require the stringent UHV conditions of inorganic templates.     

Non-covalent interaction controlled 2D organic semiconductor films: Molecular self-assembly,electronic and optical properties,and electronic devices

The establishment of electronic and opto-electronic products relying on organic semiconductors (OSCs) has been intensely explored over the past few decades due to their great competitiveness in large area, low cost, flexible, wearable and implantable devices. Many of these products already entered our daily lives, such as organic light-emitting diodes-based displays, portable organic solar cells and organic field-effect transistors. The device performance of OSC devices are determined by the supramolecular organization (orientation, morphology) as well as the supramolecular organization dependent energy level alignment at various interfaces (organic/electrode, organic/dielectric, organic/organic). This review focuses on the impact of non-covalent interaction on the molecular self-assembly of organic thin films, their electronic and optical properties, as well as the device performance. Beginning with the growth of multiple OSCs on substrates with different interfacial interaction strengths (metals, insulators, semiconductors), the critical roles of molecule-substrate and intermolecular interactions in determining the thin film organization have been demonstrated. Several non-covalent interactions that contribute to the energy levels of organic materials in solid phase are summarized, mainly including the induction contributions, electrostatic interactions, band dispersions and interface dipoles. The excitonic coupling in specific aggregations of organic molecules and the corresponded effect on their optical properties are also discussed. Finally, the influences of weak intermolecular interactions on the device performance are presented.     

Influence of urea on polyvinyl alcohol molecular superstructure formation

Whiskers up to 1 cm in length were grown in polyvinyl alcohol (PVA) and urea solution. Raman and IR spectra discover an interaction between PVA and urea molecules. Optical and electronic microscopy data show that urea influences on PVA molecular superstructure formation. PVA whiskers prepared in urea solution can be used for organic semiconductors production which properties are determined by arrangement of polymer macromolecules.     

Electronic structure of organic interfaces – a case study on perylene derivatives

Organic semiconductors have attracted increasing interest owing to their potential application in various electronic and opto-electronic devices. Here, interfaces play an important role since they are responsible for the accumulation of charge carriers at and the efficiency of charge injection across interfaces. Both mechanisms are determined by the alignment of energy levels at the interface. This report is divided into two parts and presents some of the major physical mechanisms which determine the energy level alignment at interface of thin films of low molecular weight organic semiconductors. In the first part, the origin of interface dipoles, interface states, and surface band bending is discussed. In the second part, investigations on the properties of metal/perylene derivatives/inorganic semiconductor structures give further insight into the mechanisms at work, especially under non-thermal equilibrium conditions. PACS 73.20.-r; 73.40.-c; 79.60.Jv; 79.60.Fr     

The ‘size matching rule’ in di-, tri-, and tetra-cationic charged porphyrin/synthetic clay complexes: effect of the inter-charge distance and the number of charged sites

Novel inorganic/organic hybrids formed from cationic porphyrins and synthetic clay were investigated. Di-, tri- and tetra-cationic charged porphyrins with different distances between adjacent cationic sites within the molecules were incorporated into the hybrids with synthetic clay. When tetra-cationic porphyrins were used, in which distances between adjacent cation sites were 1.05 and 1.31 nm, the porphyrin molecules adsorb on the clay surfaces with high density, neutralizing all of the negative charges of the clay surface, i.e. 100% adsorption vs. the cation exchange capacity (CEC), without aggregation, even though it is generally difficult to control or suppress the aggregation of organic molecules on inorganic surfaces. The mean center-to-center distance between porphyrin molecules in the hybrids was estimated to be 2.4 nm. When Δl (the difference between the inter-cationic charge distance in the porphyrin molecule and the inter-anionic charge distance on the clay surface) was larger than ca. 0.2 nm, the porphyrin molecules adsorbed in amounts smaller than 100% vs. CEC. In the cases of di- and tri-cationic charged porphyrins, similar adsorption behavior was observed. The formation of these unique hybrids was rationalized by a size-matching of distances between the charged sites in the porphyrin molecule and on the clay surface (‘size-matching rule’).     

Electronic correlations in oligo-acene and -thiopene organic molecular crystals

From first-principles calculations we determine the Coulomb interaction between two holes on oligo-acene and -thiophene molecules in a crystal, as a function of the oligomer length. The electronic polarization of the molecules that surround the charged oligomer reduces the bare Coulomb repulsion between the holes by approximately a factor of 2. The effects of relaxing the molecular geometry in the presence of holes is found to be significantly smaller. In all cases the effective hole-hole repulsion is much larger than the valence bandwidth, which implies that at high doping levels the properties of these organic semiconductors are determined by electron-electron correlations.     

有机超微粒的制备及其尺寸效应的研究

有机超微粒是国际上刚刚起步的研究领域，是纳米科技领域和有机光电子领域的重要前沿课题，文章从有机功能小分子出发，在制备粒径和形状可控的，高度单分散的纳米超微粒的基础上，首次系统地研究了有机超微粒的电子态随尺寸大小的变化过程，发现有机超微粒和无机超微粒一样具有显著的尺寸效应，而且更具多样性，该项研究工作为探索和比较无机和有机材料介观尺寸效应的异同点这一科学问题奠定了坚实的基础，对于理解有机分子晶体这类传统材料中的基本过程和现象以及开发新型光电材料和器件也极具意义。     

有机超微粒的制备及其尺寸效应的研究

有机超微粒是国际上刚刚起步的研究领域,是纳米科技领域和有机光电子领域的重要前沿课题.文章从有机功能小分子出发,在制备粒径和形状可控的、高度单分散的纳米超微粒的基础上,首次系统地研究了有机超微粒的电子态随尺寸大小的变化过程.发现有机超微粒和无机超微粒一样具有显著的尺寸效应,而且更具多样性.该项研究工作为探索和比较无机和有机材料介观尺寸效应的异同点这一科学问题奠定了坚实的基础,对于理解有机分子晶体这类传统材料中的基本过程和现象以及开发新型光电材料和器件也极具意义.     

Alkali metal doping and energy level shift in organic semiconductors

We have investigated Cs and Na doping in copper phthalocyanine (CuPc) and tris(8-hydroxyquinoline) aluminum (Alq) using photoemission spectroscopy. We observed valence and core level spectra changes at different doping levels, and found that the doping induces an energy level shift that can be seen in two different stages. The first stage is predominantly due to the Fermi level moving in the energy gap as a result of the doping of electrons from the alkaline metal to the organic, and the second stage is characterized by a significant modification of organic energy levels, such as the introduction of a new gap state, new core level components and a change of binding energies. Furthermore, we observed that the energy level shift in the first stage depends in a semi-logarithmic fashion on the doping concentration, whose slope cannot be explained by the conventional model used in inorganic semiconductors. These results indicate that the molecular nature and strong correlation must be considered for doping in organic semiconductors.     

Evolution of the unoccupied states in alkali metal-doped organic semiconductor

The evolution of the electronic structure, especially the unoccupied states, induced by alkali metal doping has been investigated with photoemission and inverse photoemission spectroscopy for organic semiconductors, such as copper-phthalocyanine (CuPc) and tris(8-hydroxyquinoline) aluminum (Alq). The n-type doping leads to a downward shift for the lowest unoccupied molecular orbital (LUMO) of the organic semiconductors, until the edge of the LUMO reaches the Fermi level. After that, the LUMO intensity decreases monotonically, while a gap state grows in the valence spectra, which gives direct evidence for the origin of the doping-induced gap state in organic molecules. The modification of the LUMO intensity, as well as that of the gap state, suggests the formation of multiply charged anions in heavily doped film.