The interplay of topography and energy dissipation in pentacene thin films

Nonlinear photoemission electron microscopy was used to study the morphology-dependent lifetime of electronic excitations in pentacene islands on Si(0 0 1) and (√3 × √3)R30°-Ag/Si(1 1 1). After an optical excitation of electrons by a λ = 400 nm femtosecond laser pulse the characteristic decay times were measured with spatial resolution in a pump-probe setup. For pentacene on Si(0 0 1), the observed lifetimes vary by a factor of two between the wetting layer and the fractal-shaped pentacene islands. The measured lifetime difference is explained by a difference in the electronic coupling of the pentacene islands and the wetting layer to the substrate. For pentacene on (√3 × √3)R30°-Ag/Si(1 1 1), similar lifetimes are found, although the orientation of the pentacene molecules in the compact islands is rotated. Our findings suggest that electronic excitations in higher layers of the pentacene islands do not diffuse to the interface before they decay.     

Work function, valence band and secondary ion intensity variations noted during the initial stages of SIMS depth profiling of Si and SiO2 by Cs

Work function, valence band and ²⁸Si⁻ secondary ion intensity variations from various Si substrates sputtered by 1 keV Cs⁺ at 60° were measured. Oxide free Si wafers and native oxide terminated wafers did not reveal any appreciable valence band variations close to the Fermi edge. Their work functions however, decreased substantially with an exponential trend noted between this and Si⁻ secondary ion intensities from the O free Si wafer. This is consistent with the electron tunneling model which assumes a resonance charge transfer process. Native oxide terminated wafers exhibited deviations from this exponential trend, while Si wafers with thicker oxides revealed the growth of sub-band features in the valence band spectra on sputtering with Cs⁺. These features, may partially, if not fully, explain the Cs⁺ induced enhancement effect noted on SiO₂ substrates where work function based models are not applicable.     

Growth and characterization of thin PTCDA films on 3C-SiC(0 0 1)c(2 × 2)

The growth of thin 3,4,9,10-perylene tetracarboxylic dianhydride (PTCDA) films on a 3C-SiC(0 0 1)c(2 × 2) substrate has been studied by means of photoelectron spectroscopy (PES) and atomic force microscopy (AFM). In the first monolayer the molecules interact with the substrate mainly through the O atoms in the end groups of the molecule. The O atoms have a higher binding energy in the first molecular layer compared to the following layers. No chemical shifts are observed in the Si 2p spectra or in the C 1s spectra from the perylene core of the molecules. From the VB spectra and LEED pattern we conclude that the substrate remains in the c(2 × 2) reconstruction after PTCDA deposition. For thicker films a Stranski-Krastanov film growth was observed with flat lying molecules relative to the substrate.     

Impact of interface geometric structure on organic–metal interface energetics and subsequent films electronic structure

We present the electronic structure of various pentacene thin films grown on Au(1 1 1), Cu(1 1 1), Cu(1 0 0), and Cu(1 1 0) surfaces studied by angle-resolved ultraviolet photoemission spectroscopy using synchrotron radiation. A systematic variation of the metal surface such as the substrate metal and its surface symmetry allows a comprehensive discussion on the correlation between the electronic structure and the interface geometric structure. In the monolayer regime, we observed the evidence of the formation of the organic–metal interface state depending on the metal surface, i.e., the interface geometric structure. This evidence is explained by the different organic–metal and intermolecular interactions, which originate from the hybridization of the molecular orbitals with the metal wavefunction. These interface geometric and electronic phenomena can be a seed for the subsequent film growth and resultant films electronic structure.     

Adsorption of thiophene on Al(1 1 1) and deposition of aluminum on condensed thiophene

The adsorption of thiophene on clean Al(1 1 1) at 90 and 130 K has been studied with X-ray and ultraviolet photoelectron spectroscopy (XPS and UPS) and work function measurements. Relatively weak chemisorption compared to adsorption on transition metals is indicated by minor changes in the valence spectrum in progressing from monolayer to multilayer thiophene, a modest work function change of −0.50 eV due to saturation dosing, and return of the work function and valence spectrum to that of clean Al(1 1 1) upon annealing at 210 K. The complementary experiment in which aluminum is thermally deposited on multilayer thiophene condensed on gold at 130 K has also been performed. XPS peak area analysis shows that metal doses less than 14×10¹⁵ atoms/cm² result in penetration through the physisorbed thiophene, but higher doses lead to the gradual build up of metal throughout the organic layer. Persistence of the thiophene UPS valence features for metal doses of 50×10¹⁵ atoms/cm² is consistent with penetration and aluminum island formation. For aluminum deposition on thiophene, charge transfer from aluminum is evidenced by metal-induced low binding energy components in the C 1s and S 2p spectra at 282.6 and 162.5 eV, respectively, and a shift in the Al 2p spectrum of 0.5 eV to higher binding energy compared to metallic aluminum. UPS also indicates progression of the frontier orbital toward the Fermi level as aluminum is deposited.     

Mapping of the electronic work function anisotropy of RF sputtered molybdenum thin film electrodes for piezoelectric devices

Amplitude modulated Kelvin probe force microscopy was performed on molybdenum (Mo)-thin films deposited on Si(001) substrates by RF magnetron sputtering. Evolution of film microstructure from amorphous to crystalline was observed with increasing RF power from 25 W to 200 W. Spatial mapping of work function across the film surface revealed that the Mo-thin film deposited at 200 W possesses an average work function ~4.94 ± 0.06 eV while higher values were observed at lower RF powers. The genesis of distinct periodic changes in work function is attributed to the formation of the surface dipole layer associated with the adsorbates of different polarities (O₂⁻/OH⁻ or H⁺). A phenomenological model is also presented to elucidate their effect.     

Co掺杂ZnO薄膜的局域结构和电荷转移特性研究

采用磁束缚电感耦合等离子体溅射沉积法在不同的氧气分压下制备了Zn_0.95Co_0.05O和Zn_0.94Co_0.05Al_0.01O薄膜.利用X射线吸收精细结构技术对薄膜O-K,Co-K和Co-L边进行了局域结构研究,结果表明：Co²⁺取代了四配位晶体场中的Zn²⁺而未改变ZnO的六方纤锌矿结构,高真空条件下制备的薄膜 关键词： Co掺杂ZnO 稀磁半导体 X射线吸收精细结构 共振非弹性X射线散射     

The relationship between the crystallographic order and electronic structure of mercury thin films

Thin (1–7 monolayer) well ordered, disordered, and liquid Hg overlayers on Ag (100) have been investigated with angle resolved photoemission and low energy electron diffraction. The well ordered overlayers exhibit new electronic states as a result of the strained, cubic, overlayer crystallographic structure. The photoemission cross section of the electronic states depends on the overlayer long range crystallographic order and cannot be explained by photoelectron diffraction. The new electronic states depend upon the long range crystallographic order of the overlayer not simply the local crystallographic symmetry, a heretofore unreported result.     

PEEM study of work function changes in Cu, Au and Pd metal surfaces with surface acoustic wave propagation

The effects of surface acoustic wave (SAW) on the work function of Cu, Au and Pd metal surfaces with different surface structures were studied by photoelectron emission microscopy (PEEM). SAW propagation produced bright PEEM images for Cu, Au and Pd metal surfaces consisting of high-index planes and step sites, whereas it yielded dark images for the metals exposing low-index planes, indicating that the SAW enhanced photoemission from rough metal surfaces containing coordinatively-unsaturated metal atoms and lowered that from densely packed smooth metal surfaces. Changes in the PEEM images with SAW-on and SAW-off were reversible and were associated with decreases and increases in the work function of the metal surfaces, respectively. The SAW caused periodic and vertical lattice displacement, and it was demonstrated that large lattice displacement was responsible for work function changes from coincidence between the patterns of photoemission and lattice displacement. A mechanism for work function changes is proposed on the basis of effects on the spatial structures and electronic properties of metal surfaces.     

Molecular level alignment and work function change of dimethyl-disulfide physisorbed thin films on Au(1 1 1)

The formation and the electronic properties of a dimethyl-disulfide (DMDS) thin film adsorbed at low temperature on the Au(1 1 1) surface has been studied by means of Ultraviolet Photoemission Spectroscopy. The dependence of the binding energy of the molecular states as a function of coverage has been analyzed and compared to the corresponding work function change. A deviation from the expected rule for the molecular level alignment is observed and attributed to the differences between local and average work function. The effect of a buffer thiolated monolayer, obtained by dosing DMDS at room temperature, on the evolution of the interface electronic properties is also analyzed and discussed.     

The effect of carbon contamination and argon ion sputtering on the work function of chlorinated indium tin oxide

The work function of indium tin oxide (ITO) was increased by treating ITO with dichlorobenzene with UV light. Carbon contamination of the Cl-ITO was measured using X-ray Photoelectron Spectroscopy (XPS) and argon ion sputtering was used to remove the carbon from the surface. It was found that the carbon contamination from residual dichlorobenzene significantly lowered the work function of the ITO and after argon ion sputtering the work function increased to 5.8 eV. It was found that chlorination of ITO occurs after more than 6 min of UV exposure. Further sputtering of ITO resulted in the removal of the functionalized chlorine, the introduction of argon ion contaminants on the ITO decreases its work function.     

The influence of using different substrates on the structural and optical characteristics of ZnO thin films

ZnO thin films with thikness d = 100 nm were deposited onto different substrates such as glass, kapton, and silicon by radio frequency magnetron sputtering. The structural analyses of the films indicate they are polycrystalline and have a wurtzite (hexagonal) structure.The ZnO layer deposited on kapton substrate shows a stronger orientation of the crystallites with (0 0 2) plane parallel to the substrate surface, as compared with the other two samples of ZnO deposited on glass and silicon, respectively.All three layers have nanometer-scale values for roughness, namely 1.7 nm for ZnO/glass, 2.4 nm for ZnO/silicon, and 6.8 nm for ZnO/kapton. The higher value for the ZnO layer deposited on kapton substrate makes this sample suitable for solar cells applications. Transmission spectra of these thin films are strongly influenced by deposition conditions. With our deposition conditions the transparent conducting ZnO layer has a good transmission (78-88%) in VIS and NIR domains. The values of the energy gap calculated from the absorption spectra are 3.23 eV for ZnO sample deposited onto glass substrate and 3.30 eV for the ZnO sample deposited onto kapton polymer foil substrate. The influence of deposition arrangement and oxidation conditions on the structural, morphological, and optical properties of the ZnO films is discussed in the present paper.     

Growth mode and electronic structure of Au nano-clusters on NiO(0 0 1) and TiO2(1 1 0)

The growth mode and electronic structure of Au nano-clusters grown on NiO and TiO₂ were analyzed by reflection high-energy electron diffraction, a field-emission type scanning electron microscope, medium energy ion scattering and photoelectron spectroscopy. Au was deposited on clean NiO(0 0 1)-1 × 1 and TiO₂(1 1 0)-1 × 1 surfaces at room temperature with a Knudsen cell at a rate of 0.25-0.35 ML/min (1 ML = 1.39 × 10¹⁵ atoms/cm²:Au(1 1 1)). Initially two-dimensional (2D) islands with thickness of one Au-atom layer grow epitaxially on NiO(0 0 1) and then neighboring 2D-islands link each other to form three-dimensional (3D)-islands with the c-axis oriented to the [1 1 1] direction. The critical size to form 3D-islands is estimated to be about 5 nm². The shape of the 3D-islands is well approximated by a partial sphere with a diameter d and height h ranging from 2.0 to 11.8 nm and from 0.95 to 4.2 nm, respectively for Au coverage from 0.13 to 4.6 ML. The valence band spectra show that the Au/NiO and Au/TiO₂ surfaces have metallic characters for Au coverage above 0.9 ML. We observed Au 4f spectra and found no binding energy shift for Au/NiO but significant higher binding energy shifts for Au/TiO₂ due to an electron charge transfer from Au to TiO₂. The work function of Au/NiO(0 0 1) gradually increases with increase in Au coverage from 4.4 eV (NiO(0 0 1)) to 5.36 eV (Au(1 1 1)). In contrast, a small Au deposition(0.15 to 1.5 ML) on TiO₂(1 1 0) leads to reduction of the work function, which is correlated with an electron charge transfer from Au to TiO₂ substrate.     

有机半导体perylene和tetracene在Ag(110)表面上有序薄膜的结构与电子态研究

利用紫外光电子能谱(UPS)和低能电子衍射(LEED)对银(110)表面上perylene与tetracene的生长进行了研究.LEED的结果表明：一个分子单层的perylene在银(110)表面上会形成C(6×2)的有序结构；一个分子单层的tetracene，观察到的则是C(4×2)的有序结构.根据UPS的测量，与perylene分子轨道有关的4个特征峰分别位于Frimi能级以下35，48，64和85eV处，与tetracene分子轨道有关的4个特征峰的结合能分别为3．4，49，59和94eV.角分辨紫外光电子能谱(ARUPS)的测量表明，表面附近的perylene和tetracene分子平面平行于银衬底表面，tetracene分子的长轴可以确定沿［110］晶向. 关键词： 有机半导体材料 紫外光电子能谱 结构和电子结构     

Study of the interactions between the overlayer and the substrate in the early stages of palladium growth on TiO2(1 1 0)

The interaction between palladium and the (1 1 0) surface of a TiO₂ single crystal and the electronic properties of the system were studied by means of photoelectron spectroscopy (core levels and valence band) and resonant photoemission for Pd coverage in the sub- and monolayer range. We performed the metal depositions at room temperature. Similarly to copper, platinum and rhodium, palladium does not reduce titanium, has metallic character already from a quite early deposition, grows with a 3D-island mode and the interactions between palladium and TiO₂ are very weak. Annealing treatments at 400 °C provoke a change in the morphology of the palladium clusters and the formation of islands characterized by a higher ratio between volume and area in contact with the substrate.