Chemical bonding and electronic structures at magnesium/copper phthalocyanine interfaces

Chemistry, electronic structure and electrical behavior at the interfaces between copper phthalocyanine (CuPc) and Mg with a reverse formation sequence were investigated using X-ray photoemission spectroscopy (XPS), ultraviolet photoemission spectroscopy (UPS), and current-voltage (I-V) measurements. A chemical reaction occurs between CuPc and Mg irrespective of the deposition sequence. Despite having different reaction zone thicknesses, both the CuPc-on-Mg and the Mg-on-CuPc interfaces exhibit chemistry-induced gap states and identical carrier injection barriers, which are confirmed by the symmetric electrical behavior obtained from I-V characteristics of devices with a structure of Mg/CuPc/Mg. These findings contrast with those expected from physisorptive noble metal-CuPc interfaces and suggest that strong local chemical bonding is a primary factor determining molecular level alignment at reactive metal-CuPc interfaces.     

Structure modification of highly ordered pyrolytic graphite by Ar plasma beam scanning at different incident angles

The surface of highly ordered pyrolytic graphite (HOPG) was modified by Ar plasma beam scanning at a controllable angle of incidence. The characteristics of plasma modified HOPG were investigated by atomic force microscope (AFM), micro-Raman, X-ray photoemission spectroscopy (XPS), and grazing incident angle of X-ray diffraction (GIAXRD). A smooth surface of HOPG can be obtained by adjusting the incident angles of Ar plasma beam scanning. The surfaces of HOPG become smoother with increasing angle of incidence after Ar plasma beam scanning. Raman spectra indicate that the plasma beam scanning breaks the hexagonal structures of sp² C=C bonds near the surface of HOPG. The broken hexagonal network structures can form C–O bonds that increase the amount of oxygen on the surface of HOPG, supported by C_1s and O_1s XPS spectra. GIAXRD data support that the co-existence of both crystalline structures of 2H and 3R in HOPG. The carbon bond breaking in 2H and 3R is different and depends on the angle of incidence. Most broken carbon bonds form damaged aromatic rings near the surface of HOPG.     

Charge transfer at F<Subscript>16</Subscript>CoPc and CoPc interfaces to Au

We analyze the electronic properties of the interfaces between cobalt phthalocyanine (CoPc), as well as fluorinated cobalt phthalocyanine (F₁₆CoPc), and an Au(100) single-crystal using X-ray photoemission spectroscopy and valence band ultraviolet photoemission spectroscopy. Our data demonstrate that for the monolayers of both materials a charge transfer occurs from the substrate to the center of the organic molecules resulting in a central Co(I) ion. This leads to the conclusion that this effect essentially is fluorination- and ligand-independent.     

Work function measurements on indium tin oxide films

We determined the work function of indium tin oxide (ITO) films on glass substrates using photoemission spectroscopy (PES). The ITO coated glass substrates were chemically cleaned ex-situ, oxygen plasma treated ex-situ, or sputtered in-situ. Our results suggest that the performance of ultraviolet photoemission spectroscopy (UPS) measurements can induce a significant work function reduction on the order of 0.4–0.5 eV, on ex-situ chemically and oxygen-plasma treated ITO samples. This was demonstrated by the use of low intensity X-ray photoemission spectroscopy (XPS) work function measurements before and after the UPS measurements were carried out.     

Fabrication of Mg-doped ZnO thin films by laser ablation of Zn:Mg target

Mg-doped ZnO thin films were fabricated by laser ablation of Zn:Mg targets consisting of Mg metallic strips and Zn disk in oxygen atmosphere with a goal to facilitate convenient control of Mg contents in the films. The characteristics of the deposited films were examined by analyzing their photoluminescence (PL), X-ray diffraction and X-ray photoelectron spectroscopy (XPS) spectra. Mg contents as analyzed by XPS indicate that the target composition is fairly transferred to the deposited films. The wurtzite structure of ZnO was conserved even for the highly doped ZnO films and there was no Mg- or MgO-related XRD peaks. With increase in the Mg content, the bandgap and PL peak energy shifted to blue and the Stokes shift became larger.     

X-ray photoelectron spectroscopic,electrical and magnetic studies on Mg2NiH4

X-ray photoelectron and X-ray induced Auger spectroscopic (XPS and XAES) investigations show that, in Mg₂NiH₄, both Mg and Ni are in the metallic state. Support for this observation has been obtained from thermopower and magnetic measurements.     

X-ray photoemission study of MgB<Subscript>2</Subscript> films synthesized from in-situ annealed MgB<Subscript>2</Subscript>/Mg multilayers

Superconducting MgB₂ films were obtained by in-situ annealing of precursor multilayers deposited at low substrate temperature by sputtering from a MgB₂ stoichiometric target and by thermal evaporation of pure Mg. After an in-situ annealing at 500–600 °C, the films showed a zero resistance critical temperature up to 31 K. The as-obtained MgB₂ films were investigated by X-ray photoelectron spectroscopy (XPS) and X-ray auger electron spectroscopy (XAES). The electronic structure was studied by monitoring the B 1s, Mg 2p, O 1s core-levels and the Mg KL₂L₃ Auger line. For comparison, the electronic structure of an MgB₂ commercial superconducting sputtering target, of a not-annealed precursor film and of a sample obtained by direct sputtering from the MgB₂ target have also been investigated. Electron spectroscopy showed that in the superconducting systems the Mg KL₂L₃ Auger line kinetic energy position is always higher by about 0.9 eV with respect to the energy position of the same Auger line measured in the non-superconducting samples. PACS 74.25Jb; 74.78.Bz; 74.70.Ad     

Electronic structure of the organic semiconductor copper tetraphenylporphyrin (CuTPP)

The electronic structure of thin films of the organic semiconductor copper tetraphenylporphyrin (CuTPP) has been studied using synchrotron radiation-excited resonant soft X-ray emission spectroscopy (RSXE), near edge X-ray absorption fine structure (NEXAFS) spectroscopy, and X-ray photoemission spectroscopy (XPS). The C and N partial density of states for both the valence and conduction band electronic structure has been determined, while XPS was used to provide information on the chemical composition and the oxidation states of the copper. Good agreement was found between the experimental measurements of the valence and conduction bands and the results of density functional theory calculations.     

Structural and magnetic characterization of soft-magnetic FeCo alloy nanoparticles

Soft-magnetic FeCo alloy nanoparticles with diameters less than 100 nm are prepared by ball milling. X-ray photoemission spectroscopy (XPS) and X-ray magnetic circular dichroism (XMCD) are used to characterize these particles. While the XPS spectrum from the as-prepared sample clearly shows Co photoemission peaks, no sign of Fe is observed in the same spectrum. However, Fe photoemission peaks appear after 1 h of Ar ion sputtering. A quantitative analysis of the XPS spectra shows an increase of Fe concentration versus sputtering time until the Fe:Co ratio of the bulk alloy is reached. In addition, the narrow scan Fe and Co 2p XPS spectra show that Co is more oxidized than Fe. All these measurements indicate that the nanoparticles have a Co shell and an Fe-rich core. They further demonstrate the usefulness of XPS combined with depth-profiling via sputtering to obtain element- and chemically-sensitive structural information on nanoparticles. XMCD as an element-specific magnetic analysis tool further reveals that Fe and Co are ferromagnetically coupled in these particles. The information obtained is useful for establishing a structure–property relation for the studied material that is expected to have applications as a soft magnetic material at high temperatures.     

Photoelectron spectroscopy of nanocrystalline anatase TiO2 films

Nanocrystalline TiO₂ (anatase) films were prepared using either colloidal suspensions or a sol-gel route. The electronic structure of these films was analyzed using X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS). Apart from pristine films, films containing defects introduced by annealing under ultra-high vacuum conditions or by ion bombardment were investigated. Generally, annealing in the temperature range up to 720 K results in no significant changes in the XPS and UPS spectra as compared to the pristine state, indicating that the amount of defect formation is too low to be observable by these techniques. On the other hand, ion irradiation causes the appearance of distinct defect states; these could be identified in agreement with previous data from photoemission studies on rutile and anatase single crystals. From UPS, a valence-band width of ∼4.6 eV was determined for the nanocrystalline anatase films.     

Effect of heat treatment on chemical and electronic structure of solid SiO : An electron spectroscopy study

Photoelectron spectroscopy (XPS and UPS) and X-ray excited Auger electron spectroscopy (XAES) measurements for commercial SiO powder and for SiO thin films show direct evidence for the evolution of the chemical structure of SiO from a characteristic metastable phase to a microscopic mixture of Si and SiO₂ when the temperature increases.     

Spectroscopic analysis of CIGS2/CdS thin film solar cell heterojunctions on stainless steel foil

This paper presents a spectroscopic analysis of the interface between a CuIn_1−xGa_xS₂ (CIGS2) absorber and a CdS buffer layer on stainless steel foil by Auger electron spectroscopy (AES), inverse photoemission spectroscopy (IPES) and photoelectron spectroscopy (PES) such as X-ray photoelectron spectroscopy (XPS), and ultraviolet photoelectron spectroscopy (UPS). By combining these spectroscopic techniques, detailed information about the electronic and chemical properties of the CIGS2 surface and the CdS/CIGS2 interface can be obtained. The gallium concentration in CIGS2 films was found to increase continuously towards the Mo back contact. XPS analysis showed the presence of KCO₃ on the surface of CdS, deposited on etched and un-oxidized samples indicating diffusion of potassium. No potassium was observed on oxidized as well as samples having thicker CdS (50 nm) indicating the effectiveness of oxidation and chemical bath deposition (CBD) process in cleaning the sample surface effectively. In addition, investigation of the electronic level alignment at the interface has been carried out by combining PES and IPES. Conduction band offset of −0.45 (±0.15) eV and a valence band offset of −1.06 (±0.15) eV were measured. These unfavorable conditions limit efficiency of CIGS2 thin film solar cells.     

Defect induced ferromagnetism in carbon-doped ZnO thin films

We report on room temperature ferromagnetism in C-doped ZnO thin films prepared by electron beam evaporation. Magnetization, Hall effect, X-ray photoemission spectroscopy (XPS) and X-ray diffraction studies have been conducted to investigate the source and nature of ferromagnetism in C-doped ZnO. The samples were observed to have n-type conduction with the carrier concentration increasing with C doping. XPS does not give any evidence for C substituted at the O site, and is more consistent with the formation of C-O bonds and with the presence of C primarily in the +4 state. It is suggested that the ferromagnetism originates in the development of Zn vacancies that are stabilized due to the incorporation of C in a high valence state (C⁴⁺).     

Chemical and microstructural study of the oxygen passivation behaviour of nanocrystalline Mg and MgH2

Nanocrystalline Mg and MgH₂ samples have been prepared by high-energy ball milling and gas phase condensation methods. Starting from these materials in their “as received” state without air exposure, a study of the oxygen and air passivation behaviour was carried out by “in situ” analysis of the samples by X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM). The binding energy and photoemission Auger parameters have been determined for metallic magnesium as well as for magnesium hydride, oxide and hydroxide species. Values of the MgH₂ material were reported for the first time. The study clearly shows the formation of an oxide passivation layer of ca. 3-4 nm in thickness for all the nanocrystalline magnesium samples handled under controlled inert gas atmospheres. A hydroxide like amorphous layer is formed at the topmost surface layers of the nanocrystalline Mg and MgH₂ samples. The implication of these studies for H₂ storage and transport applications of nanocrystalline magnesium is discussed.     

Thermally activated dewetting of organic thin films: the case of pentacene on SiO<Subscript>2</Subscript> and gold

The morphology of pentacene organic thin films deposited on SiO₂ and Au(111) surfaces using organic molecular beam deposition (OMBD) has been characterized by a multi-technique approach. Among the techniques applied were X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), scanning electron microscopy (SEM) and thermal desorption spectroscopy (TDS). Our rather detailed studies reveal that on both substrates the growth is strongly influenced by dewetting and islanding phenomena, yielding very rough surfaces. Surprisingly, substantial changes in the morphology were observed also after deposition on room-temperature samples on a time scale of several hours. The rather extensive set of in situ XPS data was analyzed in the framework of a simple model, which allows us to derive rather detailed information on the roughness parameters.     

Thickness dependence of X-ray absorption and photoemission in Fe thin films on Si(0 0 1)

To investigate the initial growth of Fe films on Si(0 0 1) and the Fe/Si interface, Fe films at various thicknesses have been systematically studied by soft X-ray absorption spectroscopy (XAS) and X-ray photoemission spectroscopy (XPS). The Fe L edge XAS spectrum shows a strong thickness dependence with broader line-width for thinner films. Detailed analysis of the Fe absorption signal as a function of the thickness shows that the broad linewidth of Fe L edge XAS spectra is mostly contributed by the first Fe layer at the Fe/Si interface. In contrast to XAS, Fe 2p photoemission spectra for these films are identical. However, valence band photoemission also shows a strong thickness dependence. Comparing the valence band photoemission spectra of the thin Fe/Si(0 0 1) films with that of pure Si and the thickest Fe film, the difference spectra at all thicknesses show almost identical shape indicating the same origin: the Fe/Si interface. Thus, it is mainly the first Fe layer at Fe/Si layer that is reactive with the Si substrate changing its electronic structure.     

Orientation studies of Si-phthalocyanine sulfonic acids cast on SiOx substrates

Layers of dihydroxy silicon phthalocyanine tetrasulfonic acid and oligo-μ-oxo silicon phthalocyanine tetrasulfonic acid were prepared by solution-casting methods. The purity of the material was checked by X-ray photoemission spectroscopy. The orientation of the molecules in respect to the substrate plane was investigated by angle-dependent near-edge X-ray absorption fine-structure spectroscopy. The morphology was characterized by atomic force microscopy. Most samples exhibited a significant orientation that was accompanied by crystalline structures; others had no orientation at all with a dominant amorphous morphology. This behavior indicates that several preparation parameters affect the crystallinity and the orientation of the phthalocyanines. Received: 16 January 2002 / Accepted: 11 February 2002 / Published online: 3 May 2002 RID="*" ID="*"Corresponding author. Fax: +1-919/515-7331, E-mail: harald_ade@ncsu.edu RID="**" ID="**"Present address: Southern Illinois University, Physics, Mailcode 4401, Carbondale, IL 62901, USA     

Synthesis of silica supported titania nanocomposite in controllable phase content and morphology

The silica supported titania nanocomposite thin films with controllable particle size and phase content were successfully prepared by a convenient post annealing approach involving in solid-solid interfacial reaction. The effects of growth conditions, such as the annealing temperature and silicon concentration on the particle size and phase content, were systematically studied by using Atomic force microscopy (AFM), Raman spectroscopy, X-ray diffraction (XRD), and X-ray spectroscopy (XPS). The results indicate that the silicon concentration is a dominant factor in the morphology, crystallization and phase transformation of these nanocomposites. A mechanism for the high temperature phase transformation is also proposed based on the migration of the oxygen vacancies.     

The electronic structure of SrTiO3 and some simple related oxides (MgO,Al2O3, SrO,TiO2)

The valence band density of states (VBDOS) of the insulating oxides SrTiO₃, TiO₂, SrO, MgO and Al₂O₃ obtained by X-ray photoelectron spectroscopy (XPS), are reported. Qualitatively, the VBDOS of these oxides are similar to one another. The XPS results are compared with results from soft X-ray emission spectroscopy (XES), ultraviolet photoemission spectroscopy (UPS), and theoretical calculations. There are some differences (in particular for TiO₂) between the XES and XPS results, which are probably due to matrix element effects enhancing different features of the VBDOS in the two techniques. The XPS results definitively establish the position of the O 2s level, which had been erroneously assigned in previous low-energy UPS measurements. Cluster-type calculations are demonstrated to give a reasonable representation of the VBDOS for the oxides.     

Metal-insulator transition and superconductivity in Hg-doped BaPb0.75Bi0.25O3

The effects of mercury doping on the superconductivity, crystal structure, and electronic structure have been investigated in Hg-doped BaPb_0.75Bi_0.25O₃ (BaPb_0.75−xHg_xBi_0.25O₃, BPHBO) by magnetic measurement, powder X-ray diffraction (XRD), and X-ray photoemission spectroscopy (XPS). At lower doping levels, the system is metallic and superconducting. However, the superconductivity is fully suppressed by Hg doping at x>0.25 and recovered with further increase in Hg content at x>0.3, showing a superconductivity reentrant phenomenon. XPS analysis reveals that BPHBO experiences dual metal-insulator transitions (MITs) at these two superconductivity points, which are accompanied by lattice distortions, suggesting that they may be driven by Peierls transitions. The first MIT may be a Mott-transition, while the second may be due to competition between the band filling effect and modification of the charge-disproportionate state.