Influence of substrate doping on the surface chemistry and morphology of Copper Phthalocyanine ultra thin films on Si (111) substrates

16 nm thick Copper Phthalocyanine (CuPc) films were deposited at room temperature in Ultra High Vacuum onto “n” and “p” type doped Si(111) substrates covered with a native SiO₂ overlayer. Atomic Force Microscopy indicates that the two substrates are both atomically flat (0.15 nm root mean square roughness). Angle dependent X-ray photoemission spectroscopy shows that the thickness of the native SiO₂ over-layer is 0.8 nm (both for the “n” and “p” type Si substrate). Despite the identity of the substrate roughness, of the SiO₂ thickness, and of the CuPc film growth conditions, the organic films (made out of crystallites in the α-phase, as checked with X-ray Diffraction) grown on the “p” and “n” type substrate show clearly different morphological features (determined with Atomic Force Microscopy and Scanning Electron Microscopy measurements). While the CuPc film on “p” Si(111) shows a compact network of densely packed crystallites with sizes (along the substrate plane) ranging from 50 to 100 nm, the CuPc film on “n” Si(111) shows a slightly more open network of larger crystallites (with 75-150 nm size range). Accordingly, the CuPc film roughness is 0.67 nm and 1.15 nm for the “p” and “n” type substrate respectively. Due to the increased surface to volume effects (lower crystallite size) affecting the CuPc film on “p” Si(111), this film exhibits stronger interaction with oxygen and water vapor of the ambient air, as determined by photoemission spectroscopy experiments performed on samples as grown “in situ” and after prolonged (1 year) exposure to air.     

Comparative study of surface morphology of copper phthalocyanine ultra thin films deposited on Si (111) native and RCA-cleaned substrates

Comparative study of substrate doping influence on surface morphology of 16-nm CuPc ultra-thin layers deposited on RCA-cleaned Si (111)/SiO₂ substrates was carried out. The structure and the morphology of thin films were investigated by X-ray photoelectron spectroscopy and atomic force microscopy. The investigations were aimed to provide information whether substrate doping type can be used as one of the parameters for engineering of the sensing layers structure. Atomic force microscopy images and results of photoemission experiments did not reveal any significant differences in morphology and surface chemistry between used substrates. Observed differences in surface morphology of organic overlayer could be caused by different substrate doping. The CuPc film grown on p-type RCA-Si (111) shows a compact network of densely packed crystallites, while the CuPc film deposited on n-type RCA-Si (111) reveals a slightly more open network of larger crystallites. These observations are confirmed by values of roughness, which is 0.97 nm and 1.47 nm for CuPc film on RCA-cleaned p- and n-type substrates, respectively. Results were compared with data obtained for similar 16-nm-thick CuPc layers deposited on n- and p-type Si (111) covered with native oxide. Good agreement between results of both studies was found out.     

X-ray Photoelectron Spectroscopy characterization of native and RCA-treated Si (111) substrates and their influence on surface chemistry of copper phthalocyanine thin films

In this paper native and RCA-treated n- and p-doped Si(111) substrates and ultra-thin 16-nm copper phthalocyanine (CuPc) layers deposited thereon were investigated using X-ray Photoemission Spectroscopy and Angle-Resolved X-ray Photoemission Spectroscopy. The oxide layer thickness was determined to be 1.3 nm on the RCA-treated substrates and 0.8 nm on the native ones. The analysis of substrate carbon contamination showed the existence of C-H, C-OH and COOH components on all substrates. The RCA clean removes more readily the carbon components with the OH group from the n-type Si and causes the segregation of the contaminants. The initial carbon species propagate in the evaporated CuPc layer up to a thickness of about 5 nm affecting the shape of the C1s peak. Additionally, the behavior of the binding energy difference between N1s and Si2p peaks upon the CuPc growth shows that there may occur various CuPc molecule adsorption modes on investigated Si substrates. It could be a useful information, from the technological point of view, especially for low dimensional electronic device preparation.     

On the correlation between morphology and electronic properties of copper phthalocyanine (CuPc) thin films

The morphology of vacuum deposited copper phthalocyanine (CuPc) thin films surface deposited on Si(111) have been studied using the contact mode Atomic Force Microscope (AFM). The influence of substrate temperature during deposition and of the post-deposition UHV annealing on surface roughness as well as on the average and maximum grain height was determined. The observed changes of surface morphology were in a good correlation with the shift of surface Fermi level position in the band gap after O₂ exposure determined in our recent photoemission studies.     

Influence of thermal annealing on microstructural,morphological, optical properties and surface electronic structure of copper oxide thin films

In this study, effect of the post-deposition thermal annealing on copper oxide thin films has been systemically investigated. The copper oxide thin films were chemically deposited on glass substrates by spin-coating. Samples were annealed in air at atmospheric pressure and at different temperatures ranging from 200 to 600°C. The microstructural, morphological, optical properties and surface electronic structure of the thin films have been studied by diagnostic techniques such as X-ray diffraction (XRD), Raman spectroscopy, ultraviolet–visible (UV–VIS) absorption spectroscopy, field emission scanning electron microscopy (FESEM), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). The thickness of the films was about 520 nm. Crystallinity and grain size was found to improve with annealing temperature. The optical bandgap of the samples was found to be in between 1.93 and 2.08 eV. Cupric oxide (CuO), cuprous oxide (Cu₂O) and copper hydroxide (Cu(OH)₂) phases were observed on the surface of as-deposited and 600 °C annealed thin films and relative concentrations of these three phases were found to depend on annealing temperature. A complete characterization reported herein allowed us to better understand the surface properties of copper oxide thin films which could then be used as active layers in optoelectronic devices such as solar cells and photodetectors.     

Experiments and theory on pentacene in the thin film phase: structural, electronic, transport properties, and gas response to oxygen, nitrogen, and ambient air

We investigated the morphological, structural, electronic, and transport properties of pentacene thin films grown by vacuum thermal evaporation on different inert substrates at room temperature. The results of our atomic force microscopy (AFM), X-ray diffraction and scanning tunnelling microscopy (STM) analysis show a structure in the so called “thin film phase” with 1-2 μm sized grains. Atomic terraces are clearly evidenced with AFM and give an inter-planar spacing of 1.54 nm corresponding to the (001) distance. The Scanning Tunneling Spectroscopy measurements show an HOMO-LUMO gap of 2.2 eV. After vacuum thermal evaporation on patterned substrates with different inter-electrodes distances, we have performed in situ measurements of the electrical response of such thin films. We found for these films a resistivity of ρ = 4.7 ± 0.2 · 10⁴ Ω m, that is an order of magnitude lower than the value reported to date in literature for single crystals of pentacene. This value is not affected by the presence of grain boundaries. The resistivity is further reduced by a factor 8.9 ± 0.7, 14 ± 1, 2.3 ± 0.3 upon exposure to oxygen, nitrogen and ambient air, respectively. In addition density functional theory calculations have been performed to investigate the electronic structure of pentacene in this specific phase, focusing on the effects on the relevant electronic properties of the relative orientation of the molecules within the crystalline unit cell, so far experimentally unknown. Our results show that the energy bandwidth and band-gap are crucially affected by the molecular stacking. Furthermore, by comparing our theoretical spectra with the scanning tunneling spectroscopy (STS) measurements, we propose a molecular arrangement that gives a good agreement with experiments as far as the relevant orbitals are concerned. For this polymorph, we find a HOMO and LUMO bandwidth of ≈ 0.7 eV and ≈ 0.8 eV, respectively, which are significantly larger than those obtained for the pentacene bulk-phase and are consistent with the larger conductivity experimentally observed in pentacene thin films.     

Electrophoretic deposition of siderite thin layers: Influence of electrode potential and deposition time

Siderite thin layers have been obtained by electrophoretic deposition on an inert substrate (gold). Scanning electron microscopy image exhibits a compact and homogeneous film composed of round grains which diameter is about 1-2 µm. The influence of two parameters, namely the electrode potential and the deposition time, on its thickness and its microstructure was investigated. The thickness was shown to be slightly dependent of the electrode potential (1.2 µm for − 0.70 V and 1.7 µm for − 0.95 V after 17 h). The crystallite size, estimated by X-ray diffraction patterns, was about 5 nm, depending on both electrode potential and deposition time. Despite its high sensitivity to oxygen, X-ray photoelectron spectroscopy spectra prove that the siderite surface has been kept out from oxidation. These siderite thin layers could be used as modified electrodes for further interaction studies.     

Interfacial electronic structures between fullerene and calcium for high performance n-type organic semiconducting devices

The electronic structure of fullerene (C₆₀) deposited on calcium (Ca) was investigated using in-situ ultraviolet photoelectron spectroscopy. The energy level alignment at the C₆₀/Ca interface was estimated by combining both shifts of the highest occupied molecular orbital (HOMO) level and of the vacuum level during the step-by-step deposition of C₆₀ on Ca. The HOMO level of C₆₀ shows shifts relating to band-bending, resulting in an electron injection barrier of 0.2 eV with accumulation contact with the Ca substrate. The vacuum level reveals an interface dipole of 1.11 eV with negative poles on the C₆₀ side. Noticeably, gap states are formed at the interface region, which might pin the Fermi level and be responsible for the formation of the interface dipole. The complete interfacial energy level diagram of C₆₀/Ca is presented.     

Studies on the electronic transport properties of some organic semiconductors in thin films

The investigated compounds are some derivatives of orthotolidin-N,N-bis (4-aminobenzene-2-sulphonic) acid. The temperature dependences of the electrical conductivity and Seebeck coefficient are studied on the thin films deposited from dimethylformamide solution onto glass substrates. It is known that the investigated compounds have typical semiconducting properties. The values of some important parameters of the films (thermal activation energy of electrical conduction, concentrations and mobilities of charge carriers) have been determined. The correlations between some of these parameters and molecular structure of the respective compounds are discussed.     

Influence of heat treatment on indium-tin-oxide anodes and copper phthalocyanine hole injection layers in organic light-emitting diodes

Modifications of indium-tin-oxide (ITO) and copper phthalocyanine (CuPc) layers by heat treatment aimed at lowering driving voltage in organic light-emitting diodes (OLEDs) are examined. Significant changes were observed in the surface morphology and carrier injection properties of ITO and CuPc layers after annealing at T = 250 °C for 0-60 min in a glove box. In the case of ITO annealing, although the ITO work function gradually decreased and the surface of the ITO layer became smoother than that of an unannealed ITO layer, we observed an appreciable decrease in the driving voltage with an increase in annealing time. In the case of CuPc annealing, on the other hand, we observed deterioration of the OLED's characteristics. All devices demonstrated an increase in driving voltage due to the pronounced crystallization of the CuPc layer.     

Shelf-life time test of p- and n-channel organic thin film transistors using copper phthalocyanines

P- and n-type channel thin film transistors (OTFTs) were fabricated by using hexadecahydrogen copper phthalocyanine (H₁₆CuPc) and hexadecafluoro copper phthalocyanine (F₁₆CuPc) molecules, respectively. Top-contact and bottom-contact source-drain configurations were used for both semiconductors. Furthermore, the temperature and film thickness dependences on the mobility values were measured in the saturation regime of source-drain current. Unipolar mobilities in such single-layer OTFTs were correlated to thin film morphology by X-ray diffraction analysis and atomic force microscopy measurements. Shelf-life time tests of p-type and n-type OTFTs are detailed as OTFT configuration and substrate temperature dependence over a time period of 100 days.     

The effect of the terminating bonds on the electronic properties of sputtered carbon nitride thin films

Amorphous carbon nitride films (a-CN_x) were grown by reactive radio-frequency magnetron sputtering of a graphite target in an argon/nitrogen gas mixture. The total discharge pressure was 1 Pa and the total nitrogen partial pressure (NPP) in plasma was varied between 0 and 100%. The correlation between the microstructure changes, the optoelectronic properties and the internal stress has been investigated in order to prevent the limiting role of the terminating bonds on the electronic properties of the a-CN_x films, and to determine the range of the nitrogen content improving these properties. The analysis of the results reveals that below 3%, the nitrogen incorporation induces an increase in the density of π-bonds, which promotes the enhancement of the conductivity and the reduction of the optical gap. With increasing NPP ratio up to 6%, the formation of terminating bonds within the network reduces the connectivity of the graphitic network, decreasing the conductivity. For higher N content, the reaction of the bonds terminating with water can increase the compressive stress, leading to spontaneous delamination of films.     

Influence of Nb dopant on the structural and optical properties of nanocrystalline TiO2 thin films

In this study, preparation of Nb-doped (0-20 mol% Nb) TiO₂ dip-coated thin films on glazed porcelain substrates via sol-gel process has been investigated. The effects of Nb on the structural, optical, and photo-catalytic properties of applied thin films have been studied by X-ray diffraction, Raman spectroscopy, and scanning electron microscopy. Surface topography and surface chemical state of thin films was examined by atomic force microscope and X-ray photoelectron spectroscopy. XRD and Raman study showed that the Nb doping inhibited the grain growth. The photo-catalytic activity of the film was tested on degradation of methylene blue. Best photo-catalytic activity of Nb-doped TiO₂ thin films were measured in the TiO₂-1 mol% Nb sample. The average optical transmittance of about 47% in the visible range and the band gap of films became wider with increasing Nb doping concentration. The Nb⁵⁺ dopant presented substitutional Ti⁴⁺ into TiO₂ lattice.     

Growth, structure and properties of sputtered niobium oxide thin films

Niobium oxide (NbO_x) films were deposited by pulsed dc magnetron sputtering at different total gas pressures and oxygen flow rates. Various film properties were characterized by X-ray photoelectron spectroscopy, atomic force microscopy, variable angle spectroscopic ellipsometry and four point probe. It was found that oxygen flow rates required for preparing NbO, NbO₂ and Nb₂O₅ at a constant total pressure of 0.93 Pa were approximately 2, 4 and > 6 sccm, respectively. The results showed that the film properties, specifically composition can be significantly changed by the total gas pressure and the oxygen flow rate.     

有机半导体二萘嵌苯在Ru(0001)表面上有序结构的电子态

在Ru(0001)表面上,四个与有机半导体二萘嵌苯(Perylene)分子轨道相关的谱峰分别位于费米能级以下4.5、6.3、7.2、9.9 eV处.在界面处它们的结合能相对较低,反映了界面处有机吸附层与衬底之间的相互作用,衬底中的电子部分地转移到了有机分子的一个或几个轨道上了.低能电子衍射的结果表明:当沉积厚度接近一个单层时,Perylene分子在Ru(0001)表面上形成一种类似(4×4)的有序结构.角分辨紫外光电子能谱的结果表明:Perylene分子平面平行于Ru(0001)表面,而分子的长轴沿[1000]方向取向.随着衬底温度的上升,有机半导体材料在Ru(0001)表面以脱附的形式逐渐减少,在150 ℃以下没有分解发生.     

Morphology and electronic structure of thin 3,4,9,10-perylenetetracarboxylic dianhydride layers on Si(001)

The growth of 3,4,9,10-perylenetetracarboxylic dianhydride on Si(001) was examined in the light of varying flux of impinging molecules. Using atomic force microscopy and synchrotron radiation photoelectron spectroscopy Vollmer-Weber growth mode was observed on a wide range of growth rates. The island size initially decreases rapidly with growth rate, for the low growth rate reaches a minimum, and then gradually increases. Polarization dependent photoemission indicates that the orientation of the molecules within the islands remains flat on the substrate.     

Contribution study of properties of copper indium diselenide thin films

Stoichiometric powder of CuInSe₂ (CIS) was prepared from molten stoichiometric quantities of the elements. The structure analyzed by X-ray diffraction powder (XRD), shows mainly the chalcopyrite phase. CIS polycrystalline thin films deposited from this powder have been grown on glass substrates in vacuum by thermal evaporation method. The structural and electrical properties of both as-deposited and annealed films were studied using X-ray diffraction and dark conductivity measurements respectively. As-prepared films at room temperature showed an amorphous structure. However, the chalcopyrite structure with (112) preferential orientation was observed after annealing in vacuum at 400 °C during 30 min. The influence of the annealing process on the dark conductivity of the films was also discussed.     

Nitric-phosphoric acid etching effects on the surface chemical composition of CdTe thin film

Nitric-phosphoric (NP) acid etching has been regarded as one of the most effective methods for the formation of low resistance back contact with the metal electrode in CdTe based photovoltaic cells. We studied CdTe back surfaces and the changes with time of exposure to NP acid with x-ray photoelectron spectroscopy (XPS), and atomic force microscopy. Strong etching dependence on the back surface chemical composition, and surface roughness, was observed. In order to study the effect of the NP acid etching on surface degradation, the sample was left in open ambient condition for three weeks and XPS measurement in combination with ion sputtering was performed on unetched and highly etched parts. The difference in depth profiles of the NP acid etched and unetched CdTe surface has been discussed.     

Amplitude-dependent internal friction in copper thin films on silicon substrates

Internal friction in copper thin films 0.2–1.5 μm thick on silicon substrates has been measured between 180 and 340 K as a function of strain amplitude. Analysis of the amplitude-dependent internal friction in the copper films shows the relation between the plastic strain of the order of 10⁻⁹ and the effective stress on dislocation motion. The stress–strain curves thus obtained for the copper films tend to shift to a higher stress with decreasing film thickness and also with decreasing temperature, both indicating a suppression of microplastic flow. It is concluded that the microflow stress at a constant level of the plastic strain varies inversely with the film thickness at all temperatures examined. The film thickness effect in the microplastic range can be explained on the basis of a dislocation-bowing model.     

Fractal properties of gold, palladium and gold-palladium thin films on InP

Thermal interaction of indium phosphide (InP) bulk compound semiconductor with thin gold metal films was investigated in the course of the present work. The interaction of the InP/Au system resulted in a pattern showing fractal dimensions. The temperature dependence of the fractal parameters was investigated in a broad temperature range from 200 to 600 °C. No significant temperature dependence of the fractal dimension was observed.The same calculations will be presented for Au/InP and AuPd/InP systems. Our calculations show that the Pd-based contacts have a different behaviour than AuGe metallization where a strong temperature dependence of the fractal number was observed earlier.Another topology measure, the structural entropy is also calculated for the samples. The structural entropy is usually applied for determining the type of the localization of charge distributions, but it can also be used for generalized charges, such as the lightness of the pixels of an electron microscopy picture.