Scanning tunneling microscopy and spectroscopy investigations of copper phthalocyanine adsorbed on Al2O3/Ni3Al(1 1 1)

Low temperature scanning tunneling microscopy (LT-STM) and scanning tunneling spectroscopy (STS) have been used to investigate adsorbed copper phthalocyanine (C₃₂H₁₆N₈Cu) molecules on an ordered ultrathin Al₂O₃ film on the Ni₃Al(1 1 1) surface as a function of coverage and annealing temperature. For sub-monolayer coverage and a deposition temperature of 140 K two different planar molecular adsorption configurations rotated by 30° with respect to each other were observed with submolecular resolution in the STM images. The template effect of the underlying oxide film on the CuPc orientation, however, is only weak and negligible at higher coverages. For θ_CuPc ≈ 1 ML, before completion of the first layer, the growth of a second layer was already observed. The measured spacing of 3.5 Å between first and second layer corresponds to the distance between the layers in the α-modification of crystalline CuPc. The molecules deposited at 140 K are thermally stable upon prolonged annealing to temperatures up to 250 K. By the use of STS the lowest unoccupied molecular orbital (LUMO) of the adsorbed copper phthalocyanine molecules has been identified at an energy of 1.2 eV above E_F. The lateral distribution of the electronic states of the CuPc has been analyzed and mapped by STS.     

Structure and morphology of CuPc and F16CuPc pn heterojunction

This article reports structure and morphology of copper phthalocyanine (CuPc) and fluorinated copper phthalocyanine (F₁₆CuPc) pn heterojunction. Highly ordered CuPc and F₁₆CuPc polycrystalline thin films with the 2 0 0 plane spacing s of 1.30 and 1.56 nm, respectively, could be continuously grown via an intermediate-phase layer. Compared with CuPc, the intermediate-phase layer is much thinner when F₁₆CuPc is used as the first layer. The rougher the first layer is, the thicker the intermediate-phase layer is. Similarly, the 2 0 0 plane spacings of the intermediate-phase layer are dependent on morphology of the first layer. Furthermore, morphology of the heterostructure is mainly dominated by that of CuPc films. Due to the thicker intermediate-phase layer in the CuPc/F₁₆CuPc heterostructure, the thin film transistors (TFT) performance is obviously inferior to that of the F₁₆CuPc/CuPc device.     

Electronic properties of the organic semiconductor hetero-interface CuPc/C60

We present a study of the electronic properties of the interface between the well-established molecular organic semiconductor copper phthalocyanine (CuPc) and the fullerite C₆₀ using photoelectron spectroscopy and the Kelvin-probe (KP) method. Upon deposition of CuPc on C₆₀, we found interfacial shifts of the vacuum level indicating the formation of a dipole layer, while band bending is found to be negligible. The interface dipole of 0.5 eV measured with KP is close to the difference between the work functions of bulk CuPc and C₆₀. No evidence for a chemical interaction at the interface is concluded from the absence of additional features in the core-level spectra at the earliest stages of deposition. The energy-level alignment diagram at the CuPc/C₆₀ interface is derived.     

酞菁铜薄膜的折射率及吸收特性

通过真空镀膜法在单晶硅制备了酞菁铜薄膜，在波长扫描和入射角可变全自动椭圆偏振光谱仪上研究了ＣｕＰｃ薄膜的椭偏光谱并分析了其电子结构。     

Enhanced photosensitivity of InGaZnO-TFT with a CuPc light absorption layer

A copper phthalocyanine (CuPc) organic semiconductor is capped onto an amorphous indium–gallium–zinc-oxide (InGaZnO) thin film transistor (TFT) to enhance the photosensitivity of InGaZnO-TFT. The CuPc organic semiconductor is served as a light absorption layer and forms a p–n junction with the InGaZnO film. After 60 s white light illumination, light responsivity (R) of InGaZnO-TFT with a CuPc light absorption layer reaches a value of 148.5 A/W at a gate-source voltage (V_GS) of 20 V, which is much larger than that (31.2 A/W) of the conventional InGaZnO-TFT. The results are attributed to the following mechanism. First, a CuPc layer is employed as the light absorption layer. Second, CuPc/InGaZnO p–n junction enables the injection of electron into InGaZnO film. Our results indicate that using CuPc as light absorption layer is an effective approach to improve the photosensitivity of InGaZnO-TFT.     

Low-temperature scanning tunneling microscopy and near-edge X-ray absorption fine structure investigation of epitaxial growth of F<Subscript>16</Subscript>CuPc thin films on graphite

Low-temperature scanning tunneling microscopy (LT-STM) and near-edge X-ray absorption fine structure (NEXAFS) measurements are used to study the epitaxial growth and molecular orientation of organic thin films of copper hexadecafluorophthalocyanine (F₁₆CuPc) on highly oriented pyrolytic graphite (HOPG). Our results show that F₁₆CuPc molecules lie flat on HOPG up to 5 nm thickness, stabilized by interfacial and interlayer π–π interactions. LT-STM experiments reveal the coexistence of two different in-plane orientations of the F₁₆CuPc monolayer on HOPG. On the second layer of F₁₆CuPc on HOPG, however, all F₁₆CuPc molecules possess the same in-plane orientation.     

Structural and electronic implications for carrier injection into organic semiconductors

We report on the structural and electronic interface formation between ITO (indium-tin-oxide) and prototypical organic small molecular semiconductors, i.e., CuPc (copper phthalocyanine) and α-NPD (N,N′-di(naphtalen-1-yl)-N,N′-diphenyl-benzidine). In particular, the effects of in situ oxygen plasma pretreatment of the ITO surface on interface properties are examined in detail: Organic layer-thickness dependent Kelvin probe measurements revealed a good alignment of the ITO work function and the highest occupied electronic level of the organic material in all samples. In contrast, the electrical properties of hole-only and bipolar organic diodes depend strongly on the treatment of ITO prior to organic deposition. This dependence is more pronounced for diodes made of polycrystalline CuPc than for those of amorphous α-NPD layers. X-ray diffraction and atomic force microscopic (AFM) investigations of CuPc nucleation and growth evidenced a more pronounced texture of the polycrystalline film structure on the ITO substrate that was oxygen plasma treated prior to organic layer deposition. These findings suggest that the anisotropic electrical properties of CuPc crystallites, and their orientation with respect to the substrate, strongly affect the charge carrier injection and transport properties at the anode interface.     

Influence of self-assembly monolayers on the characteristics of copper phthalacyanine thin film transistor

Self-assembly monolayers (SAMs) of octadecyltrichlorosilane (OTS) on a silicon dioxide substrate were formed in solution, or by vacuum vapor methods, and characterized by Fourier transform infrared (FTIR) spectroscopy. We found that the OTS SAMs on SiO₂ substrates greatly affect the order and connectivity of evaporated copper phthalocyanine (CuPc) thin films, as confirmed by an atomic force microscopy (AFM) and X-ray diffraction analysis. The performance of the organic CuPc thin film transistor comprising OTS SAMs interposed between a gate dielectric and an organic semiconductor layer could be effectively enhanced as a result of improvements in the quality both of the organic/dielectric interface and the evaporated CuPc thin films. The deposition of an OTS SAM leads to a mobility of 1.48×10^-3 cm²/Vs, 1–2 orders higher than that of bare silicon dioxide. PACS 73.61.Ph; 85.30.Tv; 78.66.Tr     

Orientation-dependent ionization potential of CuPc and energy level alignment at C60/CuPc interface

The electronic structure evolution of interfaces of fullerene (C₆₀) with copper phthalocyanine (CuPc) on highly oriented pyrolytic graphite (HOPG) and on native silicon oxide has been investigated with ultraviolet photoemission spectroscopy and inverse photoemission spectroscopy. The LUMO edge of C₆₀ was found to be pinned at the interface with CuPc on SiO₂. A substantial difference in the electron affinity of CuPc on the two substrates was observed as the orientation of CuPc is lying flat on HOPG and standing up on SiO₂. The ionization potential and electron affinity of C₆₀ were not affected by the orientation of CuPc due to the spherical symmetry of C₆₀ molecules. We observed band bending in C₆₀ on the standing-up orientation of CuPc molecules, while the energy levels of C₆₀ on the flat-lying orientation of CuPc molecules were observed to be flat. The observation points to a dependence of photoexcited charge transfer on the relative molecular orientation at the interface.     

Laser deposition of iron on graphite substrates

Pulsed laser deposition of iron atoms on graphite substrates was performed to produce iron carbide films. Mössbauer spectra of the sample revealed that iron carbide was produced on the substrate surface and that an α-Fe layer was produced above the iron carbide layer. When the substrate temperature was maintained at 300 K, the iron carbide layer had a hyperfine magnetic distribution because it contained high density of defects. Laser deposition of Fe at 570 K produced cementite Fe₃C with fewer defects due to enhancement of thermal reactions or annealing of the films. The orientation of hyperfine field of the Fe₃C film was parallel to the substrate surface.     

Composition depth profiles of Bi3.15Nd0.85Ti3O12 thin films studied by X-ray photoelectron spectroscopy

In the present work, X-ray photoelectron spectroscopy (XPS) was used to investigate the composition depth profiles of Bi_3.15Nd_0.85Ti₃O₁₂ (BNT) ferroelectric thin film, which was prepared on Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates by chemical solution deposition (CSD). It is shown that there are three distinct regions formed in BNT film, which are surface layer, bulk film and interface layer. The surface of film is found to consist of one outermost Bi-rich region. High resolution spectra of the O 1s peak in the surface can be decomposed into two components of metallic oxide oxygen and surface adsorbed oxygen. The distribution of component elements is nearly uniform within the bulk film. In the bulk film, high resolution XPS spectra of O 1s, Bi 4f, Nd 3d, Ti 2p are in agreement with the element chemical states of the BNT system. The interfacial layer is formed through the interdiffusion between the BNT film and Pt electrode. In addition, the Ar⁺-ion sputtering changes lots of Bi³⁺ ions into Bi⁰ due to weak Bi-O bond and high etching energy.     

酞菁铜薄膜的光记录特性

研究了有机染料酞菁铜（ＣｕＰｃ）真空蒸镀薄膜在可见及近红外区域的吸收光谱和光学常数，发现酞菁铜薄膜在５５０－７５０ｎｍ波长范围内具有较强的吸收，在静态测试仪上测试了酞菁铜薄膜的光存储记录特性，发现用低功率氦氖激光照样品时薄膜反射率变化较大，在酞菁记录层上覆盖金属反射层将提高写入激光的阈值能量并且增大反射率的对比度。     

Formation of copper islands on a native SiO2 surface at elevated temperatures

A combination of in situ X-ray photoelectron spectroscopy analysis and ex situ scanning electron- and atomic force microscopy has been used to study the formation of copper islands upon Cu deposition at elevated temperatures as a basis for the guided growth of copper islands. Two different temperature regions have been found: (I) up to 250 °C only close packed islands are formed due to low diffusion length of copper atoms on the surface. The SiO₂ film acts as a barrier protecting the silicon substrate from diffusion of Cu atoms from oxide surface. (II) The deposition at temperatures above 300 °C leads to the formation of separate islands which are (primarily at higher temperatures) crystalline. At these temperatures, copper atoms diffuse through the SiO₂ layer. However, they are not entirely dissolved in the bulk but a fraction of them forms a Cu rich layer in the vicinity of SiO₂/Si interface. The high copper concentration in this layer lowers the concentration gradient between the surface and the substrate and, consequently, inhibits the diffusion of Cu atoms into the substrate. Hence, the Cu islands remain on the surface even at temperatures as high as 450 °C.     

原子力显微镜与x射线光电子能谱对LiBq4/ITO和LiBq4/CuPc/ITO的表面分析

利用原子力显微镜对8-羟基喹啉硼化锂(LiBq₄)/铟锡氧化物和8-羟基喹啉硼化锂/酞菁铜(CuPc)/铟锡氧化物表面分别进行了扫描，显示了LiBq₄在不同衬底上的形貌差异，并进一步利用样品表面的x射线光电子能谱图验证了这一差异.实验表明，CuPc层的加入改善了LiBq₄的成膜质量，并将这种改善归因于分子构型与电子亲和势的不同. 关键词： 原子力显微镜 x射线光电子能谱 电子亲和势     

Visualization of thermally activated morphology evolution of N, N’-di(naphthalene-1-yl)- N, N’-diphthalbenzidine films on ITO/copper phthalocyanine underlying layer

The thermally activated morphological evolution of an N,N’-di(naphthalene-1-yl)-N,N’-diphthalbenzidine (NPB) thin film on an ITO-coated glass/copper phthalocyanine (CuPc) underlying layer has been studied in situ by exploiting variable-temperature tapping mode atomic force microscopy (VT-AFM) in detail. The morphological change, assumed as an apparent glass transition of the NPB thin film, was observed to initially occur at ∼60 °C, and the transition finished at about 95 °C. Crystallization of the NPB thin film from the glassy state quickly appeared at about 135 °C in N₂. The NPB thin film gradually melted and disappeared with an increase in temperature, and simultaneously revealed the ITO/CuPc underlying layer. The morphological variations of the NPB thin film have been verified by micro-Raman spectra. Moreover, it has been found that heating history and moisture seriously affect the degradation evolution of the NPB layer. These observations should shed light on the thermally activated degradation pathways and the long-term operation stability and reliability of NPB-based organic light-emitting diodes. PACS 68.55.Jk; 85.60.Jb; 64.70.Kb; 68.37.Ps     

Electronic properties of ultrathin films based on pyrrolofullerene molecules on the surface of oxidized silicon

Results of the investigation into the interface formation during the deposition of the films based on aziridinylphenylpyrrolofullerene (APP-C₆₀) up to 8 nm thick on the surface of the oxidized silicon substrate are presented. The procedure of detecting reflection of testing low-energy electron beam from the surface implemented in the total current spectroscopy mode with a change in the incident electron energy from 0 to 25 eV is used. The structure of maxima in the total current spectra induced by the APP-C₆₀ deposited film is established, and the character of interrelation of these maxima with π* and σ* energy bands in the studied materials is determined. It is revealed due to analyzing the variation in intensities of the total current spectra of the deposited APP-C₆₀ film and the (SiO₂)n-Si substrate that the APP-C₆₀ film is formed at the early deposition stage with the coating thickness thinner than one monolayer without the formation of the intermediate modified organic layer. As the APP-C₆₀/(SiO₂)n-Si interface is formed, the work function of the surface increases by 0.7 eV, which corresponds to the transfer of the electron density from substrate (SiO₂)n-Si toward the film APP-C₆₀. The optical absorption spectra of the APP-C₆₀ films are measured and compared with the spectra of films of unsubstituted C₆₀.     

Influence of the substrate temperature during deposition on film characteristics of copper phthalocyanine and field-effect transistor properties

In this paper, we employ different substrate temperatures during the deposition process and observe a highly ordered structure and strong orientation of copper phthalocyanine (CuPc) molecules on Si/SiO₂ by using X-ray-diffraction and transmission electron microscopy analysis. The results show the effect of CuPc morphology at different substrate temperatures on the organic field-effect-transistor performance. When the substrate temperature for deposition of CuPc is 120 °C, a mobility of 3.75×10^-3 cm²/V s can be obtained. PACS 73.61.Ph; 85.30.Tv; 78.66.Tr     

Improving the mobility of CuPc OFETs by varying the preparation conditions

In this work, three different preparation conditions were used for testing the performance of p-conducting copper phthalocyanine (CuPc) organic field-effect transistors (OFETs). The charge carrier mobility (μ _sat=(1.5±0.6)×10^?3 cm²/V?s) of the CuPc OFETs with the CuPc film deposited while keeping the substrate at room temperature could be improved when the gate dielectric was modified by a self-assembled monolayer of n-octadecyltrichlorosilane (μ _sat=(3.8±0.4)×10^?3 cm²/V?s) or when elevated temperatures were applied to the substrate (T _S,av=127 ^°C) during the deposition of the organic film (μ _sat=(6.5±0.8)×10^?3 cm²/V?s). For the latter case, the dependence of the mobility and threshold voltage with increasing thickness of the organic film was tested—above 13 nm film thickness, no further significant increase of the hole mobility or change in the threshold voltage could be observed. The environmental stability of the OFETs was checked by performing ex situ measurements immediately as the sample was exposed to atmosphere and after 40 days of exposure. The effect of the different preparation conditions on the morphology of the organic films prepared in this work is also discussed in this context.     

Modification of the electronic properties of the TiO2 (1 1 0) surface upon deposition of the ultrathin conjugated organic layers

A few nm thick 3,4,9,10-perylenetetracarboxylic acid dianhydride (PTCDA) and Cu-phthalocyanine (CuPc) overlayers were thermally deposited in situ in UHV onto TiO₂ (1 1 0) surface. Atomic composition of the surfaces under study was monitored using Auger electron spectroscopy (AES). The formation of the interfacial potential barrier and the structure of the unoccupied electronic states located 5-25 eV above the Fermi level (E_F) was monitored using a probing beam of low-energy electrons according to the total current electron spectroscopy (TCS) method. The work function values upon the overlayer deposition changed from 4.6 to 4.9 eV at the PTCDA/TiO₂ (1 1 0) interface and from 4.6 to 4.3 eV at the CuPc/TiO₂ (1 1 0) interface. Band bending in the TiO₂ substrate, molecular polarization in the organic film and changes in the work function due to the change in the surface composition were found to contribute to the formation of the interfacial potential barriers. Oxygen admixture related peaks were observed in the AES and in the TCS spectra of the CuPc overlayers. A mechanism of the transformations in the PTCDA and CuPc overlayers on the TiO₂ (1 1 0) upon elevating temperature from 25 to 400 °C was suggested.