Graphene as interface modifier in ITO and ITO-Cr electrodes

We explore graphene as interface modifier for electrodes in optoelectronic organic devices by measuring the electrical properties of ITO/graphene and ITO/Cr/graphene. For this purpose, exfoliated graphene (EG) was electrochemically synthesized and deposited by spray-pyrolysis. The built-in voltage (Vbi) values were 450 mV for the ITO/CuPc/Al reference, 750 mV for ITO/Cr/graphene/CuPc/Al and 1000 mV for ITO/graphene/CuPc/Al device structures. From these results, we estimate the work functions as 3.20 eV, 3.45 eV and 4.75 eV for ITO/EG, ITO/Cr/EG and ITO. To understand how the work function changes, we carried out first-principles calculations based on density-functional theory (DFT) where Cr work function (~4.2 eV) is not modified by the deposition of pristine graphene; however there is a substantial increase (from 4.2 eV to 5.2 eV), upon deposition of graphene oxide (GO), resulting from a complete transfer of O atoms from the GO sheet to the Cr surface forming a thin layer of chromium oxide.     

空穴注入层对蓝色有机电致发光器件性能的影响

以DPVBi为发光层,NPB为空穴传输层,在阳极ITO和NPB之间分别插入不同的空穴注入层CuPc和PEDOT:PSS,制备了两种结构的蓝色有机电致发光器件(OLEDs):ITO/CuPc/NPB/DPVBi/BCP/Alq3/Al和ITO/PEDOT:PSS/NPB/DPVBi/BCP/Alq3/Al,研究了不同空穴注入材料对蓝色OLEDs发光性能的影响,并与没有空穴注入层的器件进行了比较.其中CuPc分别采用旋涂和真空蒸镀两种丁艺,比较了不同成膜工艺对器件发光特性的影响.结果表明:加入空穴注入层的器件比没有空穴注入层器件性能要好,其中插入水溶性CuPc的器件,其发光亮度和效率虽然比蒸镀CuPc器件要低,但比插入PEDOT:PSS 器件发光性能要好.又由于水溶性CuPc采用旋涂工艺成膜,与传统CuPc相比,制备工艺简单,所以为一种不错的空穴注入材料.     

The fabrication and optical detection of a vertical structure organic thin film transistor

Using vacuum evaporation and sputtering process, we prepared a photoelectric transistor with the vertical structure of Cu/copper phthalocyanine (CuPc)/Al/copper phthalocyanine (CuPc)/ITO. The material of CuPc semiconductor has good photosensitive properties. Excitons will be generated after the optical signal irradiation in semiconductor material, and then transformed into photocurrent under the built-in electric field formed by the Schottky contact, as the organic transistor drive current makes the output current enlarged. The results show that the I–V characteristics of transistor are unsaturated. When device was irradiated by full band (white) light, its working current significantly increased. In full band white light, when V_ec = 3 V, the ratio of light and no light current was ranged for 2.9–6.4 times. Device in the absence of light current amplification coefficient is 16.5, and white light amplification coefficient is 98.65.     

A hybrid photodiode with planar heterojunction structure consisting of ZnO nanoparticles and CuPc thin film

A photodiode with planar heterojunction was fabricated using copper (II) phthalocyanine (CuPc) organic semiconductor and zinc oxide (ZnO) inorganic nanoparticles (NPs, ～5 nm). The current–voltage (I–V) characteristics of ITO/ZnO NPs/CuPc/Ag device in dark and under illumination with a solar simulator were investigated in detail. The measurement results showed that the device exhibited good rectifying behavior in dark and under illumination. A rectification ratio (RR) of 15.44 at 1.95 V was achieved for the device under 100 mW/cm² illumination power. Also, the RR of the device as a function of light intensity was observed. The photoresponsive mechanism of the photodiode was illuminated in term of its energy band diagram.     

Ag(110)表面吸附酞菁铜分子的紫外光电子谱研究

用紫外光电子能谱(UPS)研究了酞菁铜分子在Ag(110)单晶表面上的吸附,随着酞菁铜分子覆盖度增加,衬底Ag的3d电子信号逐渐减弱,在此能带区域出现两个新的谱峰,这两个与吸附有机分子轨道有关的谱峰的束缚能分别为4.45 和6.36 eV.随着覆盖度的增加,在结合能为1.51和9.20 eV处又出现了两个谱峰,它们同样来自吸附有机分子的轨道.随着覆盖度的继续增加,上述四个谱峰的强度逐渐增加,其能量位置均发生了明显的偏移.根据角分辨光电子能谱的实验结果,酞菁铜分子的分子平面基本与衬底表面平行.密度泛函理论计 关键词： 酞菁铜 紫外光电子谱 吸附电子态 密度泛函理论     

Modification of current-voltage characteristics of planar organic systems by nm-thick copper phthalocyanine or perylene dye interlayer

The effect of a nm-thick interlayer of copper phthalocyanine (CuPc) or perylene dye (MePTCDI) on currentvoltage characteristics of planar organic systems is discussed in this work. The MePTCDI layer in the ITO/MePTCDI/CuPc/Au system strongly reduces reverse dark current by blocking injection of holes from ITOinto CuPc leading to high values of rectification ratio. The CuPc interlayer in the ITO/CuPc/MePTCDI/Ag system causes a strong reduction in electron injection from ITOand reverses a forward polarity. Modification of current-voltage characteristics of illuminated systems with an interlayer of MePTCDI or CuPc is associated with a strong photovoltaic effect. This results from efficient excition dissociation at the CuPc/MePTCDI interface. Saturation current, determined by this process of charge carrier photogeneration, can be observed at particular voltage polarity.     

Angular-dependent photoemission studies of indium tin oxide surfaces

Indium tin oxide (ITO) surfaces were treated by solvent cleaning, by plasma of oxygen, argon, nitrogen and by argon ion (Ar⁺) sputtering. Angular-dependent X-ray photoelectron spectroscopy (ADXPS) and ultraviolet photoelectron spectroscopy (UPS) were used to determine the chemical composition, the chemical states and the work function after each treatment. It was found that oxygen plasma and nitrogen plasma chemically reacted with the ITO surfaces. Yet little etching of the surface can be observed after plasma treatments. Among all treatments, oxygen-plasma-treated ITO achieved the highest work function of 4.40 eV, whereas Ar⁺-sputtered ITO surface had the lowest work function of 3.90 eV. The stoichiometry of the ITO surface is shown to be the major controlling factor of the ITO work function. Received: 7 February 2000 / Accepted: 28 March 2000 / Published online: 13 September 2000     

CuPc/ITO结构的表面和界面电子态的XPS研究

覆盖有Indium tin oxide(ITO)膜的透明导电玻璃广泛地用作有机发光器件 (OLEDs)的空穴注入电极 ,但是ITO膜的功函数通常与空穴传输材料的最高被占据分子轨道 (HOMO)不匹配。铜酞菁 (CuPc)作为缓冲层可以提高空穴从ITO向空穴传输材料的注入效率。对CuPc ITO样品的XPS表面分析表明 ,在CuPc分子中 ,铜原子显 2价 ,通过配位键和氮原子相互作用。CuPc分子中有两类碳原子 :8个C原子与 2个N原子成键 ;其余 2 4个C原子具有芳香烃性质。N原子也处在两种化学环境中 :有 4个N原子只与 2个C原子形成CNC键 ;另外 4个N原子不仅与 2个C原子成键 ,还通过配位键与Cu原子成键。用氩离子束对样品表面进行了溅射剥蚀 ,当溅射时间分别为 2 ,5 ,10min时进行XPS采谱分析 ,结果表明 ,随着氩离子束溅射时间增长 ,C 1s,N 1s峰变弱 ,Cu 2p ,O 1s,In 3d,Sn 3d峰增强 ,C 1s,N 1s,O 1s,In 3d和Sn 3d峰都向高束缚能或低束缚能方向移动 ,但它们的情况却不相同。     

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.     

Effect on the reduction of the barrier height in rear-emitter silicon heterojunction solar cells using Ar plasma-treated ITO film

In this study, we investigated the effect of plasma treatment on an indium tin oxide (ITO) film under an ambient Ar atmosphere. The sheet resistance of the plasma-treated ITO film at 250 W (37.6 Ω/sq) was higher than that of the as-deposited ITO film (34 Ω/sq). Plasma treatment was found to decrease the ITO grain size to 21.81 nm, in comparison with the as-deposited ITO (25.49 nm), which resulted in a decrease in the Hall mobility. The work function of the Ar-plasma-treated ITO (WF_ITO=4.17 eV) was lower than that of the as-deposited ITO film (WF_ITO = 5.13 eV). This lower work function was attributed to vacancies that formed in the indium and oxygen vacancies in the bonding structure. Rear-emitter silicon heterojunction (SHJ) solar cells fabricated using the plasma-treated ITO film exhibited an open circuit voltage (V_OC) of 734 mV, compared to SHJ cells fabricated using the as-deposited ITO film, which showed a V_OC of 704 mV. The increase in V_OC could be explained by the decrease in the work function, which is related to the reduction in the barrier height between the ITO and a-Si:H (n) of the rear-emitter SHJ solar cells. Furthermore, the performance of the plasma-treated ITO film was verified, with the front surface field layers, using an AFORS-HET simulation. The current density (J_SC) and V_OC increased to 39.44 mA/cm² and 736.8 mV, respectively, while maintaining a WF_ITO of 3.8 eV. Meanwhile, the efficiency was 22.9% at V_OC = 721.5 mV and J_SC = 38.55 mA/cm² for WF_ITO = 4.4 eV. However, an overall enhancement of 23.75% in the cell efficiency was achieved owing to the low work function value of the ITO film. Ar plasma treatment can be used in transparent conducting oxide applications to improve cell efficiency by controlling the barrier height.     

Fluorescence investigations of pure and mixed evaporated dye layers

Fluorescence spectroscopy is used to investigate energy transfer processes in evaporated layers consisting of several different dyes. In this study films ofN,N-dimethylperylene-3,49,10-bis-dicarboximide (methylperylene pigment, MPP), coevaporated with copper phthalocyanine (CuPc) at varying ratios, and double layers of MPP and CuPc with different thicknesses are investigated. It is shown that energy transfer from MPP to CuPc occurs in both mixed and double layers. The energy transfer leads to a strong quenching of the MPP fluorescence and sensitized CuPc emission in the NIR region. The concentration dependence of the fluorescence quenching in mixed layers can be described by a Stern-Volmer plot. A simple model based on exciton diffusion between MPP molecules toward active quenching centers is used to determine the diffusion length.     

Effect of buffer layers on performance of organic photovoltaic devices based on copper phthalocyanine-perylene dye heterojunction

The work presents the results of research on the systems formed from thin films of copper phthalocyanine (CuPc), N-N′-dimethylperylene-3,4,9,10-dicarboximide (MePTCDI), electrodes of ITO and Ag, and from buffer layers: MoO₃ at ITO and BCP at Ag. We have observed the effect of each buffer layer on voltage dependence of dark current and photocurrent, and on open circuit voltage-light intensity relationship. The system with both buffer layers exhibited the highest values of open circuit voltage and fill factor. The buffer layers improve transport of charge carriers within near-electrode regions, reduce dissociation of excitons on electrodes and reveal processes of charge carrier generation and recombination within the CuPc/MePTCDI junction.     

Preferential regrowth of indium–tin oxide (ITO) films deposited on GaN (0001) by rf-magnetron sputter

Effects of thermal treatments on the electrical properties and microstructures of indium–tin oxide (ITO)/GaN contacts have been investigated using a rf-magnetron sputter deposition followed by rapid thermal annealing. ITO films annealed at 800 °C revealed Schottky contact characteristics with a barrier height corresponding to ITO’s work function of 4.62 eV. The evolution of electrical properties of ITO/GaN contacts was attributed to the preferential regrowth of In₂O₃ (222)//GaN (0001) with an ideal metal–semiconductor Schottky contact. The feasible use of ITO/GaN as a transparent Schottky contact would be realized by the enhanced regrowth of In₂O₃ at high temperature. Received: 1 September 2000 / Accepted: 15 November 2000 / Published online: 28 February 2001     

Electro-optical characterization and analysis of CuPc-based solar cells with high photovoltage

Organic solar cells using the CuPc and PTCBI semiconductor layers were studied. A high open circuit voltage of 1.15 V was obtained in a device with ITO/PEDOT:PSS/CuPc (15 nm)/PTCBI (7 nm)/Al structure. Results were interpreted in terms of a modified CuPc-Al Schottky diode for the thin PTCBI case and a CuPc-PTCBI heterojunction for the thick PTCBI case. Also, the formation of a thin aluminum oxide layer under the aluminum electrode was postulated. This layer has a beneficial aspect wherein shunting losses are reduced and a high photovoltage is enabled. However, it adds greatly to the series resistance to a point where the short circuit current density is reduced. CuPc Schottky diodes with an ITO/PEDOT:PSS/CuPc/Al structure yielded a high V _oc of 900 mV for a CuPc layer of thickness 140 nm. The V _oc increased with increase in CuPc layer thickness.     

Substrate dependence of energy level alignment at the donor–acceptor interface in organic photovoltaic devices

The interface energy level alignment between copper phthalocyanine (CuPC) and fullerene (C60), the widely studied donor–acceptor pair in organic photovoltaics (OPVs), on indium–tin oxide (ITO) and Mg substrate was investigated. The CuPC/C60 interface formed on ITO shows a nearly common vacuum level, but a dipole and band bending exist, resulting in a 0.8 eV band offset at the same interface on Mg. This observation indicates that the energy difference between the highest occupied molecular orbital of CuPC and the lowest unoccupied molecular orbital of C60, which dictates the open circuit voltage of the CuPC/C60 OPV, can be tuned by the work function of the substrate. Furthermore, the substrate effect on the energy alignment at the donor/acceptor interface can satisfactorily explain that a device with an anode of a smaller work function can provide a higher open circuit voltage.     

Improvement of organic solar cells by flexible substrate and ITO surface treatments

In this paper, surface treatments on polyethylene terephthalate with polymeric hard coating (PET-HC) substrates are described. The effect of the contact angle on the treatment is first investigated. It has been observed that detergent is quite effective in removing organic contamination on the flexible PET-HC substrates. Next, using a DC-reactive magnetron sputter, indium tin oxide (ITO) thin films of 90 nm are grown on a substrate treated by detergent. Then, various ITO surface treatments are made for improving the performance of the finally developed organic solar cells with structure Al/P3HT:PCBM/PEDOT:PSS/ITO/PET. It is found that the parameters of the ITO including resistivity, carrier concentration, transmittance, surface morphology, and work function depended on the surface treatments and significantly influence the solar cell performance. With the optimal conditions for detergent treatment on flexible PET substrates, the ITO film with a resistivity of 5.6 × 10⁻⁴ Ω cm and average optical transmittance of 84.1% in the visible region are obtained. The optimal ITO surface treated by detergent for 5 min and then by UV ozone for 20 min exhibits the best WF value of 5.22 eV. This improves about 8.30% in the WF compared with that of the untreated ITO film. In the case of optimal treatment with the organic photovoltaic device, meanwhile, 36.6% enhancement in short circuit current density (J_sc) and 92.7% enhancement in conversion efficiency (η) over the untreated solar cell are obtained.     

Work function changes and surface chemistry of oxygen, hydrogen, and carbon on indium tin oxide

The surface chemistry of indium tin oxide (ITO) has been investigated with Auger electron spectroscopy (AES) and high resolution electron energy loss spectroscopy (HREELS). A vibrating Kelvin probe (KP) with a graphite reference was used to monitor the absolute work function (Φ) of ITO as a function of chemical modification. The ITO was exposed in situ to molecular hydrogen (H₂), hot-filament-activated oxygen (O₂^*), and hot-filament-activated deuterium (D₂^*). The initial Φ of ITO was determined to be 5.2 eV, and surface chemical changes had strong effects on this value, as seen by KP. Exposure of clean ITO to O₂^* increased Φ to 5.6 eV, but the increase was short-lived. The changes in Φ over time were correlated with the uptake of carbon impurities in ultra high vacuum (UHV), as monitored by AES.

The HREELS of ITO revealed significant hydrocarbon impurities. Chemical reduction of ITO produced a metallic surface and dehydrogenated the adsorbed hydrocarbons. Both re-oxidation of metallic ITO and oxidation of clean ITO temporarily removed adventitious carbon from the surface, but oxidized ITO adsorbed an even larger quantity of carbon over time.     

Effect of net carriers at the interconnection layer in tandem organic solar cells

Tandem cell with structure of indium tin oxide (ITO)/molybdenum oxide (MoO₃)/fullerene (C60)/copper phthalocyanine (CuPc)/C60/tris-8-hydroxy-quinolinato aluminum (Alq₃)/Al was fabricated to study the effect of net carriers at the interconnection layer. The open circuit voltage and short circuit current were found to be 1.15 V and 0.56 mA/cm², respectively. Almost the same performance (1.05 V, 0.58 mA/cm²     

Emission characteristics of linear-chain carbon fibers

A complex investigation of the structure and emission characteristics of linear-chain carbon is accomplished. This material is demonstrated to be stable at high temperature (700°C), and the thermal emission is shown to be governed by the Schottky mechanism with the material characteristics reaching record-breaking values: an emission threshold of 800 V/mm and a thermoionic work function of 0.43 eV. These values are found to arise during sp ¹ carbon crystallization and vanish after its graphitization. The very low value of the work function of linear-chain carbon is theoretically substantiated.