LiBq4/ITO和LiBq4/CuPc/ITO表面的AFM与XPS分析

用 AFM 对蓝色 OLED 的空穴传输层 LiBq4/ITO 和 LiBq4/CuPc/ITO 表面扫描。结果均呈岛状结构。LiBq4沉积在 ITO 上成膜较差,在 CuPc 上成膜较好。说明加入 CuPc 能有效改善 LiBq4的成膜质量。XPS 对样品表面 In3d 和 Sn3d 的电子状态分析也证实 ITO 表面沉积 LiBq4膜存在裂缝,加入 CuPc 可抑制裂缝出现。分析指出,CuPc 由于 Cu(II)离子半满的 dx2-y2轨道在卟啉环平面内和氮强烈作用形成离域大π键,使 LiBq4的沉积状态改善。     

铜酞菁与富勒烯共混层对柔性薄膜太阳电池光伏性能的影响

在柔性PET-ITO衬底上制备了结构为ITO/CuPc/CuPc:C60/C60/Al的柔性薄膜太阳电池.结果发现,共混层的嵌入,可增大给体/受体界面,提高激子扩散效率,从而提高器件光电转换效率.当共混层CuPc与C60>的摩尔比为1 : 2时,光吸收效率较高,且共混层颗粒均匀分散,光电转换效率达0.63%.     

原子力显微镜与X射线光电子能谱对ITO表面改性的研究

采用氧气等离子体(OP)处理对氧化铟锡(ITO)薄膜进行表面改性,通过原子力显微镜(AFM)、X射线光电子能谱(XPS)和四探针等测试手段对薄膜样品进行表征,研究了OP处理对ITO表面性质的影响.实验结果表明OP处理有效去除了ITO表面的污染物,优化了ITO表面的化学组分,降低了ITO表面的粗糙度和方块电阻,改善了ITO的表面形态.与此同时,通过XPS监测研究了OP处理后ITO表面化学组分随老化时间的变化,结果显示经过优化的化学组分随老化时间增加而逐渐退化.另外,以OP处理后经过不同老化时间的ITO样品作为空穴注入电极,制备了有机电致发光器件(OELD),通过测试器件的电压-电流-亮度特性,进一步研究了ITO表面性质对于OELD光电性能的影响.     

真空热蒸发酞菁铜(CuPc)薄膜的结构及光学、电学性能研究

为研究衬底温度对酞菁铜(CuPc)薄膜的结构、光学及光电导性能的影响,文中采用真空热蒸发方法制备了不同衬底温度的CuPc薄膜.X射线衍射和Raman光谱分析显示CuPc薄膜呈现很好的定向生长特性,随衬底温度的升高,CuPc薄膜的结晶性变好,其中α-CuPc的相对含量逐渐增加,而β-CuPc相应减少;场发射扫描电镜观察了不同衬底温度下薄膜的表面形貌和晶粒分布情况;用紫外可见光谱表征了CuPc薄膜的光学性能;CuPc薄膜的光敏性随衬底温度的升高表现出先增大后减小的变化规律.     

ITO纳米粉末爆炸压实烧结致密化陶瓷靶材研究

对ITO商业复合粉末应用爆炸冲击方法压实烧结,并对样品进行了XRD和ESM检测.通过粉末和压实后样品的XRD图及SEM照片的比较,发现在爆炸冲击压实纳米ITO陶瓷粉末时,能够使晶粒度减小,有助于后续烧结密实过程中控制ITO靶材的晶粒度的过分长大;SEM图片显示,在1200℃烧结的靶材微观结构比较均匀.本文探索了纳米ITO粉末冲击压实烧结的微观机理,并与以往人们对粉末的冲击沉能结论进行了比较,得出结论:压实烧结的主要机理是破碎填充效应,使得一部分粉末颗粒表面原子间的距离达到了点阵量级,从而产生键合力;一部分表面原子间的距离达到了一定小的程度,Vander Waals力使其结合.     

Low Temperature DC Sputtering Deposition on Indium-Tin Oxide Film and Its Application to Inverted Top-emitting Organic Light-emitting Diodes

Indium tin oxide （ITO） ultrathin films were prepared on glass substrate by DC （direct current） magnetron sputtering technique with the assistance of H2O vapor to avoid potential surface damage. The film properties were characterized by X-ray diffraction （XRD） technique, four-point probe method and spectrophotometer. The results show that the deposited ITO film with introduced H2O during sputtering process was almost amorphous. The average visible light transmission of 100 nm ITO film was around 85% and square resistivity was below 80 Ω/square. The film was used as the transparent anode to fabricate an inverted top-emitting organic light-emitting diodes （IT-OLEDs） with the structure of glass substrate/Alq3 （40 nm）/NPB （15 nm）/CuPc （x nm）/ITO anode （100 nm）, where the film thickness of CuPc was optimized. It was found that the luminance of this IT-OLEDs was improved from 25 cd/m^2 to more than 527 cd/m^2 by increasing the thickness of CuPc, and luminance efficiency of 0.24 lm/W at 100 cd/m^2 was obtained, which indicated that the optimized thickness of CuPc layer was around 15 nm.     

酞菁铜（CuPc）薄膜器件的制备及其电双稳特性

一些无机半导体器件和许多有机薄膜器件都具有电双稳特性.通过对CuPc有机薄膜器件的,I-V曲线的分析,说明CuPc薄膜器件具有明显的电双稳特性.研究了膜厚对器件I-V特性的影响,结果表明CuPc膜厚达到750 nm器件才表现出明显的电双稳特性,此时跳变电压为7.51V.Ag底电极器件的转变电压(9.6V)与ITO底电极器件的转变电压(7.47V)不同,简要分析了造成这种区别的原因.并对器件电双稳态特性的形成机理进行了解释.     

氢气退火对ITO纳米颗粒能带结构的影响

采用共沉淀法合成了高质量的ITO纳米颗粒,研究了H_2退火对ITO结构及能带的影响。通过扫描电子显微镜对ITO颗粒的形貌进行分析,发现其颗粒尺寸均匀;采用傅里叶变换红外光谱分析退火前后ITO中化学键的类型,发现退火之后In-O键的振动峰减弱,这是ITO颗粒表面氧溢出并形成In-Sn合金所致;同时X射线衍射曲线在退火前后并未发生变化,表明ITO纳米颗粒主体的晶体结构并没有发生改变;通过H_2气氛下退火后样品的吸收光谱可以看出,随着退火温度的升高,ITO的带隙逐渐增大,这是由表面的In-Sn合金所引起的。     

CuPc/C60薄膜太阳能电池的制备及膜厚对其光电性能的影响

本文采用CuPc作为电子给体,C60作为电子受体制备了ITO/CuPc/C60/Al异质结太阳能电池。实验表明器件中活性层(CuPc/C60)对太阳能电池的光电性能有很大的影响。主要原因是有机物的激子扩散长度大约是十几纳米左右,产生的激子大多数在未到达异质结之前就已经复合。本文讨论了活性层(CuPc/C60)的厚度比,并获得其最优比例。     

ITO作为源漏电极的有机场效应晶体管

报道了一种OFET,它采用ITO作为源漏电极,聚酰亚胺为绝缘层,CuPc为半导体层.实验结果表明,该器件具有明显的场效应性质,性能较好,载流子迁移率和开关比分别达2.3×10-3 cm2/V.s、800,表明ITO是一种合适的、有前途的p型OFET源漏极材料.为此,本文对由电极材料和半导体材料间形成的接触电阻对OFET性能影响进行了分析.     

柔性ITO衬底上铜酞菁薄膜有序生长的X射线衍射研究

采用石英晶体微天平实时监测薄膜生长速率,通过控制衬底温度与薄膜生长速率,在柔性ITO导电衬底上真空蒸发沉积了铜酞菁薄膜.X射线衍射分析表明,适当提高衬底温度与薄膜生长速率,可促进薄膜的有序生长.当衬底温度为90℃,生长速率为10nm/min时,薄膜的有序度最高,薄膜晶型呈(相和(200)晶面.     

Surface potential measurement of organic photo-diode consisting of fullerene/copper phthalocyanine double layered device

We investigated the surface potential built across the electrode/fullerene (C₆₀) or copper phthalocyanine (CuPc) interface and C₆₀/CuPc interface as a function of the thickness of the semiconductor film in the dark condition and under illumination. The surface potential of C₆₀ on Au, Al and Mg changes negatively with the increment of film thickness and it saturates at − 0.25, − 1.0 and − 1.5 V within 20 nm. The Fermi level alignment at C₆₀/electrode interface is established within ∼ 20 nm from electrode, and very high electric field exists due to the displacement of negative electronic charges from electrode into C₆₀. On the other hand, the surface potential of CuPc on ITO changes to + 0.1 V, and the work functions of C₆₀ and CuPc were estimated as 5.0 eV and 4.7 eV. C₆₀ film also accepts electrons from CuPc at hetero-junction interface, and the Fermi-level alignment was again obtained at C₆₀/CuPc interface under illumination. The built-in potential of ca. 0.3 V formed at C₆₀/CuPc interface was considered as the origin of the reduction of open-circuit voltage in ITO/CuPc/C₆₀/Au device compared with the optimum value of 0.6 V. On the other hand, the very high electric field formed at C₆₀/Mg contact improved the photovoltaic properties.     

Nanostructured organic-inorganic photodiodes with high rectification ratio

High quality organic-inorganic heterojunction photodiodes based on nanostructured copper (II) phthalocyanine (CuPc) and intrinsic zinc oxide (i-ZnO) have been fabricated. The i-ZnO thin films/layers were grown by RF magnetron sputtering on clean indium tin oxide (ITO) coated glass substrates. These films have been characterized by optical absorption and field emission scanning electron microscopy (FESEM). CuPc thin films deposited at room temperature on i-ZnO have exhibited a change in their surface morphology with the post-deposition annealing temperature under normal atmosphere. The electrical dark conductivity and the photoconductivity of ITO/i-ZnO/CuPc/Au sandwich structures have been measured under various photoexcitation intensities using a xenon light source. The devices have shown excellent reproducibility of their electrical characteristics and high rectification ratios. The highest rectification ratio is nearly 831 calculated above the threshold voltage at room temperature for the sample annealed at 250?°C (i.e.?Pc 250). The effects of the annealing temperature of CuPc on the surface morphology, rectification ratio, and optical properties have been 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.     

Photovoltaic characteristics of TCNQ-incorporated CuPc-poly(p-phenylene) composite films

Composite films (CuPc–PPP–TCNQ) were produced by simultaneous deposition using copper phthalocyanine (CuPc) as a carrier generation material, poly(p-phenylene) (PPP) as a hole transport material, and tetracyanoquinodimethane (TCNQ) as a incorporation material. Schottky barrier photovoltaic cells, consisting of a semitransparent aluminum and the CuPc–PPP–TCNQ composite films, were fabricated. The junction properties and the photovoltaic properties on Al/CuPc–PPP–TCNQ/ITO sandwich cells were investigated. As well as a composite film of the CuPc and the PPP (CuPc–PPP), the conductivity of the CuPc–PPP–TCNQ composite film is improved as the TCNQ is simultaneously deposited in the CuPc–PPP composite film. Therefore, it is proven that the short circuit photocurrent density (J _sc) and the photovoltaic property increases significantly. The J _sc of the Al/CuPc–PPP–TCNQ/ITO cell is 2.60 A/cm², and it is found that the J _sc is about 20 times that of an Al/CuPc/ITO cell and double that of an Al/CuPc–PPP/ITO cell. Consequently, the power conversion efficiency of the Al/CuPc–PPP–TCNQ/ITO cell obtained was 3.68%.     

Novel hybrid solar cells based on α-copper phthalocyanine–cadmium sulfide planar heterojunction

Cadmium sulfide (CdS) has been employed as an alternative acceptor for planar heterojunction solar cell based on copper phthalocyanine (CuPc). Spin-coated poly-3,4-ethylenedioxythiophene:polystyrenesulfonate (PEDOT:PSS) on indium tin oxide (ITO)-coated glass substrates was used for the vacuum deposition of CuPc and CdS planar heterojunction. In the present study, we have fabricated two different architectures of CuPc/CdS devices: (1) ITO/PEDOT:PSS/CuPc/CdS/Al and (2) ITO/PEDOT:PSS/CuPc/CdS/LiF/Al. Our results indicate that the CdS could effectively facilitate charge transport in the nanostructured network, and be a good acceptor. The fabricated bare CuPc/CdS device shows 0.13 % conversion efficiency while incorporation of LiF layer between CuPc/CdS and Al contact facilitates low-recombination rate results ~43 % enhancement in efficiency. The ITO/PEDOT:PSS/CuPc/CdS/LiF/Al device shows 0.30 % power conversion efficiency.     

Morphological control of CuPc and its application in organic solar cells

We have prepared organic photovoltaic (OPV) cells possessing an ideal bulk heterojunction (BHJ) structure using the self-assembly of copper phthalocyanine (CuPc) as the donor material and fullerene (C(60)) as the acceptor. The variable self-assembly behavior of CuPc on a diverse range of substrates (surface energies) allowed us to control the morphology of the interface and the degree of carrier transportation within the active layer. We observed rod-like CuPc structures on indium-tin oxide (ITO), poly(3,4-ethylenedioxythiophene)-poly(4-styrenesulfonate) (PEDOT:PSS) and Au substrates. Accordingly, the interfaces and continuing transport path between CuPc and fullerene domains could be greatly improved due to the ideal BHJ structure. In this paper, we discuss the mechanisms of producing CuPc rod-like films on ITO, PEDOT:PSS and Au. The OPV cell performance was greatly enhanced when a mixture of horizontal and vertical CuPc rods was present on the PEDOT:PSS surfaces, i.e.?the power conversion efficiency was 50 times greater than that of the corresponding device featuring a planar CuPc structure.     

Work function and valence band structure of tin-doped indium oxide thin films for OLEDs

Transparent conducting ITO thin film has been widely used as anode material in OLEDs due to its good optical transparency, low electrical resistivity, ease of patterning, high work function and efficient hole injection properties. The interface between ITO and organic layer in OLED device is thus important and can influence the electrical and luminescent properties. In this report, ITO substrates were treated with 20% H₃PO₄ solution. The corresponding changes in crystalline morphology were studied by X-ray diffraction. X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS) were performed at ∼10⁻⁹ Torr to study the work function and the valence band structure of ITO substrates. It was found that work function became slightly lower after the treatment, probably caused by the formation of metal complex compounds and metal hydroxides. The binding energy of In 3d_5/2 shifted from 444.6 to 445.3 eV. This shifting was referred to the formation of In-OH bonding. It would be easier to provide electron by In-OH bonding than by In-O-In or Sn-O-Sn when photons reached ITO surface. The interface between ITO and CuPc was improved through polar surface and less aggregation. In addition, the OLED devices exhibited improved performance in both external quantum efficiency and luminescence efficiency.