Transparent conductors with an ultrathin nickel layer for high-performance photoelectric device applications

A thin nickel (Ni) layer of thickness 5 nm was inserted in between the indium tin oxide (ITO) layers of thickness 50 nm each so as to increase the conductivity of ITO without affecting much of its transmittance nature. ITO layers with and without Ni film were prepared by reactive DC sputtering on both Si and glass substrates. The influence of Ni layer on the optical and electrical properties of prepared devices was investigated. Due to the insertion of thin Ni layer, the resistivity of ITO/Ni/ITO sample (3.2×10⁻⁴ Ω cm) was reduced 10 times lesser than that of ordinary ITO layer (38.6×10⁻⁴ Ω cm); consequently it increased the mobility of ITO/Ni/ITO device. The external and internal quantum efficiencies (EQE and IQE) of ITO/Ni/ITO device exhibited better performance when compared to ITO layer that has no Ni film. At wavelengths of 350 and 600 nm, the photoresponses of ITO/Ni/ITO device were predominant than that of reference ITO device. This highly conductive and photoresponsive Ni inserting ITO layers would be a promising device for various photoelectric applications.     

ITO薄膜的制备及其光电特性研究

采用直流磁控溅射法,分别用ITO陶瓷靶、In-Sn合金靶,在玻璃基片上镀膜。研究ITO透明导电膜其膜厚、靶材、溅射气压和溅射速率等工艺对光电特性的影响。结果表明,采用陶瓷靶镀膜要比合金靶效果好,膜厚70nm以上、溅射气压0.45Pa和溅射速率23nm/min左右为最佳工艺条件,并得到了ITO薄膜电阻率1.8×10–4Ω.cm、可见光透过率80%以上。     

聚酰亚胺衬底柔性非晶硅薄膜电池集成串联组件的研究

研究了柔性Si基薄膜太阳电池集成串联组件的制备与关键技术。对导电栅线在柔性薄膜太阳电池集成串联组件中的重要性进行了模拟计算,对柔性薄膜太阳电池激光刻蚀进行了理论分析与实验优化,并对柔性Si基薄膜太阳电池集成串联组件进行了设计与研制。在聚酰亚胺(PI)衬底上,通过卷对卷磁控溅射与卷对卷等离子增强化学气相沉积(PECVD)依次沉积复合背反射层Ag/ZnO、Si基薄膜层和透明导电膜层,采用激光刻蚀与丝网印刷工艺相结合实现集成串联,制备了柔性非晶Si(a-Si)薄膜太阳电池集成串联组件。柔性单结集成串联组件有效面积转换效率达到了4.572%(AM0),开路电压Voc=5.065V,填充因子FF=0.552。     

工艺条件对柔性衬底ITO薄膜光电性能的影响

采用直流磁控溅射法在柔性衬底上镀制ITO透明导电薄膜,全面研究了薄膜厚度、氧气流量、溅射速率、溅射气压和镀膜温度等工艺条件对ITO薄膜光电性能的影响。结果表明,当膜厚大于80nm、氧氩体积比为1∶40、溅射速率为5nm/min、溅射气压在0.5Pa左右、镀膜温度为80～160℃时,ITO薄膜的光电性能较好,其电阻率小于5×10–4?·cm、可见光透光率大于80%。     

ITO薄膜的近零介电常数波长的调控研究

近年来,氧化铟锡(ITO)薄膜因其可实现介电常数近零(Epsilon-Near-Zero,ENZ)且易于调制的特性,已经成为非线性光学和微纳光学等领域的研究热点.文章先使用射频磁控溅射法在硅基底上制备ITO薄膜,再通过椭圆偏振光谱仪测试并拟合其光学参数,探究了本底真空度、溅射功率、溅射气压、衬底温度和膜厚等因素对ITO薄膜ENZ波长的调节机制.通过优化工艺,使ITO薄膜最短ENZ波长蓝移至1 094.4 nm,突破了以往文献报道的极限.该研究将ITO薄膜的ENZ波长延伸至近红外短波区域,有望实现微纳光电器件相关领域向短波方向的应用拓展.     

ITO薄膜厚度和含氧量对其结构与性能的影响

在玻璃衬底上用直流磁控溅射的方法镀制ITO透明半导体膜,采用X射线衍射技术分析了膜层晶体结构与薄膜厚度和氧含量的关系,并测量了薄膜电阻率及透光率分别随膜厚和氧含量的变化情况。以低氧氩流量比(1/40)并控制膜厚在70nm以上进行镀膜,获得了结晶性好、电阻率低且透光率高的ITO透明半导体薄膜,所镀制的ITO膜电阻率降到1.8×10–4?·cm,可见光透光率达80%以上。     

Reflectivity and Abnormal Absorption at ITO/Al Interface

The electrical and optical thermal stability of indium tin oxide (ITO)/Al bilayers are investigated in this study. The electrical resistivity of ITO and ITO/Al multilayers, both about 1 × 10⁻³ Ω cm after annealing at 300°C for 1 min, are measured by the four-probe measurement method. In addition to the electrical measurements, we also observe the rapid initial diffusion of Al atoms into the ITO thin films. When the diffusing elemental Al atoms occupy interstitial sites they tend to form defects, causing a serious decrease in the reflectance of the a-ITO/Al bilayer in the wavelength region from 400 nm to 600 nm.     

Effects of post-thermal treatment on the properties of rf reactive sputtered ITO films

Indium tin oxide (ITO) thin film prepared by rf sputtering at various Ar-O₂ mixtures, were annealed at several temperatures. The electrical, optical and structural properties of the film were systematically investigated before and after post-thermal treatment. The influence of a reactive gas (O₂) on the sputtering rate of a metallic (indium/tin) alloy target was also investigated. The films were characterized by X-ray diffraction (XRD) measurement, scanning electron microscopy, and transmittance as a function of wavelength. The resistivity of 8.3×10⁻⁴ Ω cm has been achieved for the film thickness of 250 nm, deposited in pure Ar at room temperature (RT).     

光谱法在线控制ITO膜的制备

ＩＴＯ膜的特性受到溅射过程中很多因素的影响，但是实验证明ＩＴＯ膜的沉积速率与溅射过程中等离子体的特征光谱强度及此时靶电流比值成正比。本文提出了用光谱法在线控制ＩＴＯ透明导电膜的制备过程、实验结果。     

Photoelectric properties of ITO thin films deposited by DC magnetron sputtering

As anti-reflecting thin films and transparent electrodes of solar cells,indium tin oxide（ITO） thin films were prepared on glass substrates by DC magnetron sputtering process.The main sputtering conditions were sputtering power,substrate temperature and work pressure.The influence of the above sputtering conditions on the transmittance and conductivity of the deposited ITO films was investigated.The experimental results show that, the transmittance and the resistivity decrease as the sputtering power increases from 30 to 90 W.When the substrate temperature increases from 25 to 150℃,the transmittance increases slightly whereas the resistivity decreases.As the work pressure increases from 0.4 to 2.0 Pa,the transmittance decreases and the resistivity increases.When the sputtering power,substrate temperature and work pressure are 30 W,150℃,0.4 Pa respectively,the ITO thin films exhibit good electrical and optical properties,with resistivity below 10^-4Ω·cm and the transmittance in the visible wave band beyond 80%.Therefore,the ITO thin films are suitable as transparent electrodes of solar cells.     

ITO薄膜的电阻并联效应研究

采用电子束蒸发镀膜方法在K9玻璃基底上分别镀制了ITO/SiO₂/ITO,ITO/Ti₂O₃/ITO和ITO/MgF₂/ITO结构的多层薄膜,用四探针方块电阻仪测量薄膜表面的方块电阻,用原子力显微镜观测样品的表面微观形貌。结果显示,当ITO薄膜的粗糙度较大且介质薄膜的物理厚度小于100nm时,各层ITO薄膜之间通过山峰状的凸起结构相连通,导致样片表面的方块电阻测量值与各层ITO薄膜电阻的并联值相当。这表明,当ITO薄膜的粗糙度较大且介质薄膜厚度较小时,各层ITO薄膜表现出电阻并联效应。利用多层ITO薄膜的电阻并联效应设计并制备了450～1200nm超宽光谱透明导电薄膜,用四探针方块电阻仪测量了试验样片的表面方块电阻,用紫外-可见-近红外分光光度计测试了样片的光谱透射率。结果显示,在相同表面方块电阻条件下,相比于单层ITO薄膜,利用ITO薄膜电阻并联效应所制备的多层透明导电薄膜具有更高的光谱透射率。     

制备工艺对ITO薄膜的电阻率及沉积速率的影响

采用射频磁控溅射法制备了氧化铟锡[ITO,In2O3:SnO2=90:10(质量比)]薄膜,详细探讨了溅射气氛氧氩体积比、溅射功率及溅射气压对ITO薄膜电阻率和沉积速率的影响。结果表明:溅射工艺参数对ITO薄膜电阻率和沉积速率的影响十分明显。随着氧氩体积比的增大,样品的电阻率显著增大,沉积速率下降;随着溅射功率的增加,ITO薄膜的电阻率先减小后略微增大,沉积速率上升;随着溅射气压升高,ITO薄膜的电阻率先减小后增大,当溅射气压增大到较大值时,ITO薄膜的电阻率又开始减小,而沉积速率则先上升后下降。     

Electrical and optical properties of Ni-assisted grown single crystalline and transparent indium-tin-oxide nanowires

Transparent and single crystalline indium-tin-oxide (ITO) nanowires (NWs) were grown by sputtering method. A thin Ni film of 5 nm was deposited before ITO sputtering. Thermal treatment forms Ni nanoparticles, which act as templates to diffuse Ni into the sputtered ITO layer to grow single crystalline ITO NWs. This Ni diffusion through an ITO NW was investigated by transmission electron microscope to observe the Ni-tip sitting on a single crystalline ITO NW. Meanwhile, a single crystalline ITO structure was found at bottom and body part of a single ITO NW without remaining of Ni atoms. This indicates the Ni atoms diffuse through the oxygen vacancies of ITO structure.Rapid thermal process (RTP) applied to generate an initial stage of a formation of Ni nanoparticles with variation in time periods to demonstrate the existence of an optimum condition to initiate ITO NW growth. Modulation in ITO sputtering condition was applied to verify the ITO NW growth or the ITO film growth. The Ni-assisted grown ITO layer has an improved electrical conductivity while maintaining a similar transmittance value to that of a single ITO layer. Electrically conductive and optically transparent ITO nanowire-coated surface morphology would provide a great opportunity for various photoelectric devices.     

Solution-processed fabrication of highly transparent mono- and tri-colored quantum dot-light-emitting diodes

Analogous to organic light-emitting diode (OLED), quantum dot-light-emitting diode (QLED) possesses a high eligibility with respect to device structure for the transformation to transparent device that may be pursued as a next-generation display. We report the fabrication of a series of highly transparent mono-colored blue, green, and red QLEDs with a standard architecture simply by replacing thermally evaporated Al with sputtered indium tin oxide (ITO) film as a top cathode. To alleviate the sputtering damage on the underlying electron transport layer while securing a reasonable sheet resistance of ITO film, a moderate sputtering power is judiciously chosen to attain high device performance. Fabrication of a transparent tri-colored white or full-color-capable QLED, comprising an emitting layer mixed with three primary colored QDs, is also demonstrated and further implemented on a flexible substrate of polyethylene naphthalate to additionally offer its feasibility toward transparent flexible device.     

Preparation,structural and optical investigations of ITO nanopowder and ITO/epoxy nanocomposites

Indium Tin Oxide (ITO) nanopowder was synthesized by a sol–gel method. It was characterized by X-ray diffraction (XRD) and transmission electron microscopy. ITO/epoxy nanocomposites (ITO–EP-NCs) were prepared by mechanically dispersing the as-prepared ITO nanopowder into epoxy matrix. The XRD patterns show structural changes depending on ITO content. The interdependence of structural, morphological, optical properties and the dispersed concentration of ITO nanoparticles were investigated. The UV–visible absorption spectra revealed that the ITO–EP-NCs exhibit enhanced UV light absorption properties and wide absorption bandwidth ranging up to 400 nm from 2 wt% ITO loading. Thus, it indicated that UV and IR-shielding properties have been improved with the incorporation of ITO nanoparticles into the epoxy matrix.The gap energy of epoxy matrix was reduced by adding the ITO-NPs, leading to the improvement of its electrical conductivity. Indeed, the AC electrical conductivity of ITO–EP-NCs showed a critical percolation threshold p_c=0.21 wt% ITO. For low loading (<2 wt% ITO), the ITO–EP-NCs have combined good transparency in the visible range and enhanced electrical conductivity, which are required for optoelectronics devices.     

4H-SiC metal–semiconductor–metal ultraviolet photodetectors with Ni/ITO electrodes

Indium–tin-oxide (ITO), Ni/ITO and Ni layers were deposited onto glass and/or SiC substrates by DC sputtering under different deposition conditions. SiC-based metal–semiconductor–metal (MSM) ultraviolet (UV) photodetectors were also fabricated using these materials as contract electrodes. It was found that ITO film deposited without oxygen gas could provide us a better optical property and a better electrical property. It was also found that the dark current of the ITO/SiC MSM UV photodetector was extremely large. Furthermore, it was found that the insertion of a 10 nm Ni layer could significantly reduce the dark current. It was also found that the photo-current to dark current contrast was more than 3 orders of magnitude with a 5 V applied bias for the SiC MSM UV photodetector with 10 nm Ni/90 nm ITO contact electrodes. With an even larger 40 V applied bias, the photo-current to dark current contrast could almost reach 4 orders of magnitude.     

High efficient ITO free inverted organic solar cells based on ultrathin Ca modified AZO cathode and their light soaking issue

Aluminum doped zinc oxide (AZO) was used to be the cathode instead of indium-tin-oxide (ITO) in the poly (3-hexylthiophene-2,5-diyl):[6,6]-phenyl C₆₁ butyric acid methyl ester (P3HT:PCBM) based bulk heterojunction inverted organic solar cells (IOSCs). For the AZO only IOSC, the device shows a poor power conversion efficiency (PCE) of 1.34% and a light soaking issue related to the energy barrier at the AZO/P3HT:PCBM interface. When a 5 nm Ca modifying layer is inserted between AZO and P3HT:PCBM, the obtained AZO/Ca (5 nm) IOSC shows an increased PCE from 1.74% to 2.69% after 15 min illumination. It is thought that the increased photoconductivity of AZO/Ca (5 nm) film upon illumination and the enhanced electron transport across the AZO/Ca interface may be responsible for the light soaking issue. When an ultrathin Ca modifying layer of 1 nm is employed, a further improved PCE of 3.17% is obtained, and remarkably, no light soaking issue is observed in this case. However, this unexpected issue appears after the un-encapsulated AZO/Ca (1 nm) IOSC has been stored in air for several days, which may be due to the energy loss in the electron transport across the interface between partly oxidized Ca and AZO layers induced by the oxidization of Ca. Furthermore, the AZO/Ca (1 nm) IOSC has a comparable PCE to the referenced ITO/Ca (1 nm) IOSC and presents a better air-stability. It is thus concluded that the AZO cathode is a promising alternative of ITO to fabricate the high efficient and long-lifetime IOSCs.     

Effects of surface treatment of ITO anode layer patterned with shadow mask technology on characteristics of organic light-emitting diodes

We investigated the effects of various surface treatments of indium tin oxide (ITO) on the electrical and optical characteristics of organic light-emitting diodes (OLEDs). A 150-nm-thick ITO anode layer was patterned directly with a shadow mask during the sputtering process without the use of a conventional photolithography patterning method. The sputtered ITO layer was subjected to thermal and oxygen plasma treatments to reduce the sheet resistance and improve surface roughness. The thermal treatment was performed for 1 h at temperatures of 250 and 380 °C, which were chosen so that the glass substrates would not deform from thermal damage. The measured sheet resistance decreased from 30.86 Ω/sq for the as-sputtered samples to 8.76 Ω/sq for the samples thermally treated at 380 °C for 1 h followed by oxygen plasma treatment. The root-mean-square surface roughness measured by atomic force microscopy considerably decreased to 3.88 nm with oxygen plasma treatment. The thermal treatment considerably decreased the sheet resistance of the ITO anode layer patterned with the shadow mask. The spike-like structures that are often formed and observed in shadow mask-patterned ITO anode layers were almost all removed by the oxygen plasma treatment. Therefore, a smooth surface for shadow mask-patterned ITO layers with low sheet resistance can be obtained by combining thermal and oxygen plasma treatments. A smooth surface and low sheet resistance improves the electrical and optical characteristics of OLEDs. The surface-treated ITO layer was used to fabricate and characterize green phosphorescent OLED devices. The typical characteristics of OLED devices based on surface-treated shadow mask-patterned ITO layers were compared with those fabricated on untreated and photolithography-patterned ITO layers to investigate the surface treatment effects. The OLED devices fabricated by thermal treatment at 380 °C for 1 h followed by oxygen plasma treatment for 180 s showed the highest luminance and current density. Furthermore, the leakage current that might be induced by the rough ITO surface was dramatically reduced to 0.112 mA/cm². Our study showed that the shadow mask-patterned ITO anode layer treated by heat and plasma and having a low sheet resistance and surface roughness yielded excellent electrical and optical properties for OLEDs compared to those based on an untreated ITO layer. The fabricated OLED devices using the surface-treated shadow mask-patterned ITO layer exhibited comparable characteristics to those obtained from a conventional photolithography-patterned ITO anode.     

Influence of mechanical stress on adhesion properties of DC magnetron sputtered Ti/NiV/Ag layers on nSi substrate

Due to insufficient adhesion of sputtered Ti/NiV/Ag metallization scheme on n⁺Si substrate when annealed below 550 °C, investigation was focused on the influence of process parameters on adhesion properties. Adhesion between metallic stack and Si substrate was found to be a strong function of annealing temperature. Additional investigations showed that the cause for poor adhesion was also rather high residual stress in metal thin layers, particularly stress in sputtered NiV layer. High residual stress was measured for NiV (1883 ± 252 MPa) and lower for Ti (334 ± 60 MPa) and Ag (310 ± 10 MPa) layer, respectively. The influence of sputtering parameters on the stress behavior was experimentally verified. By reducing the cathode DC power and Ar working pressure during NiV sputtering we were able to reduce the stress within the structure. A clear correlation was found between the residual stress magnitude and adhesion properties within the temperature range from room temperature to 550 °C. By residual stress reduction within a metallic stack, the necessary annealing temperature to obtain optimal adhesion was reduced from 550 to 500 °C.