Soft chemistry based sponge-like indium tin oxide (ITO) ---- a prospective component of photoanode for solar cell application

Previously we reported the synthesis of novel organic-inorganic composite indium tin oxide (ITO) foam precursor leading to the formation of “sponge-like” ITO by burning away the organics. This newly made sponge-like ITO possesses relatively high electrical conductivity due to phonon confinement with reasonable pore structure and may have potential application as functional materials in semiconducting dye absorbing layer in dye-sensitized solar cell (DSSC) and also as the receptor of electrons injected from the quantum dots (QDs) of organic--inorganic hybrid QD based solar cell. This report is a short review of “sponge-like” ITO described as a lecture note on its future use as an alternative new prospective material for photoanode of solar cell in the domain of sustainable energy.     

退火处理对铟锡氧化物粉末的影响

对两种不同比表面积(BET)的铟锡氧化物(ITO)纳米粉末进行退火处理,研究和比较了温度对两种粉末微观组织和结构的影响,并对这两种粉末烧结的靶材进行了比较。结果表明,在800～1500℃进行不同温度的退火处理后,在1200℃以上,两种比表面积的ITO粉末粒径增长显著,颗粒之间出现了相互合并和结合长大现象,而高BET粉末的粒径增加幅度比低BET粉末的更大;在1525℃烧结后,用高BET粉末烧成的靶材的晶粒和气孔尺寸更大,气孔数量也更多。     

Low temperature processing of hybrid nanoparticulate Indium Tin Oxide (ITO) polymer layers and application in large scale lighting devices

We report on transparent conductive indium tin oxide (In₂O₃:Sn; ITO) nanoparticle films processed at a low temperature of 130 °C for the application in lighting devices using spin coating and doctor blading techniques. Major emphasis is put on the beneficial application of the particular transparent electrode material for the fabrication of patterned large area electroluminescence lamps. In order to improve film properties like adhesion and conductivity, hybrid nanoparticle-polymer blends out of ITO particles and organic film-forming agent polyvinylpyrrolidone (PVP) and the organofunctional coupling agent 3-methacryloxypropyltrimethoxysilane (MPTS) have been developed. The layers were cured by UV-irradiation, which was also used for lateral structuring of the transparent, conductive electrode. Additional low-temperature heat treatment (T = 130 °C) in air and forming gas improved the electronic properties. While pure ITO nanoparticulate layers processed at 130 °C exhibited conductance of up to 3.1 Ω^− 1 cm^− 1, the nanocomposite coatings showed a conductance of up to 9.8 Ω^− 1 cm^− 1. Corresponding layers with a sheet resistance of 750 Ω/□ were applied in electroluminescent lamps.     

氯离子与铟离子的总浓度比对铟锡氧化物前驱体氢氧化物)粒径的影响

用络盐法制备了铟锡氧化物(ITO)纳米粉末. 通过对铟和锡的络合盐[(NH₄)₂InCl₅·H₂O和(NH₄)₂SnCl₆]的制备研究, 证实了反应初始溶液中络离子的存在. 通过调节氯离子与铟离子的总浓度比研究了络离子对ITO前驱体(氢氧化物)粒径的影响. 提出了络离子对纳米ITO粉末粒径的影响原理: 络离子的存在, 降低了反应初始溶液中游离In ³⁺和Sn ⁴⁺的浓度, 有利于纳米级ITO粉末的生成. 通过XRD和激光粒度仪对ITO前驱体(氢氧化物)进行了表征.     

溶剂热-煅烧法合成纳米ITO粉体

本文采用溶剂热-煅烧法制备纳米铟锡复合氧化物(ITO).以In(4N)、SnCl4·5H2O为起始原料,通过XRD、SEM及微波吸收性能的分析,考察了溶剂热反应中溶剂对ITO粉体结构及性能的影响.研究表明以1,4-丁二醇为溶剂,KBr为矿化剂(浓度0.5mol/L)在260℃下醇热6h,得到结晶性良好的羟基氧化铟和锡掺杂氧化铟的混合物.溶剂热产物在550℃下煅烧2h得到纳米ITO粉体,醇热-煅烧产物的吸波性能良好.     

制备工艺对纳米级铟锡氧化物(ITO)形貌和电性能的影响

以SnCl4·5H2O、In和浓盐酸为原料,采用化学共沉淀法制备出了纳米级锡掺杂氧化铟(ITO)导电微粉,系统地研究了掺杂量,共沉淀温度,pH值,热处理时间、温度对粉体粒度、形貌和电性能的影响规律。研究表明,合成的ITO粉体分散性较好、导电性能优异,粒径在40nm左右具有立方铁锰矿结构。在ITO纳米导电粉的制备过程中,共沉淀温度和滴定终点pH值对其形貌和性能有很大影响,当共沉淀温度在60℃左右,pH=6时制得的粉体性能最佳。煅烧条件对粉体的形貌、粒度和导电性也有较大的影响,在700℃,4h条件下可以制得导电性能良好,结晶完好,粒度分布均匀的ITO粉体。掺入Sn(Ⅳ)的量对载流子的迁移率有很大的影响,在掺杂浓度为10%左右可制得导电性极佳的纳米ITO粉体。     

磁控溅射ITO薄膜的退火处理

采用直流磁控溅射方法在室温下玻璃基板上制备ITO(Indium tin oxide)薄膜,并在真空中不同温度(100℃~400℃)下退火处理.研究了退火对薄膜表面形貌、电光特性的影响.XRD测试发现薄膜在200℃退火后结晶,优选晶向为(222).随退火温度升高,方块电阻迅速下降,表面更加平整,薄膜在可见光范围平均透过率提高到85%.     

聚邻甲氧基苯胺薄膜对pH的光学响应

在盐酸介质中,应用循环伏安法通过电聚合在氧化铟锡(ITO)透明导电玻璃上形成聚邻甲氧基苯胺薄膜.用紫外可见光谱方法测定了聚合物薄膜在不同pH下的特征吸收光谱,聚邻甲氧基苯胺薄膜的λmax在557～746nm之间,作出了相应的滴定曲线.结果表明,在pH为1～12范围内聚合物薄膜对pH的变化表现了极高的光学敏感性,其表观pKa约为6.4.应用聚邻甲氧基苯胺薄膜测定了不同pH的溶液,其测定结果与精密酸度计相比误差＜±4%.     

集成电极的复合混沌混合芯片的快速制备及表征

试剂的有效混合是化学和生化反应的前提条件,因此混合成为微全分析系统的重要功能单元.本文介绍了一种通道中集成氧化铟锡(ITO)电极的聚二甲基硅氧烷(PDMS)-玻璃复合混沌混合芯片的快速制备方法,对PDMS的混合通道表面进行了硅溶胶改性.首次用集成的电极和酸碱反应过程中的电导变化对其混合效果进行了评价.利用玻璃各向同性刻蚀特点,一次曝光和一次刻蚀得到了混沌混合微通道结构的母板.利用光辅助原位聚合的方法快速制备了与母板微结构互补的聚甲基丙烯酸甲酯(PMMA)阳模,利用PI)MS原位聚合的方法复制得到了与玻璃母板结构相同的混沌混合通道结构的芯片.用电导法对芯片的混合有效性进行了表征.PDMS复制芯片与ITO玻璃永久封合即得全透明的复合混沌混合芯片.本文介绍的加工方法无需二次曝光及SU-8光刻胶,容易多次复制,在微流控分析芯片中将有广泛应用.     

溅射及RTA处理对ITO薄膜特性的影响

采用RF-磁控溅射生长铟锡氧化物薄膜(ITO),研究了生长条件、快速热退火(RTA)温度对薄膜的晶化情况、透过率、电导率以及表面形貌的影响.结果表明:改变In2-x3 (Snx4 ·e)O3制备过程中的氧含量使Sn4 ·e对电子束缚能力发生变化,过高的氧分压使费米能级EF降低,功函数Ws增大,氧气流量为2 ml/min、退火温度为450℃时薄膜电阻率最低为2.5×10-4 Ω·cm,透过率达88%以上.     

The growth of indium-tin-oxide thin films on glass substrates using DC reactive magnetron sputtering

The growth of indium-tin-oxide thin films as a function of thickness using DC reactive magnetron sputtering was investigated. As the film thickness grew, the crystallinity increased showing both (2 2 2) and (4 0 0) planes. However, the peak intensity ratio of I₂₂₂/I₄₀₀ in the X-ray diffraction pattern decreased with the thickness, implying a preferred orientation along the (4 0 0) planes at the higher thickness. The grain sizes and domain boundaries grew clearly and the specific resistivities decreased with the film thickness. Two components of the specific resistivities, carrier mobility and carrier concentration, showed opposite behaviour: (i) increasing carrier concentration; (ii) decreasing carrier mobility with increase in the film thickness. Furthermore, the graded growth of the ITO thin film could also be shown from the optical properties and morphological properties by UV/Vis/NIR spectroscopy and scanning electron microscopy.     

Influence of ITO patterning on reliability of organic light emitting devices

Indium tin oxide (ITO) films are widely used for a transparent electrode of organic light emitting devices (OLEDs) because of its excellent conductivity and transparency. Two types of ITO substrates with different surface roughness were selected to use as anode of OLEDs. In addition, two types of etching process of ITO substrate, particularly the etching time, were also carried out. It was found that the surface roughness and/or the etching process of ITO substrate strongly influenced on an edge of ITO surface, further affected the operating characteristics and reliability of devices.     

Effect of oxygen flow rate on ITO thin films deposited by facing targets sputtering

Tin-doped indium oxide (ITO) thin films were deposited on glass substrates at various oxygen flow rates using a planar magnetron sputtering system with facing targets. In this system, the strong internal magnets inside the target holders confine the plasma between the targets. High resolution transmission electron microscopy revealed a combination of amorphous and crystalline phases on the glass substrate. X-ray photoelectron spectroscopy suggested that the decrease in carrier concentration and increase in mobility were caused by a decrease in the concentration of Sn⁴⁺ states. The electrical and optical properties of the ITO films were examined by Hall measurements and UV-visible spectroscopy, which showed a film resistivity and transmittance of 4.26 × l0⁻⁴ Ω cm, and > 80% in the visible region, respectively.     

Laser direct write patterning technique of indium tin oxide film

The circuit patterns of transparent conductive oxide films (TCO films) have widely formed using the traditional photolithography method. The indium tin oxide (ITO) films of flat panel displays are one of the TCO films and usually ablated using the wet etching, which is widely adopted in the semiconductor processing. However, the chemical wet etching techniques usually appear with more disadvantages in the procedure, including the chemical pollution, the under-cut effect, the swelling and the costly. Therefore, the dry etching would be replaced the photolithography procedures. The laser directing method is one of the dry etching techniques and could form the circuit pattern on the ITO glasses. Moreover, the laser directing techniques could flexibility make the circuit pattern in the TCO film and the substrate would be not eroded by the laser ablation. The investigation is interested in circuit patterning of glass substrate using the laser direct writing techniques to ablate the ITO films by a UV laser materials processing system. The UV laser is a third-harmonic Nd: YAG laser with a 355 nm of wavelength and the power is 1.0 W. In this paper, the ITO films are ablated by the UV laser materials processing system which used the different repetition rate and the feeding speeds of tables. The results of laser pattering of ITO films are measured using the optical microscope (OM) and the scanning electron microscope (SEM), and it indicates the repetition rate of laser would affect the width of line.     

Growth and characterization of indium tin oxide thin films deposited on PET substrates

Transparent and conductive indium tin oxide (ITO) thin films were deposited onto polyethylene terephthalate (PET) by d.c. magnetron sputtering as the front and back electrical contact for applications in flexible displays and optoelectronic devices. In addition, ITO powder was used for sputter target in order to reduce the cost and time of the film formation processes. As the sputtering power and pressure increased, the electrical conductivity of ITO films decreased. The films were increasingly dark gray colored as the sputtering power increased, resulting in the loss of transmittance of the films. When the pressure during deposition was higher, however, the optical transmittance improved at visible region of light. ITO films deposited onto PET have shown similar optical transmittance and electrical resistivity, in comparison with films onto glass substrate. High quality films with resistivity as low as 2.5 × 10^− 3 Ω cm and transmittance over 80% have been obtained on to PET substrate by suitably controlling the deposition parameters.     

Preparation and characterization of ceramic thin film thermocouples

Indium tin oxide (ITO), alumina doped zinc oxide (ZnO) and NiCrCoAlY/alumina nanocomposites were systematically investigated as thermoelements. These ceramic thermoelements were initially tested relative to a platinum reference electrode and the resulting thermoelectric properties were evaluated. Bi-ceramic junctions comprised of the most stable and responsive ceramic thermoelements, i.e. those thermoelements with the largest and most stable Seebeck coefficients relative to platinum, were fabricated and tested. A bi-ceramic junction based on nitrogen-doped ITO:oxygen-doped ITO exhibited excellent high temperature stability and reproducibility, however, this thermocouple pair had a relatively low Seebeck coefficient (6 μV/°C). Alumina doped ZnO:ITO thermocouples generated a very large electromotive force at low temperatures but lacked high temperature stability. When nitrogen-doped ITO was combined with a NiCoCrAlY/alumina nanocomposite, a very large and stable Seebeck coefficient (375 μV/°C) was realized. Ceramic thermocouples based on several candidate materials were demonstrated at temperatures up to 1200 °C and the potential of using these materials in other thermoelectric devices including those for energy harvesting is discussed.     

Effect of barrier layers on the properties of indium tin oxide thin films on soda lime glass substrates

In this paper, the electrical, structural and optical properties of indium tin oxide (ITO) films deposited on soda lime glass (SLG) haven been investigated, along with high strain point glass (HSPG) substrate, through radio frequency magnetron sputtering using a ceramic target (In₂O₃:SnO₂, 90:10 wt.%). The ITO films deposited on the SLG show a high electrical resistivity and structural defects compared with those deposited on HSPG due to the Na ions from the SLG diffusing to the ITO film by annealing. However, these properties can be improved by intercalating a barrier layer of SiO₂ or Al₂O₃ between the ITO film and the SLG substrate. SIMS analysis has confirmed that the barrier layer inhibits the Na ion's diffusion from the SLG. In particular, the ITO films deposited on the Al₂O₃ barrier layer, show better properties than those deposited on the SiO₂ barrier layer.     

Electrical and optical properties of indium tin oxide films prepared on plastic substrates by radio frequency magnetron sputtering

The influence of deposition power, thickness and oxygen gas flow rate on electrical and optical properties of indium tin oxide (ITO) films deposited on flexible, transparent substrates, such as polycarbonate (PC) and metallocene cyclo-olefin copolymers (mCOC), at room temperature was studied. The ITO films were prepared by radio frequency magnetron sputtering with the target made by sintering a mixture of 90 wt.% of indium oxide (In₂O₃) and 10 wt.% of tin oxide (SnO₂). The results show that (1) average transmission in the visible range (400-700 nm) was about 85%-90%, and (2) ITO films deposited on glass, PC and mCOC at 100 W without supplying additional oxygen gas had optimum resistivity of 6.35 × 10⁻⁴ Ω-cm, 5.86 × 10⁻⁴ Ω-cm and 6.72 × 10⁻⁴ Ω-cm, respectively. In terms of both electrical and optical properties of indium tin oxide films, the optimum thickness was observed to be 150-300 nm.     

Properties of ITO on plastics and glass by Nd:YAG laser deposition at 355 and 532 nm

Indium tin oxide (ITO) was deposited on polycarbonate (PC), polyethylene terephthalate (PET) and glass substrates at room temperature and in a low-pressure oxygen environment by a pulsed Nd:YAG laser at 355 and 532 nm. The ITO film resistivity varied with the oxygen pressure, which achieved the lowest value of 1.5 × 10⁻³ Ω cm from the four-point probe measurements. The highest optical transmittance which depended on the target-to-substrate distance, was determined from UV-vis-NIR spectrophotometer. The highest optical transmission was 94% at 5 cm. The carrier concentration, of the order of 10¹⁹ cm⁻³ was determined from the Hall-effect measurements. Those films deposited at 355 nm of laser wavelength did show some better properties as compared to 532 nm. Attempts were made to use these ITO-coated plastic substrates for the fabrication of a organic light-emitting device that was based on single-layer, molecularly doped (poly(N-vinyl carbazole)) (PVK) with a mixture of tris(8-hydroxyquinoline) aluminum (III) (Alq₃) and N,N'-bis (3-methylphenyl)-N,N'-bis-(phenyl)-benzidine (TPD) of 1:1 ratio.