Eco-friendly method of fabricating indium-tin-oxide thin films using pure aqueous sol-gel

An indium-tin-oxide (ITO) thin film with approximately 50 nm thickness was successfully synthesized on glass substrates by using a fully aqueous sol-gel process. The sol was prepared from indium nitrate hydrate and tin fluoride as a precursor. Thermogravimetric analysis confirmed that the sol converted into crystalline ITO at 286 °C. The optical band gap and transmittance of the thin film were observed to increase with annealing temperature and plasma treatment time. X-ray photoelectron spectroscopy and transmittance studies established that the number of oxygen vacancies in the thin film drastically increased with increasing temperature and plasma treatment. The annealing temperature and argon plasma treatment time appear to be key factors in reducing resistivity and increasing the transmittance of the thin film. A considerable decrease in the resistivity of the ITO thin film was observed after Ar plasma treatment. This eco-friendly sol-gel ITO thin film may find potential applications in n-type ohmic electrodes for ink-jet printable electronics.     

Transparent and conductive indium tin oxide/polyimide films prepared by high‐temperature radio‐frequency magnetron sputtering

A highly transparent and thermally stable polyimide (PI) substrate was prepared and used for the fabrication of indium tin oxide (ITO)/PI films via radio‐frequency magnetron sputtering at an elevated substrate temperature. The effect of the deposition conditions, that is, the oxygen flow rate, substrate temperature, sputtering power, and working pressure, on the optical and electrical properties of the ITO/PI films were investigated from the microstructural aspects. The results indicate that the optical and electrical properties of ITO were sensitive to the oxygen. Moreover, it was beneficial to the improvement of the ITO conductivity through the adoption of a high substrate temperature and sputtering power and a low working pressure in the deposition process. A two‐step deposition method was developed in which a thick bulk ITO layer was overlapped by deposition on a thin seed ITO layer with a dense surface to prepare the highly transparent and conductive ITO/PI films. The ITO/PI film after annealing at 240°C gave a transmittance of 83% and a sheet resistance of 19.7 Ω/square. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42753.     

高密度ITO靶材烧结方法及发展趋势

简要介绍了铟（In）的用途及国内铟产业的现状,对ITO薄膜的特性、应用领域及高密度ITO靶材溅射镀膜的优点进行了描述。重点对高密度ITO靶材的烧结工艺和成形方法的优缺点及发展现状进行了阐述。探讨了高密度ITO靶材生产技术的发展趋势。     

Influence of Ag incorporation on the structural,optical and electrical properties of ITO/Ag/ITO multilayers for inorganic all-solid-state electrochromic devices

Indium tin oxide/silver/indium tin oxide (ITO/Ag/ITO, IAI) multilayer structures were prepared by DC magnetron sputtering as a conductive transparent electrode for inorganic all-solid-state electrochromic devices. A thin layer of silver (Ag) with various thicknesses was inserted between two layers of ITO films. The XRD and SEM results revealed that the microscopic morphology of Ag film was closely related to the thickness. Besides, the electrical and optical properties of the IAI multilayers were significantly influenced by the Ag layer thickness. The optimized IAI multilayers demonstrated the best combination of electrical and optical properties with a figure of merit of 54.05 (sheet resistance of 6.14 Ω/cm²and optical transmittance of 90.83%) when the Ag film was 10 nm thick. In order to evaluate the IAI multilayers as a transparent electrode for electrochromic applications, two ECDs with the structures of ITO/NiO_x/LiPON/WO₃/ITO and ITO/NiO_x/LiPON/WO₃/IAI were prepared, and their electro-optical properties were characterized by cyclic voltammetry (CV), chronoamperometry (CA) and spectroscopic measurements. Compared with ECD the pure ITO top electrode (ITO/NiO_x/LiPON/WO₃/ITO), the ECD with the IAI top electrode (ITO/NiO_x/LiPON/WO₃/IAI) presented a slightly smaller optical modulation amplitude, but a faster switching speed. All our findings indicate that the IAI multilayer structure is a promising alternative to the ITO thin film for inorganic all-solid state electrochromic applications.     

Rapid thermal annealing effect of transparent ITO source and drain electrode for transparent thin film transistors

We investigated the rapid thermal annealing (RTA) sequence effect on the electrical, optical, morphological, and structural properties of transparent thin film transistors (TTFTs) with an indium gallium zinc oxide (IGZO) channel and an indium tin oxide (ITO) source/drain. The electrical and optical properties of the IGZO channel and the ITO source/drain electrodes were compared as a function of RTA temperature in ambient air. The performance of a TTFT with only an RTA-processed IGZO channel was compared with that of a TTFT with an RTA-processed IGZO channel and ITO source/drain electrodes. Using the circular transmission line measurement (CTLM) method, we suggest a possible mechanism that explains the effect of the RTA process on the performance of the TTFT with only an annealed IGZO channel vs. that with an annealed IGZO/ITO multilayer. The TTFT with an RTA-processed IGZO/ITO multilayer showed a threshold voltage shift, an improved on/off ratio of 3.54 × 10¹¹, a subthreshold swing of 0.33 V/decade, and a high mobility of 8.69 cm²/V·s. This indicates that simultaneous RTA processing for an IGZO channel and an ITO electrode is beneficial for the fabrication of high-performance TTFTs.     

Indium tin oxide exhibiting high poly-crystallinity on oxygen plasma-treated polyethylene terephthalate surface

Low-resistivity indium tin oxide [ITO] film was successfully deposited on oxygen plasma-treated polyethylene terephthalate [PET] surfaces at room temperature. X-ray diffraction [XRD] measurements demonstrated that the film deposited on the PET surface that had not been treated with oxygen plasma had an amorphous structure. In contrast, after the low-power oxygen plasma treatment of the PET surface, the ITO film deposited on the PET surface had a poly-crystalline structure due to interactions between electric dipoles on the PET surface and electric dipoles in the ITO film. The minimum resistivity of the poly-crystalline ITO was about 3.6 times lower than that of the amorphous ITO film. In addition, we found that the resistivity of ITO film is proportional to the intensity of the (400) line in the film''s XRD spectra.     

Transmission electron microscope observation of organic–inorganic hybrid thin active layers of light-emitting diodes

Low-resistivity indium tin oxide [ITO] film was successfully deposited on oxygen plasma-treated polyethylene terephthalate [PET] surfaces at room temperature. X-ray diffraction [XRD] measurements demonstrated that the film deposited on the PET surface that had not been treated with oxygen plasma had an amorphous structure. In contrast, after the low-power oxygen plasma treatment of the PET surface, the ITO film deposited on the PET surface had a poly-crystalline structure due to interactions between electric dipoles on the PET surface and electric dipoles in the ITO film. The minimum resistivity of the poly-crystalline ITO was about 3.6 times lower than that of the amorphous ITO film. In addition, we found that the resistivity of ITO film is proportional to the intensity of the (400) line in the film's XRD spectra.     

Influence of an In2O3 buffer layer on the properties of ITO thin films

In the present study, an indium oxide (In₂O₃) thin film was deposited as a buffer layer between ITO (indium tin oxide) and PES (polyestersulfone) by RF (radio frequency) magnetron sputtering at room temperature, and X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM) were conducted to characterise the structural variation. The random texture of the ITO/In₂O₃ multilayered film favoured the (2 2 2) crystallographic plane rather than the (4 0 0) plane, which was favoured in single-layer ITO films. Transmission electron microscopy (TEM) observations further indicated that the buffer layer of In₂O₃ film was amorphous, while the ITO film was characterised by a columnar structure that was oriented perpendicular to the substrate surface. The electrical and optical properties of ITO/In₂O₃ multilayered films were enhanced due to the superior crystallinity and larger grain size of the material, as observed by XRD and FESEM. The multilayered film presented an electrical resistivity of 3.1 × 10⁻⁴ Ω cm, which is significantly better than that of a single-layer ITO film without an In₂O₃ buffer layer (4.7 × 10⁻⁴ Ω cm). In addition, optical transmission through the multilayered film increased by 2-4% due to the widening of the band gap by 0.2 eV, which was attributed to a Burstin-Moss shift.     

Nanoscale coaxial cables produced from vertically aligned carbon nanotube arrays grown via chemical vapor deposition and coated with indium tin oxide via ion assisted deposition

A highly conformal homogeneous indium tin oxide (ITO) thin film coating has been produced on vertically aligned carbon nanotube arrays by ion assisted deposition. The deposition process generates, in effect, a coaxial cable structure of ITO about a carbon nanotube. The deposited ITO films are uniformly 5 nm thick and have high crystallinity and excellent optical absorption properties, indicating they would be good candidates for use in solar cells, flexible electronics and displays. The materials are analyzed by scanning and transmission electron microscopy, X-ray diffraction, and visual light spectrometry.     

Effective hole‐injection characteristics of organic light‐emitting diodes due to fluorinated self‐assembled monolayer embedded as a buffer layer

The electrical and optical properties of organic light‐emitting diodes (OLEDs) are demonstrated by varying the length of the alkyl chain of a fluorinated self‐assembled monolayer (F‐nSAM). OLEDs containing F‐nSAMs that have a long alkyl chain length were found to exhibit excellent properties in terms of current density, luminance, turn‐on voltage, etc. The obtained current density at 6 V, which was the highest measurement voltage, was up to about 36 times higher for an OLED including an F‐12SAM thin film with the longest chain length than for an OLED including only an indium tin oxide (ITO) substrate. With regard to luminance characteristics depending on voltage, the luminance was about 13 times higher for the OLED including the F‐12SAM thin film than for the OLED including only the ITO substrate. Also, the turn‐on voltage of the OLED including the F‐12SAM thin film was decreased by approximately 1 V compared to that of the OLED including only the ITO substrate. Although F‐nSAMs with alkyl chains have insulating film properties, F‐nSAMs with long alkyl chains exhibited good electrical and optical properties because of an improvement in the hole‐injection barrier due to a large positive shift of the vacuum level and smooth carrier injection resulting from a high contact angle due to strong hydrophobic properties caused by the good alignment properties of F‐nSAMs resulting from strong van der Waals forces between the molecules due to the long alkyl chains. © 2019 Society of Chemical Industry     

Properties of polymer light‐emitting diodes coated on surface‐treated ITO/glass substrates

We fabricated blue polymer light‐emitting diodes (PLEDs) with indium tin oxide (ITO)/PEDOT : PSS/PVK/PFO‐poss/LiF/Al structures. All of the organic film layers were prepared by the spin‐coating method on plasma and heat‐treated ITO/glass substrates. The dependences of the optical and electrical properties of the PLEDs on the plasma and heat treatment of the ITO film and the introduction of poly(N‐vinylcarbazole) (PVK) layer were investigated. The AFM measurements indicated that the surface roughness of the ITO transparent film was improved by the plasma and heat treatment. In the emission spectra, the intensity of the excimer peaks of the PFO‐poss [polyhedral oligomeric silsesquioxane‐terminated poly(9,9‐dioctylfluorene)] emission layer were decreased for the PLED device with the PVK film layer compared with the one without the PVK layer. The maximum current density, luminance and current efficiency of the PLEDs were found to be about 470 mA/cm², 486 cd/m² at an input voltage of 12 V and 0.55 cd/A at 100 cd/m² in luminance, respectively. The color coordinates (CIE chart) of the blue PLEDs were in the range of x = 0.17 ～ 0.20, y = 0.13 ～ 0.16, and the peak emission spectrum was about 430 nm, showing a good blue color. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

ITO薄膜的研究进展

ITO是锡掺杂氧化铟薄膜的简称,属于透明导电氧化物材料。常规沉积方法制备的ITO薄膜通常为非晶态或体心立方晶系晶体,为n型半导体材料,其载流子为自由电子,主要来源于沉积过程中薄膜化学计量比偏离或阳离子掺杂形成的施主杂质。ITO薄膜是当前研究和使用最为广泛的透明导电氧化物薄膜材料,由于具有低电阻率、高可见光透过率、高红外反射率等独特物理特性而被大量应用于平板显示器、太阳能电池、发光二极管、气体传感器、飞机风挡玻璃除霜器等领域。此外,ITO薄膜对微波还具有高达85%的衰减作用,因而在电磁屏蔽等军用领域显示出巨大的潜在应用价值。过去几十年里,针对ITO薄膜的研究工作主要聚焦于薄膜的光电性能上。当前,伴随着ITO薄膜的应用范围在航空航天和军用武器装备等领域的拓展,ITO薄膜在恶劣力学环境中的使用日渐增多。因此,除光电性能外,ITO薄膜的力学性能也开始受到研究者越来越多的关注,人们对薄膜器件在各类恶劣使用环境中的稳定性及耐久性提出了更高的要求,这一要求使得对ITO薄膜力学性能的深入研究分析有了重要的理论及实际意义。本文综述了近年来ITO薄膜在微结构特性、能带结构、光电性能及力学性能等方面的研究进展,简略探讨了ITO薄膜的研究发展方向。     

W18O49/PET-ITO柔性电致变色薄膜制备及其变色性能

采用溶剂热法制备W18O49纳米线电致变色材料，喷涂在聚对苯二甲酸乙二醇酯?氧化铟锡(PET?ITO)(方阻35 Ω)柔性透明导电基底上得到柔性电致变色薄膜。采用X射线衍射仪、扫描电子显微镜、高分辨场透射电子显微镜和X射线光电子能谱对W18O49的微观结构和价态等进行表征，用电化学工作站与紫外?可见光分光光度计对W18O49/PET?ITO柔性电致变色薄膜的光学调制范围、响应时间和循环稳定性等进行了表征和分析。结果表明，光谱扫描波长?=633 nm时，W18O49/PET?ITO柔性电致变色薄膜的光学调制范围ΔT=23%。薄膜透光率变化90%时，着色和褪色时间分别为12.8和10.6 s。W18O49/PET?ITO柔性电致变色薄膜具有优异的循环稳定性，连续着色褪色循环3000 s薄膜透光率仍达80.9%。     

Effect of heat treatment on the dispersion and sintering behaviour of tin doped indium oxide powders

Due to the importance of structural uniformity of ITO targets on the properties of ITO films, the untreated and heat treated tin doped indium oxide powders were used to study the effects of four different dispersants on the dispersion behaviour of nanosized ITO powders. The optimum dispersant is NH₄PAA and its optimum amount is 1.00?wt% when the pH value is 9.0. In addition, the effect of the treatment temperature of nanosized ITO powders on the dispersion and sintering behaviour was also studied by SEM, TEM and XRD. The solid loading of ITO slurries and the relative density of the sintered bodies prepared with ITO powders treated at 900?°C could reach 40?vol% (untreated, 25?vol%) and 98.53% (untreated, 95.04%), respectively. The results indicate that the heat treatment of powders at 900?°C allowed obtaining powders from which ITO aqueous suspensions with high solid loading could be prepared and dense bodies after sintering. In another word, the appropriate heat treatment process for tin doped indium oxide powders could reduce the sintering temperature by 50?℃ and refine the grain size.     

Thin‐film polyimide/indium tin oxide composites for photovoltaic applications

Soluble polyimides were prepared from suitable monomers and were evaluated for their thermal and mechanical properties. The polymers were processed into films for use as supports for transparent, conductive indium tin oxide (ITO) layers. After deposition, annealing in vacuo at temperatures up to 400°C was performed to test the ability of the materials to endure typical device fabrication temperatures without damage to the ITO‐coated polymeric substrate. The evolution of the structural, optical, and electrical characteristics with the annealing temperature was analyzed and compared with that of polymeric and conventional glass substrates as references. Polyimide 6F6F, synthesized from hexafluoroisopropylidene diphthalic dianhydride and hexafluoroisopropylidene dianiline, had optimal characteristics for photovoltaic applications, permitting the achievement of conductive, ITO‐coated samples with optical transmission greater than 75% in the visible and near‐infrared wavelength ranges, without significant deterioration of their properties after vacuum annealing at temperatures up to 350°C. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3491–3497, 2007     

Seed-mediated electrochemical growth of gold nanostructures on indium tin oxide thin films

Two-dimensional gold nanostructures (Au NSs) were fabricated on amine-terminated indium tin oxide (ITO) thin films using constant potential electrolysis. By controlling the deposition time and by choosing the appropriate ITO surface, Au NSs with different shapes were generated. When Au NSs were formed directly on aminosilane-modified ITO, the surface roughness of the interface was largely enhanced. Modification of such Au NSs with n-tetradecanethiol resulted in a highly hydrophobic interface with a water contact angle of 144°. Aminosilane-modified ITO films further modified with colloidal Au seeds before electrochemical Au NSs formation demonstrated interesting optical properties. Depending on the deposition time, surface colors ranging from pale pink to beatgold-like were observed. The optical properties and the chemical stability of the interfaces were characterized using UV-vis absorption spectroscopy. Well-defined localized surface plasmon resonance signals were recorded on Au-seeded interfaces with λ_max = 675 ± 2 nm (deposition time 180 s). The prepared interfaces exhibited long-term stability in various solvents and responded linearly to changes in the corresponding refractive indices.     

Optical and electrochemical evaluation of colloidal Au nanoparticle-ITO hybrid optically transparent electrodes and their application to attenuated total reflectance spectroelectrochemistry

Colloidal Au nanoparticle monolayers covalently deposited on conductive layers of indium tin oxide (ITO) were fabricated and evaluated as optically transparent electrodes (OTEs) for spectroelectrochemical applications. Specifically, the electrodes were characterized using UV-Vis spectroscopy and cyclic voltammetry; comparisons are made with other types of hybrid ITO optically transparent electrodes. The optical modulation of surface-bound colloidal Au in response to potential cycling over a wide potential window (0.6 to −1.0 V) was acquired in an attenuated total reflectance (ATR) spectroelectrochemical cell. Finally, uptake of a model analyte, tris-(2,2′-bipyridyl)ruthenium(II) chloride, into a Nafion charge selective film spin coated onto the colloidal Au-ITO hybrid electrode was examined using ATR absorbance spectroelectrochemistry. Dependence of uptake on film thickness is addressed, and non-optimized detection limits of 10 nM are reported.     

Effect of Ar:N2 flow rate on morphology,optical and electrical properties of CCTO thin films deposited by RF magnetron sputtering

Calcium copper titanate (CCTO) thin films were deposited on indium tin oxide (ITO) substrates using radio frequency (RF) magnetron sputtering, at selected Ar:N₂ flow rates (1:1, 1:2, 1:4, and 1:6 sccm) at ambient temperature. The effect of Ar:N₂ flow rate on the morphology, optical and electrical properties of the CCTO thin films were investigated using FESEM, XRD, AFM, Hall effect measurement, and UV–Vis spectroscopy. It was confirmed by XRD analysis that the thin films were produced is CCTO with cubic crystal structure. As the flow rate of Ar:N₂ increased up to 1:6 sccm, the thin film thickness reduced from 87 nm to 35 nm while the crystallite size of CCTO thin film decreased from 27 nm to 20 nm. Consequently, the surface roughness of thin film was halved from 8.74 nm to 4.02 nm. In addition, the CCTO thin films deposited at the highest Ar:N₂ flow rate studied, at 1:6 sccm; are having the highest sheet resistivity (13.27 Ω/sq) and the largest optical energy bandgap (3.68 eV). The results articulate that Ar:N₂ flow rate was one of the important process parameters in RF magnetron sputtering that could affect the morphology, electrical properties and optical properties of CCTO thin films.     

Molecular mechanism of monodisperse colloidal tin-doped indium oxide nanocrystals by a hot-injection approach

Molecular mechanisms and precursor conversion pathways associated with the reactions that generate colloidal nanocrystals are crucial for the development of rational synthetic protocols. In this study, Fourier transform infrared spectroscopy technique was employed to explore the molecular mechanism associated with the formation of tin-doped indium oxide (ITO) nanocrystals. We found that the reaction pathways of the indium precursor were not consistent with simple ligand replacements proposed in the literature. The resulting understanding inspired us to design a hot-injection approach to separate the ligand replacements of indium acetate and the aminolysis processes, generating quality ITO nanocrystals with decent size distributions. The hot-injection approach was readily applied to the synthesis of ITO nanocrystals with a broad range of tin doping. Structural, chemical, and optical analyses revealed effective doping of Sn⁴⁺ ions into the host lattices, leading to characteristic and tunable near-infrared surface plasmon resonance peaks. The size control of ITO nanocrystals by multiple hot-injections of metal precursors was also demonstrated.     

从废ITO玻璃回收铟及制备高品质玻璃

为回收废弃LCD面板中的金属铟及高品质玻璃,提出了一种铟锡氧化物(ITO)玻璃资源化回收方法,用HF溶液浸蚀ITO玻璃碎片得富铟溶液和经表面除杂的玻璃基板,富铟溶液经蒸发、浓缩得富铟物,将富铟物溶解并经铝置换、熔炼、提纯得到粗铟,玻璃基板作为配合料进行再生制样. 结果表明,ITO玻璃破碎会造成铟流失,8 mol/L HF在3 h内即可有效回收ITO中的铟,制得纯度达92.3%的粗铟,回收率达89.2%. 再生玻璃试样成型温度为1462℃,热膨胀系数最大为3.2′10-6/℃,维氏硬度平均值为584.9,密度为2.43097 g/cm3,可见光透射比为75.2,部分性能有所下降,可降低配合料用量,以实现ITO玻璃基板的资源化回收.