Study of optoelectronics and microstructures on the AZO/nano-layer metals/AZO sandwich structures

In this study, growth nano-layer metals (Al, Cu, Ag) and Al-doped ZnO (AZO) thin films are deposited on glass substrates as the transparent conducting oxides (TCOs) to form AZO/nano-layer metals/AZO sandwich structures. The conductivity properties of thin films are enhanced when the average transmittance over the wavelengths 400–800 nm is maintained at higher than 80 %. A radio frequency magnetron sputtering system is used to deposit the metal layers and AZO thin films of different thickness, to form AZO/Al/AZO (ALA), AZO/Cu/AZO (ACA) and AZO/Ag/AZO (AGA) structures. X-ray diffraction and field emission scanning electron microscopy are used to analyze the crystal orientation and structural characteristic. The optical transmission and resistivity are measured by UV–VIS–NIR spectroscopy and Hall effect measurement system, respectively. The results show that when the Ag thickness is maintained at approximately 9 nm, the TCOs thin film has the lowest resistivity of 8.9 × 10^?5 Ω-cm and the highest average transmittance of 81 % over the wavelengths 400–800 nm. The crystalline Ag nano-crystal structures are observed by high-resolution transmission electron microscopy. In addition, the best figure of merit for the AZO/Ag/AZO tri-layer film is 2.7 × 10^?2 (Ω^?1), which is much larger than that for other structures.     

透明导电AZO/Cu双层薄膜制备及其性能

采用直流磁控溅射方法在玻璃衬底上室温生长了AZO/Cu双层薄膜,Cu层厚度控制在9nm,研究了AZO层厚度对薄膜电学和光学性能的影响。当AZO层厚度为20～80nm时,AZO/Cu双层薄膜具有良好的综合光电性能,方块电阻为12～14Ω/sq,可见光平均透过率为70～75%,品质因子为2×10-3～5×10-3Ω-1。AZO/Cu双层薄膜可以观察到Cu（111）和ZnO（002）的XRD衍射峰。通过退火研究表明,AZO/Cu双层薄膜的光电性能可在400℃下保持稳定,具有良好的热稳定性。本研究制备的透明导电AZO/Cu双层薄膜具有室温制程、综合光电性能良好、结晶性能较好、稳定性高的优点,可以广泛应用于光电器件透明电极及镀膜玻璃等领域。     

Structural, optical and electrical properties of AZO/Cu/AZO tri-layer films prepared by radio frequency magnetron sputtering and ion-beam sputtering

Highly conducting tri-layer films consisting of a Cu layer sandwiched between Al-doped ZnO (AZO) layers (AZO/Cu/AZO) were prepared on glass substrates at room temperature by radio frequency (RF) magnetron sputtering of AZO and ion-beam sputtering of Cu. The tri-layer films have superior photoelectric properties compared with the bi-layer films (Cu/AZO, AZO/Cu) and single AZO films. The effect of AZO thickness on the properties of the tri-layer films was discussed. The X-ray diffraction spectra show that all films are polycrystalline consisting of a Cu layer with the cubic structure and two AZO layers with the ZnO hexagonal structure having a preferred orientation of (0 0 2) along the c-axis, and the crystallite size and the surface roughness increase simultaneously with the increase of AZO thickness. When the AZO thickness increases from 20 to 100 nm, the average transmittance increases initially and then decreases. When the fixed Cu thickness is 8 nm and the optimum AZO thickness of 40 nm was found, a resistivity of 7.92 × 10⁻⁵ Ω cm and an average transmittance of 84% in the wavelength range of visible spectrum of tri-layer films have been obtained. The merit figure (F_TC) for revaluing transparent electrodes can reach to 1.94 × 10⁻² Ω⁻¹.     

Quality enhancement of AZO thin films at various thicknesses by introducing ITO buffer layer

Due to the simultaneously superior optical transmittance and low electrical resistivity, transparent conductive electrodes play a significant role in semiconductor electronics. To enhance the electrical properties of these films, one approach is thickness increment which degrades the optical properties. However, a preferred way to optimize both electrical and optical properties of these layers is to introduce a buffer layer. In this work, the effects of buffer layer and film thickness on the structural, electrical, optical and morphological properties of AZO thin films are investigated. Al-doped zinc oxide (AZO) is prepared at various thicknesses of 100 to 300 nm on the bare and 100 nm-thick indium tin oxide (ITO) coated glass substrates by radio frequency sputtering. Results demonstrate that by introducing ITO as a buffer layer, the average values of sheet resistance and strain within the film are decreased (about 76 and 3.3 times lower than films deposited on bare glasses), respectively. Furthermore, the average transmittance of ITO/AZO bilayer is improved nearly 10% regarding single AZO thin film. This indicates that bilayer thin films show better physical properties rather than conventional monolayer thin films. As the AZO film thickness increases, the interplanar spacing, d₍₀₀₂₎, strain within the film and compressive stress of the film in the hexagonal lattice, decreases indicating the higher yield of AZO crystal. Moreover, with the growth in film thickness, carrier concentration and optical band gap (E_g) of AZO film are increased from 4.62?×?10¹⁹ to 8.21?×?10¹⁹ cm^?3 and from 3.55 to 3.62 eV, respectively due to the Burstein-Moss (BM) effect. The refractive index of AZO thin film is obtained in the range of 2.24–2.26. With the presence of ITO buffer layer, the AZO thin film exhibits a resistivity as low as 6?×?10^?4 Ω cm, a sheet resistance of 15 Ω/sq and a high figure of merit (FOM) of 1.19?×?10⁴ (Ω cm)^?1 at a film thickness of 300 nm. As a result, the quality of AZO thin films deposited on ITO buffer layer is found to be superior regarding those grown on a bare glass substrate. This study has been performed over these two substrates because of their significant usage in the organic light emitting diodes and photovoltaic applications as an enhanced carrier injecting electrodes.     

Ag层厚度对AZO/Ag/AZO透明导电薄膜性能的影响

在室温条件下,采用磁控溅射技术在玻璃衬底上生长了AZO/Ag/AZO多层透明导电薄膜。主要研究了Ag层厚度对多层透明导电薄膜结构和性能的影响。研究表明,AZO和Ag分别延(002)面和(111)面高度择优生长,随着Ag层厚度的增加,多层透明导电薄膜的电阻率不断降低,透过率呈现先降低再增加最后再降低的变化趋势,其中Ag层厚度为8nm的样品获得最大品质因子33.1×10^-3Ω^-1,综合性能最佳。     

Effect of Cu layer thickness on the structural, optical and electrical properties of AZO/Cu/AZO tri-layer films

Highly conducting AZO/Cu/AZO tri-layer films were successfully deposited on glass substrates by RF magnetron sputtering of Al-doped ZnO (AZO) and ion-beam sputtering of Cu at room temperature. The microstructures of the AZO/Cu/AZO multilayer films were studied using X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) and atomic force microscope (AFM). X-Ray diffraction measurements indicate that the AZO layers in the tri-layer films are polycrystalline with the ZnO hexagonal structure and have a preferred orientation with the c-axis perpendicular to the substrates. With the increase of Cu thickness, the crystallinity of AZO and Cu layers is simultaneously improved. When the Cu thickness increases from 3 to 13 nm, the resistivity decreases initially and then varies little, and the average transmittance shows a first increase and then decreases. The maximum figure of merit achieved is 1.94 × 10⁻² Ω⁻¹ for a Cu thickness of 8 nm with a resistivity of 7.92 × 10⁻⁵ Ω cm and an average transmittance of 84%.     

Cu基Al掺杂ZnO多层薄膜的生长及其性能

本文采用直流磁控溅射技术在玻璃衬底上制备了AZO/Cu、Cu/AZO和AZO/Cu/AZO三种复合结构多层膜,研究了生长温度对多层膜特性的影响,发现AZO/Cu双层薄膜具有最优的光电性能,其最佳生长温度为100~150℃。文中进一步考察了生长温度对AZO/Cu双层薄膜结构性能和表面形貌的影响,结果表明：合适的生长温度有...     

Passivation and antireflection AZO:H layer in AZO:H/p-Si heterojunction solar cells

In this work, aluminum-doped zinc oxide (AZO)/p-Si heterojunction solar cells were prepared by sputtering of ~120 nm AZO thin films in Ar or Ar–H₂ atmosphere on textured p-Si wafers, and the effects of hydrogen incorporation on the solar cell performance were investigated. Results showed that the performance of AZO/p-Si heterojunction solar cells was improved with the increase of hydrogen volume concentration from 0 to 23 %. The AZO:H/p-Si heterojunction solar cells prepared in Ar–23 % H₂ exhibited a short-circuit current density of 29 mA/cm² and a conversion efficiency of 2.84 %. The reflectance measurement indicated that the reflectance of p-Si surface in the range of 400–1,100 nm decreased from 13 to 4 % after AZO:H films coating; and the capacitance–voltage measurement indicated that the density of defect states at AZO/p-Si interface was decreased after hydrogen incorporation. Passivation and antireflection functions can be realized in AZO:H films deposited in Ar–H₂, which opens a novel route to prepare cost-effective AZO/p-Si heterojunction solar cells.     

Electrical,optical, and structural properties of thin films with tri-layers of AZO/ZnMgO/AZO grown by filtered vacuum arc deposition

Transparent conductive oxides (TCO) are indispensable as front electrode for most of thin film electronic devices such as transparent electrodes for flat panel displays, photovoltaic cells, windshield defrosters, transparent thin film transistors, and low emissivity windows. Thin films of aluminum-doped zinc oxide (AZO) have shown to be one of the most promising TCOs. In this study, three layered Al-doped ZnO (AZO)/ZnMgO/AZO heterostructures were prepared by filtered cathodic arc deposition (FCAD) on glass substrates. The objective is to find a set of parameters that will allow for improved optical and electrical properties of the films such as low resistivity, high mobility, high number of charge carriers, and high transmittance. We have investigated the effect of modifications in thickness and doping of the ZnMgO inner layer on the structural, electrical, and optical characteristics of the stacked heterostructures.     

Improving efficiency of organic light-emitting diodes fabricated utilizing AZO/Ag/AZO multilayer electrode

Multilayer transparent electrode based on Al-doped zinc oxide (AZO)/Ag/Al-doped zinc oxide (AZO) was fabricated by sputtering, and a green organic light-emitting diode (OLED) device utilizing AZO/Ag/AZO as anode was fabricated. The AZO/Ag/AZO multilayer film exhibited superior square resistance and optical transmittance to those of commercial indium tin oxide (ITO). In comparison with the green OLEDs based on ITO and pure AZO anode, the green OLED based on AZO/Ag/AZO showed the highest light-emitting efficiency. The results indicate that AZO/Ag/AZO multilayer electrodes are a promising low-cost, low-toxic and low-temperature processing electrode scheme for OLED application.     

Optimization of ZnO:Al/Ag/ZnO:Al structures for ultra-thin high-performance transparent conductive electrodes

Al-doped ZnO (AZO)/Ag/AZO multilayer coatings (50-70 nm thick) were grown at room temperature on glass substrates with different silver layer thickness, from 3 to 19 nm, by using radio frequency magnetron sputtering. Thermal stability of the compositional, optical and electrical properties of the AZO/Ag/AZO structures were investigated up to 400 °C and as a function of Ag film thickness. An AZO film as thin as 20 nm is an excellent barrier to Ag diffusion. The inclusion of 9.5 nm thin silver layer within the transparent conductive oxide (TCO) material leads to a maximum enhancement of the electro-optical characteristics. The excellent measured properties of low resistance, high transmittance in the visible spectral range and thermal stability allow these ultra-thin AZO/Ag/AZO structures to compete with the 1 μm thick TCO layer currently used in thin film solar cells.     

Structural evolution,electrical and optical properties of AZO films deposited by sputtering ultra-high density target

Aluminum-doped zinc oxide (AZO) target was fabricated using AZO nanopowders synthesized by co-precipitation method and then the AZO films with different thicknesses were deposited on glass by d.c. magnetron sputtering at room temperature. AZO target is nodules free and shows homogeneous microstructure, ultra-high density and low resistivity. ZnAl₂O₄ phase appears in AZO target and disappears in AZO films. All AZO films show c-axis preferred orientation and hexagonal structure. With increasing film thickness from 153 to 1404 nm, the crystallinity was improved and the angle of (002) peak was close to 34.45°. The increase in grain size and surface roughness is due to the increase in film thickness. The decrease of resistivity is ascribed to the increases of carrier concentration and Hall mobility. The lowest resistivity is 9.6 × 10^?4 Ω·cm. The average transmittance of AZO films exceeds 80%, and a sharp fundamental absorption edge with red-shifting is observed in the visible range. The bandgap decreases from 3.26 to 3.02 eV.     

Characterization of aluminum-doped zinc oxide thin films by RF magnetron sputtering at different substrate temperature and sputtering power

In this study, transparent conductive Al doped zinc oxide (ZnO: Al, AZO) thin films with a thickness of 40 nm were prepared on the Corning glass substrate by radio frequency magnetron sputtering. The properties of the AZO thin films are investigated at different substrate temperatures (from 27 to 150 °C) and sputtering power (from 150 to 250 W). The structural, optical and electrical properties of the AZO thin films were investigated. The optical transmittance of about 78 % (at 415 nm)–92.5 % (at 630 nm) in the visible range and the electrical resistivity of 7 × 10^?4 Ω-cm (175.2 Ω/sq) were obtained at sputtering power of 250 W and substrate temperature of 70 °C. The observed property of the AZO thin films is suitable for transparent conductive electrode applications.     

膜层厚度对Ag/TiO膜透光隔热性能的影响

采用磁控溅射工艺制备了玻璃基Ag/TiO_2膜,并研究了膜层厚度对其透光隔热性能的影响。结果表明:当Ag膜厚度由6.7 nm增加到9.5 nm时,红外光的平均透过率由42.06%减小到7.70%,隔热温差由1.9℃增大到5.7℃,而可见光的平均透过率则呈现出先增加后减少的变化趋势,当Ag膜厚度为7.7 nm时,复合膜的可见光平均透过率达最大值,为70.85%;当Ti O_2膜厚度由4.1 nm增加到16.7 nm时,红外光的平均透过率由34.12%增大到38.28%,而可见光的平均透过率与隔热温差均呈现出先增大后减少的变化趋势,当Ti O_2膜厚度为10.4 nm时,复合膜的可见光平均透过率达最大值,为70.85%,而厚度为13.6 nm时,膜的隔热温差达最大值,为5.2℃。     

TiOx/Ag/TiOx multilayer for application as a transparent conductive electrode and heat mirror

Amorphous TiO_x films and Ag layer were deposited by electron-beam evaporation on soda-lime glass at room temperature. The details regarding the structure, surface morphology, and optical properties of the as-prepared TiO_x films were examined by X-ray diffraction, scanning electron microscopy, and ultra-violet (UV) -visible-near-infrared (NIR) spectrometry. The TiO_x films exhibit amorphous phase with an optical band gap of 3.35 eV. The polygrains oriented along the (111) and (200) directions in the Ag films were adopted to supply carriers into the TiO_x film and lower the sheet resistance of the stacked layer. The multilayer exhibited a sufficiently large Ag thickness (>15 nm), low resistance, high UV transmittance, visible transmittance, and high NIR reflection. Dependence of Ag thickness, TiO_x bottom-layer, and TiO_x overlayer on the optical and electrical properties of TiO_x/Ag/TiO_x were explored. A figure of merit (FOM) was used to find an optimal structure for a multilayer with superior conductivity and visible transparency. An FOM of 9.8 × 10^?2 (Ω^?1) at the visible wavelength of 550 nm for a TiO_x/Ag/TiO_x stacked layer with an 18-nm-thick Ag and a 20-nm-thick TiO_x was achieved. The TiO_x/Ag/TiO_x sample annealed at 500 °C 10 min also shows a good thermal stability.     

The properties of Al doped ZnO thin films deposited on various substrate materials by RF magnetron sputtering

Transparent conductive Al-doped ZnO (AZO) thin films were deposited on various substrates including glass, polyimide film (PI) and stainless steel, using radio frequency magnetron sputtering method. The structural, electrical and optical properties of AZO thin films grown on various substrates were systematically investigated. We observe that substrate materials play important roles in film crystallization and resistivity but little on optical transmittance. X-ray diffractometer study shows that all obtained AZO thin films have wurtzite phase with highly c-axis preferred orientation, and films on glass present the strongest (002) diffraction peaks. The presence of compression stress plays critical role in determining the crystalline structure of AZO films, which tends to stretch the lattice constant c and enlarge the (002) diffraction angle. Although the films on the glass present the finest electrical properties and the resistivity reaches 12.52 × 10-4 Ωm, AFM study manifests that films on flexible substrates, especially stainless steel, bestrew similar inverted pyramid structure which are suitable for window material and electrode of solar cells. The average optical transmittance of AZO thin films deposited on glass and PI are both around 85% in the visible light range (400–800 nm).     

Effects of sputtering pressure and Al buffer layer thickness on properties of AZO films grown by rf magnetron sputtering

Transparent and conductive Al-doped (2 wt.%) zinc oxide (AZO) films were deposited on inexpensive soda-lime glass substrates by using rf magnetron sputtering at room temperature. This study analyzed the effects of argon sputtering pressure, which varied in the range from 0.46 to 2.0 Pa, on the morphological, electrical and optical properties of AZO films. The only (0 0 2) diffraction peak of the film were observed at 2θ～34.45°, exhibiting that the AZO films had hexagonal ZnO wurtzite structure, and a preferred orientation with the c-axis perpendicular to the substrate. By applying a very thin aluminum buffer layer with the thickness of 2 nm, findings show that the electrical resistivity was 9.46 × 10⁻⁴ Ω-cm, and the average optical transmittance in the visible part of the spectra was approximately 81%. Furthermore, as for 10 nm thick buffer layer, the electrical resistivity was lower, but the transmittance was decreased.     

Effect of ZnO buffer layer on AZO film properties and photovoltaic applications

Aluminum-doped ZnO (AZO) transparent conducting films were deposited on glass substrates with and without intrinsic ZnO (i-ZnO) buffer layers by a home made and low cost radio-frequency (RF) magnetron sputtering system at room temperature in pure argon ambient and under a low vacuum level. The films were examined and characterized for electrical, optical, and structural properties for the application of CIGS solar cells. The influence of sputter power, deposition pressure, film thickness and residual pressure on electrical and optical properties of layered films of AZO, i-ZnO and AZO/i-ZnO was investigated. The optimization of coating process parameters (RF power, sputtering pressure, thickness) was carried out. The effects of i-ZnO buffer layer on AZO films were investigated. By inserting thin i-ZnO layers with a thickness not greater than 125 nm under the AZO layers, both the carrier concentration and Hall mobility were increased. The resistivity of these layered films was lower than that of single layered AZO films. The related mechanisms and plasma physics were discussed. Copper indium gallium selenide (CIGS) thin film solar cells were fabricated by incorporating bi-layer ZnO films on CdS/CIGS/Mo/glass substrates. Efficiencies of the order of 7–8% were achieved for the manufactured CIGS solar cells (4–5 cm² in size) without antireflective films. The results demonstrated that RF sputtered layered AZO/i-ZnO films are suitable for application in low cost CIGS solar cells as transparent conductive electrodes.     

Damp heat stability of AZO transparent electrode and influence of thin metal film for enhancing the stability

The electrical properties of Aluminum doped ZnO (AZO) thin films prepared by sol–gel method were investigated as a function of annealing atmosphere (vacuum, argon +5 % hydrogen and pure hydrogen) and doping concentration (1, 2, 3 and 4 wt%). An optimal annealing atmosphere (pure hydrogen) and doping concentration (2 wt%) was obtained with a minimum resistivity of 1.6 × 10^?3 Ω cm. The structural, optical and electrical stability has been investigated by a damp-heat test in an environment with 85 % relative humidity at 85 °C. The degradation of the electrical film properties was due to the decrease of carrier concentration and mobility, whereas, no significant change was observed for structural and optical properties. The thin metallic layer (Ti or Cr) was deposited on AZO by sputtering to prevent the penetration of oxygen and water into film thus increasing the electrical stability. Oxide layer of metal was formed on surface when it comes to air at room temperature which was confirmed by X-ray photoelectron spectroscopy and thus a bi-layer of metal/metal oxide layer on AZO film enhances the electrical stability.     

Low-temperature preparation of transparent conductive Al-doped ZnO thin films by a novel sol–gel method

We developed a novel sol–gel method to prepare transparent conductive Al-doped ZnO (AZO) thin film at low temperature. The AZO nanocrystals were prepared by a solvothermal method and then they were dispersed in the monoethanolamine and methanol to form AZO colloids. A (002)-oriented ZnO thin film was used as a nucleation layer to induce the (002)-oriented growth of AZO thin films. The AZO thin films were prepared on Si(100) and fused quartz glass substrates with the (002)-oriented ZnO nucleation layer and annealed at 400 °C for 60 min. All AZO thin films showed (002) orientation. For electrical and optical measurements, the films deposited on glass substrates were post-annealed at 400 °C for 30 min in forming gas (100 % H₂) to improve their conductivity. These samples had high transparency in the visible wavelength range, and also showed good conductivity. A 0.2 mol L^?1 AZO solution with 3 at.% Al content was heated in a Teflon autoclave at 160 °C for 30 min to form AZO nanocrystals, and then the AZO nanocrystals were suspended in the MEA and methanol to obtain the stable AZO colloid. The Al content in the AZO nanocrystals was 2.7 at.%, and the high Al doping coefficient was mainly attributed to the formation of AZO nanocrystals in the autoclave. The AZO thin film using this colloid had the lowest resistivity of 3.89 × 10^?3 Ω cm due to its high carrier concentration of 3.29 × 10²⁰ cm^?3.