Thermally stable transparent conducting and highly infrared reflective Ga-doped ZnO thin films by metal organic chemical vapor deposition

Highly transparent conductive Ga-doped ZnO (GZO) thin films have been prepared on glass substrates by metal organic chemical vapor deposition. The effect of Ga doping on the structural, electrical and optical properties of GZO films has been systematically investigated. Under the optimum Ga doping concentration (∼4.9 at.%), c-axis textured GZO film with the lowest resistivity of 3.6 × 10⁻⁴ Ω cm and high visible transmittance of 90% has been achieved. The film also exhibits low transmittance (<1% at 2500 nm) and high reflectance (>70% at 2500 nm) to the infrared radiation. Furthermore, our developed GZO thin film can well retain the highly transparent conductive performance in oxidation ambient at elevated temperature (up to 500 °C).     

Sputter deposition of semicrystalline tin dioxide films

Tin dioxide is emerging as an important material for use in copper indium gallium diselenide based solar cells. Amorphous tin dioxide may be used as a glass overlayer for covering the entire device and protecting it against water permeation. Tin dioxide is also a viable semiconductor candidate to replace the wide band gap zinc oxide window layer to improve the long-term device reliability. The film properties required by these two applications are different. Amorphous films have superior water permeation resistance while polycrystalline films generally have better charge carrier transport properties. Thus, it is important to understand how to tune the structure of tin dioxide films between amorphous and polycrystalline. Using X-ray diffraction (XRD) and Hall-effect measurements, we have studied the structure and electrical properties of tin dioxide films deposited by magnetron sputtering as a function of deposition temperature, sputtering power, feed gas composition and film thickness. Films deposited at room temperature are semicrystalline with nanometer size SnO₂ crystals embedded in an amorphous matrix. Film crystallinity increases with deposition temperature. When the films are crystalline, the X-ray diffraction intensity pattern is different than that of the powder diffraction pattern indicating that the films are textured with (101) and (211) directions oriented parallel to the surface normal. This texturing is observed on a variety of substrates including soda-lime glass (SLG), Mo-coated soda-lime glass and (100) silicon. Addition of oxygen to the sputtering gas, argon, increases the crystallinity and changes the orientation of the tin dioxide grains: (110) XRD intensity increases relative to the (101) and (211) diffraction peaks and this effect is observed both on Mo-coated SLG and (100) silicon wafers. Films with resistivities ranging between 8 mΩ cm and 800 mΩ cm could be deposited. The films are n-type with carrier concentrations in the 3 × 10¹⁸ cm^− 3 to 3 × 10²⁰ cm^− 3 range. Carrier concentration decreases when the oxygen concentration in the feed gas is above 5%. Electron mobilities range from 1 to 7 cm²/V s and increase with increasing film thickness, oxygen addition to the feed gas and film crystallinity. Electron mobilities in the 1-3 cm²/V s range can be obtained even in semicrystalline films. Initial deposition rates range from 4 nm/min at low sputtering power to 11 nm/min at higher powers. However, deposition rate decreases with deposition time by as much as 30%.     

Au nanopatterns on glass substrate using block copolymer and their applications in transparent conducting electrode

High density Au nanostructures were fabricated using polystyrene-block-polymethylmethacrylate (PS-b-PMMA) copolymer on glass substrate for the preparation of electrode materials with good stability, high transparency and excellent conductivity. A 1 wt.% polymer solution in toluene was spin coated on glass substrate. Samples were baked for 48 h at 200 °C with a continuous flow of Ar. Patterned polymer film was obtained by removing the PMMA region through exposing ultraviolet irradiation and rinsing in acetic acid. Au thin films with several thicknesses were then deposited onto the patterned glass substrates by thermal evaporation or sputtering. Removing PS cylinders by sonicating in acetone resulted in Au nanopattern on glass substrates. The connecting gold film acts as conductor while the holes allow light pass through it and helps to be transparent. The transmittance with Au film thickness of 7 nm and 4 nm was found to be about 63% and 70%, respectively. The resistivity was in the range 10^− 5 Ω cm-10^− 6 Ω cm which is comparable with ITO (10^− 3 Ω cm-10^− 4 Ω cm).     

Structural and tunneling properties of magnetic tunnel junctions with Al-O and MgO barrier

Two types of magnetic tunnel junctions (MTJs) with the configuration: substrate Si(1 0 0)/SiO₂ 47 nm/buffer/IrMn 12 nm/CoFe 2.5 nm/Al-O 1.5 nm/NiFe 3 nm/Ta 5 nm and Si(1 0 0)/SiO₂ 47 nm/buffer/IrMn 10 nm/CoFeB 3 nm/MgO 2 nm/CoFeB 4 nm/Ta 5 nm were prepared by the sputtering technique with two different buffers: A-Cu 25 nm and B-Ta 5 nm/Cu 25 nm. The B buffer caused a high texture of MTJs whereas in the case of the A buffer junctions texture was weak. Crystallites in the textured layers grew in a columnar like shape that induced interfacial roughness. High textured buffer B caused high interfacial roughness that reduced the resistance-area (RA) product due to a barrier thickness fluctuation. RA also changed substantially depending on the type of a barrier. The highest RA product ∼15 MΩ μm² was achieved for a low textured junction with Al-O barrier whereas in the high textured MgO sample RA product was ∼100 kΩ μm². Tunnel magnetoresistance (TMR) measured at room temperature was about 45% for the samples with Al-O barrier, whereas for the samples with MgO barrier TMR was about three times higher and achieved 140%.     

Structural, electrical and optical properties of ITO films with a thin TiO2 seed layer prepared by RF magnetron sputtering

Tin-doped indium oxide (ITO) films were deposited by RF magnetron sputtering on TiO₂-coated glass substrates (the TiO₂ layer is usually called seed layer). The properties of ITO films prepared at a substrate temperature of 300 °C on bare and TiO₂-coated glass substrates have been analyzed by using X-ray diffraction, atomic force microscope, optical and electrical measurements. Comparing with single layer ITO film, the ITO film with a TiO₂ seed layer of 2 nm has a remarkable 41.2% decrease in resistivity and similar optical transmittance. The glass/TiO₂ (2 nm)/ITO film achieved shows a resistivity of 3.37 × 10⁻⁴ Ω cm and an average transmittance of 93.1% in the visible range. The glass/TiO₂ may be a better substrate compared with bare glass for depositing high quality ITO films.     

One-minute microwave-assisted chemical bath deposition of nanostructured ZnO rod-arrays

Microwave-assisted chemical bath deposition (MACBD) is an emerging route for rapid synthesis of films and nanostructured particles. In this paper we report MACBD of ZnO rod-array films on bare glass substrates from an aqueous bath of tetra ammonium zinc complex. The deposition time is reduced to about 1 min as compared to around 60 min for conventional CBD. X-ray diffraction study shows that as-deposited films are uniaxially out-of-plane textured along the c-axis. Scanning Electron Microscopy reveals that the films consist of elongated elliptical tapered rods of diameters 250 to 350 nm. Atomic Force Microscopy shows that the films consist of about 350 nm grains. The RMS roughness is about 60 nm. The energy band gap is 3.27 eV as estimated from optical data. The films are n-type with electrical conductivity of 1 × 10^− 4 S/cm.     

Natively textured surface aluminum-doped zinc oxide transparent conductive layers for thin film solar cells via pulsed direct-current reactive magnetron sputtering

Natively textured surface aluminum-doped zinc oxide (ZnO:Al) layers for thin film solar cells were directly deposited without any surface treatments via pulsed direct-current reactive magnetron sputtering on glass substrates. Such an in-situ texturing method for sputtered ZnO:Al thin films has the advantages of efficiently reducing production costs and dramatically saving time in photovoltaic industrial processing. High purity metallic Zn-Al (purity: 99.999%, Al 2.0 wt.%) target and oxygen (purity: 99.999%) were used as source materials. During the reactive sputtering process, the oxygen gas flow rate was controlled using plasma emission monitoring. The performance of the textured surface ZnO:Al transparent conductive oxides (TCOs) thin films can be modified by changing the number of deposition rounds (i.e. thin-film thicknesses). The initially milky ZnO:Al TCO thin films deposited at a substrate temperature of ~ 553 K exhibit rough crater-like surface morphology with high transparencies (T ~ 80-85% in visible range) and excellent electrical properties (ρ ~ 3.4 × 10^− 4 Ω cm). Finally, the textured-surface ZnO:Al TCO thin films were preliminarily applied in pin-type silicon thin film solar cells.     

Effects of substrate on the structural, electrical and optical properties of Al-doped ZnO films prepared by radio frequency magnetron sputtering

Transparent and conductive Al-doped ZnO (AZO) thin films were deposited on substrates including alkali-free glass, quartz glass, Si, and SiO₂ buffer layer on alkali-free glass by using radio frequency magnetron sputtering. The effects of different substrates on the structural, electrical and optical properties of the AZO films were investigated. It was found that the crystal structures were remarkably influenced by the type of the substrates due to their different thermal expansion coefficients, lattice mismatch and flatness. The AZO film (100 nm in thickness) deposited on the quartz glass exhibited the best crystallinity, followed sequentially by those deposited on the Si, the SiO₂ buffer layer, and the alkali-free glass. The film deposited on the quartz glass showed the lowest resistivity of 5.14 × 10^− 4 Ω cm among all the films, a carrier concentration of 1.97 × 10²¹ cm^− 3 and a Hall mobility of 6.14 cm²/v·s. The average transmittance of this film was above 90% in the visible light spectrum range. Investigation into the thickness-dependence of the AZO films revealed that the crystallinity was improved with increasing thickness and decreasing surface roughness, accompanied with a decrease in the film resistivity.     

Influence of Ag thickness of aluminum-doped ZnO/Ag/aluminum-doped ZnO thin films

Highly conducting aluminum-doped ZnO (30 nm)/Ag (5-15 nm)/aluminum-doped ZnO (30 nm) multilayer thin films were deposited on glass substrate by rf magnetron sputtering (for top/bottom aluminum-doped ZnO films) and e-beam evaporation (for Ag film). The transmittance is more than 70% for wavelengths above 400 nm with the Ag layer thickness of 10 nm. The resistivity is 3.71 × 10^− 4 Ω-cm, which can be decreased to 3.8 × 10^− 5 Ω-cm with the increase of the Ag layer thickness to 15 nm. The Haacke figure of merit has been calculated for the films with the best value being 8 × 10^− 3 Ω^− 1. It was shown that the multilayer thin films have potential for applications in optoelectronics.     

Local thermal-mechanical analysis of ultrathin interfacially mixed poly(ethylene oxide)/poly(acrylic acid) layer-by-layer electrolyte assemblies

Ion conductivities of layer-by-layer (LBL) assemblies of solid thin film polyelectrolyte systems involving poly(ethylene oxide) (PEO) and poly(acrylic acid) (PAA) were found to be a strong function of the number of bilayer stacks, n, with conductivities approaching 10^− 7 S/cm for n < 10, compared to 10^− 9 S/cm for n ≥ 10 and 10^− 10 S/cm for bulk PEO. Increased ion conductivity for low LBL stack numbers (n < 10) originated to part from an effective suppression of the PEO crystallization via PEO/PAA blending, which could be inferred from local glass transition temperature measurements involving shear modulation force microscopy. Another phenomenon responsible for high conductivity in thin films was found in the in-plane phase heterogeneity of PEO and PAA. Increased ion conductivity for larger LBL stacks (n ≥ 10) were attributed to low concentration autoblending caused by PEO-PAA hydrogen bonding, and an average layer thickness of noticeably less than 100 nm. The effect of interfacial constraints was evident in the degree of intermixing, addressed by a thin film extended Fox blend analysis, in the glass and melting transitions of PEO and PAA pure film components. While the glass transition value of PAA decreased by 55% to 46 °C for an 8 nm film, the melting transition for PEO decreased by 15% to 64 °C caused by surface tension effects.     

Organic photovoltaic cells fabricated on a SnOx/Ag/SnOx multilayer transparent conducting electrode

Transparent conducting multilayer structured electrode of a few nm Ag layer embedded in tin oxide thin film SnO_x/Ag/SnO_x was fabricated on a glass by RF magnetron sputtering at room temperature. The multilayer of the SnO_x(40 nm)/Ag(11 nm)/SnO_x(40 nm) electrode shows the maximum optical transmittance of 87.3% at 550 nm and a quite low electrical resistivity of 6.5 × 10^− 5 Ω cm, and the corresponding figure of merit (T¹⁰/R_S) is equivalent to 3.6 × 10^− 2 Ω^− 1. A normal organic photovoltaic (OPV) structure of poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)/polythiophene:phenyl-C60-butyric acid methyl ester/Al was fabricated on glass/SnO_x/Ag/SnO_x to examine the compatibility of OPV as a transparent conducting electrode. Measured characteristic values of open circuit voltage of 0.62 V, saturation current of 8.11 mA/cm² and fill factor of 0.54 are analogous to 0.63 V, 8.37 mA/cm² and 0.58 of OPV on commercial glass/indium tin oxide (ITO) respectively. A resultant power conversion efficiency of 2.7% is also very comparable with the 3.09% of the same OPV structure on the commercial ITO glass as a reference, and which reveals that SnO_x/Ag/SnO_x can be appropriate to OPV solar cells as a sound transparent conducting electrode.     

Transparent conductive titanium-doped indium oxide films prepared by a magnetic null discharge sputter source

Titanium-doped indium oxide (ITiO) films were prepared on soda-lime glass substrate using a magnetic null discharge (MND) sputter source. The ITiO thin films containing 10 wt.% Ti showed the minimum resistivity of ρ = 5.5 × 10⁻³ Ω cm. The optical transmittance increases from 70% at 450 nm to 80% at 700 nm in visible spectrum. Photoelectron peaks for In 3d, Ti 2p, O 1s and C 1s were detected for the ITiO film in the binding energy range of 0-1100 eV. The surface roughness of the sample showed a change from 10 nm to 50 nm. The ITiO film used for TCO layer of DSCs exhibited an energy conversion efficiency of about 3.8% at light intensity of 100 mW/cm².     

Hybrid influences of defect dipole and intrinsic inducing field on orientation of PbTiO3 thin film deposited on Indium Tin Oxide/glass substrate

(001)/(100) oriented PbTiO₃ (PT) thin film is prepared on a non single crystal Indium Tin Oxide (ITO)/glass substrate by sol-gel method. The mechanism of orientation is investigated via dopant element, dopant amount, oxygen pressure of atmosphere, different type of substrate, different thickness of substrate, different sol concentration and blocking layer. By substituting 2% Zn^2 +, or 2% Fe^3 +, or 2% Co^2 + ions in the Ti site of PT perovskite phase and heating at the oxygen-poor atmosphere, the PT thin film grown on the ITO(260 nm)/glass substrate forms well with (001)/(100) orientation. Moreover, this orientation phenomenon only appears when the solution concentration is below 0.1 mol/L. The orientation of PT which is attributed to the hybrid influences of defect dipole from the PT and the intrinsic electrostatic field from the ITO substrate is revealed. This work represents an important step toward controllable formation of oriented thin film on a non single crystal substrate.     

Effect of sublayer surface treatments on ZnO transparent conductive oxides using dc magnetron sputtering

Novel sublayer surface treatments were investigated to improve the conductivity of aluminum-doped zinc oxide (ZnO:Al) fabricated by using dc magnetron sputtering on a glass substrate. Introducing artificial minute flaws on the surface of glass substrates enhanced the crystallinity of ZnO:Al films and decreased the resistivity accompanying the increase of electron mobility. Combination of the surface treatment and sputter beam control, i.e., interruption of high-energy oxygen with shadow masks, further reduced the resistivity of the film to 3.7 × 10^− 4 Ω cm (thickness 70 nm).     

Mn-doped ZnO transparent conducting films deposited by DC magnetron sputtering

Mn-doped zinc oxide (ZnO:Mn) thin films with low resistivity and relatively high transparency were firstly prepared on glass substrate by direct current (DC) magnetron sputtering at room temperature. Influence of film thickness on the properties of ZnO:Mn films was investigated. X-ray diffraction (XRD) and scanning electron microscopy (SEM) show that all the deposited films are polycrystalline with a hexagonal structure and have a preferred orientation along the c-axis perpendicular to the substrate. As the thickness increases from 144 to 479 nm, the crystallite size increases while the electrical resistivity decreases. However, as the thickness increases from 479 to 783 nm, the crystallite size decreases and the electrical resistivity increases. When film thickness is 479 nm, the deposited films have the lowest resistivity of 2.1 × 10^− 4 Ω cm and a relatively high transmittance of above 84% in the visible range.     

Tungsten-doped ZnO transparent conducting films deposited by direct current magnetron sputtering

Highly conducting and transparent thin films of tungsten-doped ZnO (ZnO:W) were prepared on glass substrates by direct current (DC) magnetron sputtering at low temperature. The effect of film thickness on the structural, electrical and optical properties of ZnO:W films was investigated. All the deposited films are polycrystalline with a hexagonal structure and have a preferred orientation along the c-axis perpendicular to the substrate. The electrical resistivity first decreases with film thickness, and then increases with further increase in film thickness. The lowest resistivity achieved was 6.97 × 10⁻⁴ Ω cm for a thickness of 332 nm with a Hall mobility of 6.7 cm² V⁻¹ s⁻¹ and a carrier concentration of 1.35 × 10²¹ cm⁻³. However, the average transmittance of the films does not change much with an increase in film thickness, and all the deposited films show a high transmittance of approximately 90% in the visible range.     

Influence of texture on optical and electrical properties of diamond films

The optical and electrical properties of variously textured diamond films have been investigated in this paper. SEM and Raman spectrum indicated that the films produced were of high quality with either (0 0 1) or (1 1 1) orientation. A four-layer model was used to fit the measured spectroscopic ellipsometry data. The results indicated that the properties of (0 0 1)-oriented diamond films were superior to those of (1 1 1)-oriented one. The refractive index and extinction coefficient of (0 0 1)-oriented diamond film in the infrared region of 2500-12500 nm was measured as 2.391 and of the order of 10⁻⁵, respectively and that for (1 1 1)-oriented one was 2.375 and of the order of 10⁻⁴, respectively. The dark current of the (0 0 1)-oriented diamond film was measured as 33.7 nA for an applied electric field of 100 kV cm⁻¹, its resistivity being about 2.33×10¹⁰ Ω cm. Current passing through the (0 0 1)-oriented diamond film during testing did not change significantly.     

The evolution of the structural, electrical and optical properties in indium-tin-oxide thin film on glass substrate by DC reactive magnetron sputtering

The evolution of the structural, electrical and optical properties in indium-tin-oxide (ITO) thin film on glass substrate prepared by DC reactive magnetron sputtering was investigated. The variation of the structural, electrical and optical properties could be largely divided into two regions of (i) the initial region I roughly up to the critical film thickness of 50 nm and (ii) the stable region II above the critical thickness. As the film thickness grew, X-ray diffraction (XRD) peak intensities of both (2 2 2) and (4 0 0) planes increased continuously and the film morphology became clear. The peak intensity ratio of I₂₂₂/I₄₀₀ decreased gradually with the thickness, implying a preferred orientation along the (4 0 0) plane at a higher thickness.In the region II over the critical film thickness of 50 nm, where the structural evolution was clearly observable, the carrier density also increased over 9.0×1020/cm³ and the specific resistivity was lower than 140 μΩ cm.     

Texture optimization process of ZnO:Al thin films using NH4Cl aqueous solution for applications as antireflective coating in thin film solar cells

ZnO:Al thin films varying the thickness from 80 to 110 nm were deposited on polished float zone < 100 > Si wafers by radio frequency magnetron sputtering at 100 °C. To texturize these surfaces with the aim of being used as antireflective coating, a wet etching process based on NH₄Cl was applied. Taking into account that the layer thickness was small, the control of the etch parameters such as etchant concentration and etching time was evaluated as a function of the textured film properties. An appropriate control of the etching rate to adjust the final thickness to the 80 nm required for the application was realized. Using NH₄Cl concentrations of 10 wt.% and short times of up to 25 s, an increase of the film roughness up to a factor of 5.6 of the as-deposited films was achieved. These optimized textured films showed weighted reflectance values below 15% and considerable better electrical properties than the as-deposited 80 nm-thick ZnO:Al films.     

Preparation and characterizations of polyaniline (PANI)/ZnO nanocomposites film using solution casting method

Polyaniline (PANI)-ZnO nanoparticles composites film has been successfully fabricated by solution casting technique on glass substrate in which ZnO nanopowder was prepared via auto combustion method and used as inorganic materials. The as-grown nanocomposites film has been characterized using X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, Transmission electron microscopy (TEM) and Atomic Force Microscopy (AFM) for their structural and morphological characterizations. X-ray diffraction studies of as-grown film showed the reflection of ZnO nanoparticles along with a broad peak of PANI. The AFM study of the film shows the incorporation of ZnO nanoparticles into the polymer matrix which was further supported by roughness measurement. TEM images showed that the size of ZnO nanoparticles in the nanocomposites increase from ~ 35 nm to ~ 45 nm, indicating the interaction of nanoparticles with PANI molecular chains. FTIR spectra showed a band at 501 cm⁻¹ due to ZnO nanoparticles while the hydrogen bonding between the amine group of PANI and ZnO nanoparticles had been confirmed from the presence of the absorption band at 1148 cm⁻¹.