Optimization of ZnO/Ag/ZnO multilayer electrodes obtained by Ion Beam Sputtering for optoelectronic devices

We investigated the electrical and optical properties of ZnO/Ag/ZnO multi-layer electrodes obtained by ion beam sputtering for flexible optoelectronic devices. This multi-layer structure has the advantage of adjusting the layer thickness to favor antireflection and the surface plasmon resonance of the metallic layer. Inserting a thin (Ag) metallic layer between two (ZnO) oxide layers decreases the sheet resistance while widening the optical transmittance window in the visible. We found that the optimal electrode is made up of a 10 nm thin Ag layer between two 35 nm and 20 nm thick ZnO layers, which resulted in a low sheet resistance (R_sq = 6 Ω/square), a high transmittance (T ≥ 80% in the visible) and the highest figure of merit of 1.65 × 10^-2 square/Ω.     

Conductive Ga doped ZnO/Cu/Ga doped ZnO thin films prepared by magnetron sputtering at room temperature for flexible electronics

Ga doped ZnO(GZO)/Cu/GZO multilayers were deposited by magnetron sputtering on polycarbonate substrates at room temperature. We investigated the structural, electrical, and optical properties of multilayers at various thicknesses of Cu and GZO layers. The lowest resistivity value of 3.3 × 10^− 5 Ω cm with a carrier concentration of 2.9 × 10²² cm^− 3 was obtained at the optimum Cu (10 nm) and GZO (10 nm) layer thickness. The highest value of figure of merit φ_TC is 2.68 × 10^− 3 Ω^− 1 for the GZO (10 nm)/Cu(10 nm)/GZO(10 nm) multilayer. The highest average near infrared reflectivity in the wavelength range 1000-2500 nm is as high as 70% for the GZO(10 nm)/Cu(10 nm)/GZO(10 nm) multilayer.     

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.     

Investigation of low resistance transparent MoO3/Ag/MoO3 multilayer and application as anode in organic solar cells

Depending on the resistivity and transmittance, transparent conductive oxides (TCO) are widely used in thin film optoelectronic devices. Thus doped In₂O₃ (ITO), ZnO, SnO₂ are commercially developed. However, the deposition process of these films need sputtering and/or heating cycle, which has negative effect on the performances of the organic devices due to the sputtering and heat damages. Therefore a thermally evaporable, low resistance, transparent electrode, deposited onto substrates room temperature, has to be developed to overcome these difficulties. For these reasons combination of dielectric materials and metal multilayer has been proposed to achieve high transparent conductive oxides. In this work the different structures probed were: MoO₃ (45 nm)/Ag (x nm)/MoO₃ (37.5 nm), with x = 5-15 nm. The measure of the electrical conductivity of the structures shows that there is a threshold value of the silver thickness: below 10 nm the films are semiconductor, from 10 nm and above the films are conductor. However, the transmittance of the structures decreases with the silver thickness, therefore the optimum Ag thickness is 10 nm. A structure MoO₃ (45 nm)/Ag (10 nm)/MoO₃ (37.5 nm) resulted with a resistivity of 8 × 10^− 5 Ω cm and a transmittance, at around 600 nm, of 80%. Such multilayer structure can be used as anode in organic solar cells according to the device anode/CuPc/C₆₀/Alq₃/Al. We have already shown that when the anode of the cells is an ITO film the introduction of a thin (3 nm) MoO₃ layer at the interface anode (ITO)/organic electron donor (CuPc) allows reducing the energy barrier due to the difference between the work function of ITO and the highest occupied molecular orbital of CuPc [1]. This property has been used in the present work to achieve a high hole transfer efficiency between the CuPc and the anode. For comparison MoO₃/Ag/MoO₃/CuPc/C₆₀/Alq₃/Al and ITO/MoO₃/CuPc/C₆₀/Alq3/Al solar cells have been deposited in the same run. These devices exhibit efficiency of the same order of magnitude.     

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.     

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).     

Effect of inserting a buffer layer on the characteristics of transparent conducting impurity-doped ZnO thin films prepared by dc magnetron sputtering

In transparent conducting impurity-doped ZnO thin films prepared on glass substrates by a dc magnetron sputtering (dc-MS) deposition, the obtainable lowest resistivity and the spatial resistivity distribution on the substrate surface were improved by a newly developed MS deposition method. The decrease of obtainable lowest resistivity as well as the improvement of spatial resistivity distribution on the substrate surface in Al- or Ga-doped ZnO (AZO or GZO) thin films were successfully achieved by inserting a very thin buffer layer, prepared using the same MS apparatus with the same target, between the thin film and the glass substrate. The deposition of the buffer layer required a more strongly oxidized target surface than possible to attain during a conventional dc-MS deposition. The optimal thickness of the buffer layer was found to be about 10 nm for both GZO and AZO thin films. The resistivity decrease is mainly attributed to an increase of Hall mobility rather than carrier concentration, resulting from an improvement of crystallinity coming from insertion of the buffer layer. Resistivities of 3 × 10^− 4 and 4 × 10^− 4Ω cm were obtained in 100 nm-thick-GZO and AZO thin films, respectively, incorporating a 10 nm-thick-buffer layer prepared at a substrate temperature around 200 °C.     

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.     

Characterization of ZnO:Al/Au/ZnO:Al trilayers for high performance transparent conducting electrodes

Symmetric ZnO:Al/Au/ZnO:Al trilayers were sputter-deposited and characterized for transparent conducting electrodes, varying the thickness of the ZnO:Al (AZO) and Au layers. The optical transmission for normal light incidence is optimum for an AZO thickness of 50 nm, due to the suppression of reflection. In this case, the transmittance is more than 0.7 for wavelengths above 400 nm and for a Au thickness of 5 nm. At the same time, the sheet resistance is approx. 30 Ω, which can be decreased to 12 Ω with the increase of the Au thickness to 9 nm. This is achieved with a moderate loss in the optical transmission. The figure of merit for transparent conducting electrodes, as introduced by G. Haacke (J. Appl. Phys. 47 (1976) 4086) yields values from 29.4 × 10^− 3 to 6.9 × 10^− 3 Ω^− 1, depending on the Au thickness and the considered wavelength range.     

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.     

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.     

Low-emitting surfaces prepared by applying transparent aluminum-doped zinc oxide coatings via a sol-gel process

Polycrystalline transparent conductive oxide thin films based on aluminum-doped zinc oxide (AZO) have been prepared on soda-lime glass by using an inorganic sol-gel process and the dip-coating technique. The multilayered films were crystallized on the substrate and subsequently annealed in a reducing atmosphere to enhance the number of free charge carriers. Significant characteristics of the functional coatings, such as crystallinity, surface smoothness, layer thickness, electrical conductivity, as well as the optical properties in a large spectral range between 0.25 and 35 μm were analyzed. The obtained samples are highly transparent with a visual transmittance above 0.85 and show specific resistivities of up to 1.6·10^− 3 Ω·cm. Applying an optimized AZO-coating with at most 500 nm is sufficient to reduce the surface emittance from 0.89 to less than 0.45 in the infrared.     

Effects of Ag interlayer on the optoelectrical properties of TiON films

A sandwich structure of TiON/Ag/TiON (TAgT) multilayer films was prepared onto glass substrates using RF and DC magnetron sputtering without intentional substrate heating. The thicknesses of each layer in the TAgT films were set at 50 nm, 5 nm and 45 nm. The optoelectrical properties of the TiON films were strongly influenced by the presence of an Ag interlayer. Although the optical transmittance of the film deteriorated when an Ag interlayer was added, the films had a low resistivity of 9.0 × 10⁻⁴ Ω cm due to increased carrier density. In addition, the TAgT films show work functions of 4.4 eV, which are suitable for organic light emitting diode (OLED) applications.The experimental results indicate that TiON film manufactured with a 5-nm thick Ag interlayer is an attractive candidate for use as a transparent electrode in large area electronic applications such as solar cells and displays.     

Fluorine-doped ZnO transparent conducting thin films prepared by radio frequency magnetron sputtering

Fluorine-doped ZnO transparent conducting thin films were prepared by radio frequency magnetron sputtering at 150 °C on glass substrate. Thermal annealing in vacuum was used to improve the optical and electrical properties of the films. X-ray patterns indicated that (002) preferential growth was observed. The grain size of F-doped ZnO thin films calculated from the full-width at half-maximum of the (002) diffraction lines is in the range of 18-24 nm. The average transmittance in visible region is over 90% for all specimens. The specimen annealed at 400 °C has the lowest resistivity of 1.86 × 10^− 3 Ω cm, the highest mobility of 8.9 cm² V^− 1 s^− 1, the highest carrier concentration of 3.78 × 10²⁰ cm^− 3, and the highest energy band gap of 3.40 eV. The resistivity of F-doped ZnO thin films increases gradually to 4.58 × 10^− 3 Ω cm after annealed at 400 °C for 4 h. The variation of the resistivity is slight.     

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.     

Fabrication of transparent conductive films with a sandwich structure composed of ITO/Cu/ITO

New transparent conductive films that had a sandwich structure composed of ITO/Cu/ITO multilayer films were prepared by a conventional RF and DC magnetron sputtering process on a polycarbonate substrate without intentional substrate heating. The thickness of each layer in the ITO/Cu/ITO films was kept constant at 50 nm/5 nm/45 nm. The optoelectrical and structural properties of the films were compared with conventional ITO single-layer films and ITO/Cu/ITO multilayered films. Although both films had identical thickness, 100 nm, the ITO/Cu/ITO films showed a lower resistivity, 3.5 × 10⁻⁴ Ω cm. In optical transmittance measurements, however, the ITO single-layer films showed a higher transmittance of 74% in the wavelength range of 300-800 nm. XRD spectra showed that both the ITO and ITO/Cu/ITO films were amorphous. The figure of merit, φ_TC, reached a maximum of 5.2 × 10⁻⁴ Ω⁻¹ for the ITO/Cu/ITO films, which was higher than the φ_TC of the ITO films (1.6 × 10⁻⁴ Ω⁻¹). The φ_TC results suggested that ITO/Cu/ITO films had better optoelectrical properties than conventional ITO single-layer films.     

Influence of Ag thickness on electrical, optical and structural properties of nanocrystalline MoO3/Ag/ITO multilayer for optoelectronic applications

In this study, MoO₃/Ag/ITO/glass (MAI) nano-multilayer films were deposited by the thermal evaporation technique and then were annealed in air atmosphere at 200 °C for 1 h. The effects of Ag layer thickness on electrical, optical and structural properties of the MoO₃(45 nm)/Ag(5-20 nm)/ITO(45 nm)/glass nano-multilayer films were investigated. The sheet resistance decreased rapidly with increasing Ag thickness. Above a thickness of 10 nm, the sheet resistances became somewhat saturated to a value of 3(Ω/□). The highest transparency over the visible wavelength region of spectrum (85%) was obtained for 10 nm Ag layer thickness. Carrier mobility, carrier concentrations, transmittance and reflectance of the layers were measured. The allowed direct band-gap for an Ag thickness range 5-20 nm was estimated to be in the range 3.58-3.71 eV. The XRD pattern showed that the films were polycrystalline. X-ray diffraction has shown that Ag layer has a (111) predominant orientation when deposited. The figure of merit was calculated for MAI multilayer films. It has been found that the Ag layer thickness is a very important factor in controlling the electrical and optical properties of MAI multilayer films. The optimum thickness of the Ag layer for these films was determined. The results exhibit that the MAI transparent electrode is a good structure for use as the anode of optoelectronic devices.     

Stable p-type conductivity and enhanced photoconductivity from nitrogen-doped annealed ZnO thin film

We report on the growth of p-type ZnO thin films with improved stability on various substrates and study the photoconductive property of the p-type ZnO films. The nitrogen doped ZnO (N:ZnO) thin films were grown on Si, quartz and alumina substrates by radio frequency magnetron sputtering followed by thermal annealing. Structural studies show that the N:ZnO films possess high crystallinity with c-axis orientation. The as-grown films possess higher lattice constants compared to the undoped films. Besides the high crystallinity, the Raman spectra show clear evidence of nitrogen incorporation in the doped ZnO lattice. A strong UV photoluminescence emission at ~ 380 nm is observed from all the N:ZnO thin films. Prior to post-deposition annealing, p-type conductivity was found to be unstable at room temperature. Post-growth annealing of N:ZnO film on Si substrate shows a relatively stable p-type ZnO with room temperature resistivity of 0.2 Ω cm, Hall mobility of 58 cm²/V s and hole concentration of 1.95 × 10¹⁷ cm^− 3. A homo-junction p-n diode fabricated on the annealed p-type ZnO layer showed rectification behavior in the current-voltage characteristics demonstrating the p-type conduction of the doped layer. Doped ZnO films (annealed) show more than two orders of magnitude enhancement in the photoconductivity as compared to that of the undoped film. The transient photoconductivity measurement with UV light illumination on the doped ZnO film shows a slow photoresponse with bi-exponential growth and bi-exponential decay behaviors. Mechanism of improved photoconductivity and slow photoresponse is discussed based on high mobility of carriers and photodesorption of oxygen molecules in the N:ZnO film, respectively.     

ZnO/Cu/ZnO multilayer films: Structure optimization and investigation on photoelectric properties

A series of ZnO/Cu/ZnO multilayer films has been fabricated from zinc and copper metallic targets by simultaneous RF and DC magnetron sputtering. Numerical simulation of the optical properties of the multilayer films has been carried out in order to guide the experimental work. The influences of the ZnO and Cu layer thicknesses, and of O₂/Ar ratio on the photoelectric and structural properties of the films were investigated. The optical and electrical properties of the multilayers were studied by optical spectrometry and four point probe measurements, respectively. The structural properties were investigated using X-ray diffraction. The performance of the multilayers as transparent conducting coatings was compared using a figure of merit. In experiments, the thickness of the ZnO layers was varied between 4 and 70 nm and those of Cu were between 8 and 37 nm. The O₂/Ar ratios range from 1:5 to 2:1. Low sheet resistance and high transmittance were obtained when the film was prepared using an O₂/Ar ratio of 1:4 and a thickness of ZnO (60 nm)/Cu (15 nm)/ZnO (60 nm).