Structural, electrical and optical properties of ZnO:Al films deposited on flexible organic substrates for solar cell applications

Aluminum doped ZnO thin films (ZnO:Al) were deposited on glass and poly carbonate (PC) substrate by r.f. magnetron sputtering. In addition, the electrical, optical properties of the films prepared at various sputtering powers were investigated. The XRD measurements revealed that all of the obtained films were polycrystalline with the hexagonal structure and had a preferred orientation with the c-axis perpendicular to the substrate. The ZnO:Al films were increasingly dark gray colored as the sputter power increased, resulting in the loss of transmittance. High quality films with the resistivity as low as 9.7 × 10^− 4 Ω-cm and transmittance over 90% have been obtained by suitably controlling the r.f. power.     

Contact resistivity measurements of the buried Si-ZnO:Al interface of polycrystalline silicon thin-film solar cells on ZnO:Al

An experimental method is developed for contact resistivity measurements of a buried interface in polycrystalline silicon (poly-Si) thin-film solar cell devices on aluminum doped zinc oxide (ZnO:Al) layers. The solar cell concept comprises a glass substrate covered with a temperature-stable ZnO:Al film as transparent front contact layer, a poly-Si n⁺/p⁻/p⁺ cell, as well as a metal back contact. Glass/ZnO:Al/poly-Si/metal test stripe structures are fabricated by photolithographic techniques with the ZnO:Al stripes locally bared by laser ablation. The high-temperature treatments during poly-Si fabrication, e.g. a several hours lasting high-temperature step at 600 °C, are found to have no detrimental impact on the ZnO:Al/Si interface contact resistivity. All measured ρ_C values range well below 0.4 Ω cm² corresponding to a relative power loss ΔP below 3% for a solar cell with 500 mV open circuit voltage and 30 mA/cm² short circuit current density. By inclusion of a silicon nitride (SiN_x) diffusion barrier between ZnO:Al and poly-Si the electrical material quality of the poly-Si absorber can be significantly enhanced. Even in this case, the contact resistivity remains below 0.4 Ω cm² if the diffusion barrier has a thickness smaller than 10 nm.     

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.     

Optical and electrical properties of electron-irradiated Cu(In,Ga)Se2 solar cells

The optical and electrical properties of electron-irradiated Cu(In,Ga)Se₂ (CIGS) solar cells and the thin films that composed the CIGS solar cell structure were investigated. The transmittance of indium tin oxide (ITO), ZnO:Al, ZnO:Ga, undoped ZnO, and CdS thin films did not change for a fluence of up to 1.5 × 10¹⁸ cm^− 2. However, the resistivity of ZnO:Al and ZnO:Ga, which are generally used as window layers for CIGS solar cells, increased with increasing irradiation fluence. For CIGS thin films, the photoluminescence peak intensity due to Cu-related point defects, which do not significantly affect solar cell performance, increased with increasing electron irradiation. In CIGS solar cells, decreasing J_SC and increasing R_s reflected the influence of irradiated ZnO:Al, and decreasing V_OC and increasing R_sh mainly tended to reflect the pn-interface properties. These results may indicate that the surface ZnO:Al thin film and several heterojunctions tend to degrade easily by electron irradiation as compared with the bulk of semiconductor-composed solar cells.     

Aluminium doped zinc oxide sputtered from rotatable dual magnetrons for thin film silicon solar cells

This study addresses the electrical and optical properties as well as the surface structure after wet-chemical etching of mid-frequency magnetron sputtered aluminium doped zinc oxide (ZnO:Al) films on glass substrates from rotatable ceramic targets. Etching of an as-deposited ZnO:Al film in acid leads to rough surfaces with various feature sizes. The influence of working pressure and substrate temperature on the surface topography after etching was investigated. It was found that the growth model which Kluth et al. applied to films sputtered in radio frequency mode from planar ceramic target can be transferred to film growth from tube target. Furthermore, the influence of Ar gas flow and discharge power on the film properties was investigated. We achieved low resistivity of about 5.4 × 10^− 4 Ω·cm at high growth rates of 120 nm·m/min. Finally, surface textured ZnO:Al films were applied as substrates for microcrystalline silicon solar cells and high efficiencies of up to 8.49% were obtained.     

Effect of the [Al/Zn] ratio in the starting solution and deposition temperature on the physical properties of sprayed ZnO:Al thin films

Aluminum-doped zinc oxide thin films (ZnO:Al) were deposited on sodocalcic glass substrates by the chemical spray technique, using zinc acetate and aluminum pentanedionate as precursors. The effect of the [Al/Zn] ratio in the starting solution, as well as the substrate temperature, on the physical characteristic of ZnO:Al thin films was analyzed. We have found that the addition of Al to the starting solution decreases the electrical resistivity of the films until a minimum value, located between 2 and 3 at.%; a further increase in the [Al/Zn] ratio leads to an increase in the resistivity. A similar resistivity tendency with the substrate temperature was encountered, namely, as the substrate temperature is increased, a minimum value of around 475 °C in almost all the cases, was obtained. At higher deposition temperatures the film resistivity suffers an increase. After a vacuum-thermal treatment, performed at 400 °C for 1 h, the films showed a resistivity decrease about one order of magnitude, reaching a minimum value, for the films deposited at 475 °C, of 4.3 × 10^− 3 Ω cm.The film morphology is strongly affected by the [Al/Zn] ratio in the starting solution. X-ray analysis shows a (002) preferential growth in all the films. As the substrate temperature increases it is observed a slight increase in the transmittance as well as a shift in the band gap of the ZnO:Al thin films.     

The fabrication and application of ZnO:Al thin films in low-frequency inductively coupled plasma fabricated silicon solar cell

A home-made radio frequency magnetron sputtering is used to systematically study the structural, electrical, and optical properties of aluminum doped zinc oxide (ZnO:Al) thin films. The intensity of the (002) peak exhibits a remarkable enhancement with increasing film thickness. Upon optimization, we achieved low resistivity of 4.2 × 10^− 4 Ω cm and high transmittance of ~ 88% for ZnO:Al films. Based on the present experimental data, the carrier transport mechanism is discussed. It is found that the grain boundary scattering needs to be considered because the mean free path of free carrier is comparable to the grain size. The 80 nm-ZnO:Al thin films are then deposited onto low-frequency inductively coupled plasma fabricated silicon solar cells to assess the effect of ZnO:Al thin films on the performance of the solar cells. Optimized ZnO:Al thin films are identified as transparent and conductive oxide thin film layers.     

Filtered vacuum arc deposition of transparent conducting Al-doped ZnO films

Transparent conducting ZnO:Al and ZnO films of 380-800 nm thickness were deposited on glass substrates by filtered vacuum arc deposition (FVAD), using a cylindrical Zn cathode doped with 5-6 at.% Al or a pure Zn cathode in oxygen background gas with pressure P = 0.4-0.93 Pa. The crystalline structure, composition and electrical and optical properties of the films were studied as functions of P. The films were stored under ambient air conditions and the variation of their resistance as function of storage time was monitored over a period of several months.The Al concentration in the film was found to be 0.006-0.008 at.%, i.e., a few orders of magnitude lower than that in the cathode material. However, this low Al content influenced the film resistivity, ρ, and its stability. The resistivity of as-deposited ZnO:Al films, ρ = (6-8) × 10^− 3 Ω cm, was independent of P and lower by a factor of 2 in comparison to that of the ZnO films deposited by the same FVAD system. The ρ of ZnO films 60 days after deposition increased by a factor of ∼ 7 with respect to as-deposited films. The ZnO:Al films deposited with P = 0.47-0.6 Pa were more stable, their ρ first slowly increased during the storage time (1.1-1.4 times with respect to as-deposited films), and then stabilized after 30-45 days.     

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.     

Studies on the effect of hydrogen doping during deposition of Al:ZnO films using RF magnetron sputtering

Aluminum doped ZnO (ZnO:Al) films were deposited using rf magnetron sputtering in the presence of hydrogen gas in the chamber. A comparative study of the films deposited with and without hydrogen was performed. The XPS studies indicated that the decrease in resistivity of ZnO:Al films with the introduction of hydrogen gas is attributed to the reduced adsorption of oxygen species in the film grain boundaries. The average percentage transmission in the visible region of the films was around 92–95% and band gap was found to be about in the range of 3.15–3.17 eV. The lowest resistivity of 1.8 × 10⁻⁴ Ω cm was achieved for the ZnO:Al film deposited with hydrogen.     

Improving low pressure chemical vapor deposited zinc oxide contacts for thin film silicon solar cells by using rough glass substrates

Compared to zinc oxide grown (ZnO) on flat glass, rough etched glass substrates decrease the sheet resistance (R_sq) of zinc oxide layers grown on it. We explain this R_sq reduction from a higher thickness and an improved electron mobility for ZnO layers deposited on rough etched glass substrates. When using this etched glass substrate, we also obtain a large variety of surface texture by changing the thickness of the ZnO layer grown on it. This new combination of etched glass and ZnO layer shows improved light trapping potential compared to ZnO films grown on flat glass. With this new approach, Micromorph thin film silicon tandem solar cells with high total current densities (sum of the top and bottom cell current density) of up to 26.8 mA cm^− 2 were fabricated.     

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.     

Transparent conducting Al and Y codoped ZnO thin film deposited by DC sputtering

Transparent conducting Al and Y codoped zinc oxide (AZOY) thin films with high transparency and low resistivity were deposited by DC magnetron sputtering. The effects of substrate temperature on the structural, electrical and optical properties of AZOY thin films deposited on glass substrates have been investigated. X-ray diffraction spectra indicate that no diffraction peak of Al₂O₃ or Y₂O₃ except that of ZnO (0 0 2) is observed. The AZOY thin film prepared at substrate temperature of 250 °C has the optimal crystal quality inferring from FWHM of ZnO (0 0 2) diffraction peak, but the AZOY thin film deposited at 300 °C has the lowest resistivity of 3.6 × 10⁻⁴ Ω-cm, the highest mobility of 30.7 cm² V⁻¹ s⁻¹ and the highest carrier concentration of 5.6 × 10²⁰ cm⁻³. The films obtained have disorderly polyhedral surface morphology indicating possible application in thin film solar cell with good quality and high haze factor without the need of post-deposition etching.     

Characterizations of gallium-doped ZnO films on glass substrate prepared by atmospheric pressure metal-organic chemical vapor deposition

Ga-doped zinc oxide (ZnO:Ga) films were grown on glass substrate by atmospheric pressure metal-organic chemical vapor deposition (AP-MOCVD) using diethylzinc and water as reactant gases and triethyl gallium (TEG) as an n-type dopant gas. The structural, electrical and optical properties of ZnO:Ga films obtained at various flow rates of TEG ranging from 1.5 to 10 sccm were investigated. X-ray diffraction patterns and scanning electron microscopy images indicated that Ga-doping plays an important role in forming microstructures in ZnO films. A smooth surface with a predominant orientation of (101) was obtained for the ZnO:Ga film grown at a flow rate of TEG = 7.5 sccm. Moreover, a lowest resistivity of 3.6 × 10^− 4 Ω cm and a highest mobility of 30.4 cm² V^− 1 s^− 1 were presented by the same sample, as evaluated by Hall measurement. Otherwise, as the flow rate of TEG was increased, the average transmittance of ZnO:Ga films increased from 75% to more than 85% in the wavelength range of 400-800 nm, simultaneously with a blue-shift in the absorption edge. The results obtained suggest that low-resistivity and high-transparency ZnO films can be obtained by AP-MOCVD using Ga-doping sufficiently to make the films grow degenerate and effect the Burstein-Moss shift to raise the band-gap energy from 3.26 to 3.71 eV.     

Half wave rectification of inorganic/organic heterojunction diode at the frequency of 1 kHz

An inorganic/organic vertical heterojunction diode has been demonstrated with p-type Poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) deposited by spin coating on n-type Ga-doped ZnO (GZO) thin films. Transparent conducting GZO thin films are deposited on glass substrate by rf-magnetron sputtering. Electrical properties of GZO thin films are investigated depending on the processing temperatures. The resistivity, mobility and carrier concentration of the GZO thin films deposited at processing temperatures of 500 °C are measured to be about 3.6 × 10⁻⁴ Ω cm, 23.8 cm²/Vs and 7.1 × 10²⁰ cm³, respectively. The root mean square surface roughness of the GZO thin films is calculated to be ~ 0.9 nm using atomic force microscopy. Current-voltage characteristics of the n-GZO/p-PEDOT:PSS heterojunction diode present rectifying operation. Half wave rectification is observed with the maximum output voltage of 1.85 V at 1 kHz. Low turn-on voltage of about 1.3 V is obtained and the ideality factor of the n-GZO/p-PEDOT:PSS diode is derived to be about 1.8.     

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).     

Fabrication of low resistivity tin-doped indium oxide films with high electron carrier densities by a plasma sputtering method

Tin-doped indium oxide (ITO) films fabricated on glass substrates using a hot-cathode plasma sputtering method exhibited low resistivity of 9.7 × 10⁻⁵ Ω cm, which is due to a high carrier density of 2.1 × 10²¹ cm⁻³. The change in the number of carriers, N, as a function of film thickness d, strongly suggests that oxygen extraction in the initial stages of ITO film growth on the glass substrate surface, creates oxygen vacancies as an electron carrier source for improvement in the resistivity of the films.     

Silicon metal-semiconductor-metal photodetector with zinc oxide transparent conducting electrodes

Transparent conducting oxides thin layers, due to their optical and electrical properties, can be used as transparent electrodes in various optoelectronic devices. We present a metal-semiconductor-metal photodiode (MSM-PD) on silicon as optically active layer with zinc oxide (ZnO) thin layer as interdigitated Schottky transparent electrodes. The advantage of using a ZnO thin layer as Schottky electrodes consists in the improvement of the photoresponse by eliminating the shadowing of the active area by opaque metallic electrodes. ZnO thin layers were deposited on 10 Ω cm resistivity silicon epitaxial wafers by the vacuum thermal evaporation method. High purity metallic powders were mixed with an (Al + Sn)/Zn ratio of 0.03. In order to obtain transparent layers the metallic depositions were thermally treated at 450 °C for 2 h. The Al, Sn co-doped ZnO layers of 0.5-0.8 μm were investigated regarding structural, optical and electrical properties and surface morphology. The obtained thin layers have a high transparency (T > 85%) over a large spectral range and the resistivity is quite low, ρ ~ 10^− 4 Ω cm. The interdigitated Schottky contacts of ZnO were configurated onto the optically active Si layer providing an MSM-PD structure of 0.143 mm² active area and finger spacing and finger width of 6 μm. The optoelectronic characteristics were measured and the Schottky barrier height of 0.62 eV was determined from the current-voltage characteristic. A responsivity of 0.2 A/W at 475 nm and a capacitance of 1.4 pF at 10 V bias were obtained for the MSM-PD structure with transparent conducting ZnO Schottky electrodes.     

Influence of working pressure on ZnO:Al films from tube targets for silicon thin film solar cells

Mid-frequency magnetron sputtering of aluminum doped zinc oxide films (ZnO:Al) from tube ceramic targets has been investigated for silicon based thin film solar cell applications. The influence of working pressure on structural, electrical, and optical properties of sputtered ZnO:Al films was studied. ZnO:Al thin films with a minimum resistivity of 3.4 × 10⁻⁴ Ω cm, high mobility of 50 cm²/Vs, and high optical transmission close to 90% in visible spectrum region were achieved. The surface texture of ZnO:Al films after a chemical etching step was investigated. A gradual increase in feature sizes (diameter and depth) was observed with increasing sputter pressure. Silicon based thin film solar cells were prepared using the etched ZnO:Al films as front contacts. Energy conversion efficiencies of up to 10.2% were obtained for amorphous/microcrystalline silicon tandem solar cells.     

RF diode reactive sputtering of n- and p-type zinc oxide thin films

We present the relationship between parameters of reactive RF diode sputtering from a zinc oxide (ZnO) target and the crystalline, electrical and optical properties of n-/p-type ZnO thin films. The properties of the ZnO thin films depended on RF power, substrate temperature and, particularly, on working gas mixtures of Ar/O₂ and of Ar/N₂. Sputtering in Ar+O₂ working gas (up to 75% of O₂) improved the structure of an n-type ZnO thin film, from fibrous ZnO grains to columnar crystallites, both preferentially oriented along the c-axis normally to the substrate (〈0 0 2〉 direction). These films had good piezoelectric properties but also high resistivity (ρ≈10³ Ω cm). ZnO:N p-type films exhibited nanograin structure with preferential 〈0 0 2〉 orientation at 25% N₂ and 〈1 0 0〉 orientation for higher N₂ content. The presence of nitrogen N_O at O-sites forming N_O-O acceptor complexes in ZnO was proven by SIMS and Raman spectroscopy. A minimum value of resistivity of 790 Ω cm, a p-type carrier concentration of 3.6×10¹⁴ cm⁻³ and a Hall mobility of 22 cm² V⁻¹ s⁻¹ were obtained at 75% N₂.