Structural, electrical and optical properties of zirconium-doped zinc oxide films prepared by radio frequency magnetron sputtering

Transparent and conducting zirconium-doped zinc oxide films have been prepared by radio frequency magnetron sputtering at room temperature. The ZrO₂ content in the target is varied from 0 to 10 wt.%. The films are polycrystalline with a hexagonal structure and a preferred orientation along the c axis. As the ZrO₂ content increases, the crystallinity and conductivity of the film are initially improved and then both show deterioration. Zr atoms mainly substitute Zn atoms when the ZrO₂ content are 3 and 5 wt.%, but tend to cluster into grain boundaries at higher contents. The lowest resistivity achieved is 2.07 × 10^− 3 Ω cm with the ZrO₂ content of 5 wt.% with a Hall mobility of 16 cm² V^− 1 s^− 1 and a carrier concentration of 1.95 × 10²⁰ cm^− 3. All the films present a high transmittance of above 90% in the visible range. The optical band gap depends on the carrier concentration, and the value is larger at higher carrier concentration.     

Growth and surface characterization of magnetron sputtered zinc nitride thin films

Zinc nitride films were deposited on Si(100) substrates at room temperature using RF-magnetron sputtering in pure N₂ and in Ar + N₂ atmospheres. Two active phonon modes (270.81 and 569.80 cm^− 1) are observed in Raman spectra for films deposited in Ar + N₂ atmosphere. Atomic force microscopy showed that the average surface roughness of the films deposited in pure N₂ atmosphere (1.3-3.33 nm) was less than for those deposited in a mixed Ar + N₂ atmosphere (10.3-12.8 nm). Low temperature cathodoluminescence showed two emission bands centered at 2.05 eV and 3.32 eV for both types of 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.     

High rate direct current magnetron sputtered and texture-etched zinc oxide films for silicon thin film solar cells

Aluminum-doped zinc oxide (AZO) films were prepared by in-line direct current (dc) magnetron sputtering on glass substrates. Four types of ceramic targets with 0.5 wt.% or 1 wt.% of aluminum oxide and different preparation methods, namely normal sintered, soft sintered and hot pressed, were employed. The influence of different target manufacturing processes, aluminum concentration and sputtering conditions on AZO films were investigated. Depending on the type of targets and deposition conditions, highly transparent films with low resistivity values in the range of 3.6-11 × 10^− 4 Ω cm were obtained. The etching behaviour in hydrochloric acid and the resulting light scattering properties of the AZO films were strongly influenced by the choice of the target and the deposition conditions. The most favourable films have been successfully applied in thin film solar cells with 1.1-μm microcrystalline silicon absorber layer leading to an initial efficiency of 7.8%.     

Structural and electrical properties of sputtered indium-zinc oxide thin films

In this study, indium-zinc oxide (IZO) thin films have been prepared at a room temperature, 200 and 300 °C by radio frequency magnetron sputtering from a In₂O₃-12 wt.% ZnO sintered ceramic target, and their dependence of electrical and structural properties on the oxygen content in sputter gas, the substrate temperature and the post-heat treatment was investigated. X-ray diffraction measurements showed that amorphous IZO films were formed at room temperature (RT) regardless of oxygen content in sputter gas, and micro-crystalline and In₂O₃-oriented crystalline films were obtained at 200 and 300 °C, respectively. From the analysis on the electrical and the structural properties of annealed IZO films under Ar atmosphere at 200, 300, 400 and 500 °C, it was shown that oxygen content in sputter gas is a critical parameter that determines the local structure of amorphous IZO film, stability of amorphous phase as well as its eventual crystalline structure, which again decide the electrical properties of the IZO films. As-prepared amorphous IZO film deposited at RT gave specific resistivity as low as 4.48 × 10^− 4 Ω cm, and the highest mobility value amounting to 47 cm²/V s was obtained from amorphous IZO film which was deposited in 0.5% oxygen content in sputter gas and subsequently annealed at 400 °C in Ar atmosphere.     

Improved ITO thin films with a thin ZnO buffer layer by sputtering

In this paper, we report a buffering method of improving the quality of ITO thin films on glass by r.f. magnetron sputtering. By applying a ZnO buffer before the ITO deposition in the same run of sputtering, ITO films showed single (111)-oriented highly textured structure, while ITO films showed mixed-oriented polycrystalline structure on bare glass. A design of experiment was taken out to minimize the resistivity of ITO films in the deposition parameter space (oxygen ratio, total gas pressure, and temperature). Resistance measurements showed that the ITO films with ZnO buffers had a remarkable 50% decrease of resistivity comparing to those without ZnO buffers at optimized deposition condition. Room-temperature Hall effect measurements showed that the decrease in resistivity comes from a large increase of mobility and a slight increase of carrier density after forming gas annealing. The ZnO/glass may be a good alternative substrate to bare glass for producing high quality ITO films for advanced electro-optic applications.     

Localized high-rate deposition of zinc oxide films at atmospheric pressure using inductively coupled microplasma

Linear transparent zinc oxide films were fabricated using an inductively coupled microplasma jet generated in argon under atmospheric conditions. The films were formed by the sputtering and melting of a zinc filament placed inside the plasma. Film growth rates varied between 10 to 30 nm/s for input powers between 20 and 30 W. Film roughness below 20 nm and optical transmittances up to 90% in the visible were obtained while the sheet resistances ranged between 2 × 10⁴ and 1 × 10⁵Ω/□. The presented technique may allow high-rate, localized, fabrication of functional ZnO films for optoelectronic applications.     

Magnetic and semi-conducting nano-composite films of spinel ferrite and cubic zinc oxide

Magnetic and semi-conducting nano-composite films have been prepared under bias polarization, by radio-frequency sputtering of a pure zinc ferrite target. These composite thin films are made of cubic Zn_1 − yFe_yO monoxide islands inside a spinel ferrite matrix. The relative proportion of each phase depends on the substrate polarization (i.e. bias power). When no bias is applied the films solely display the diffraction pattern of a spinel phase even if some islands inside the film can be observed by electron microscopy. When the bias power is increased, the spinel phase disappears progressively as enhanced formation of islands takes place in such a manner that the cubic Zn_1 − yFe_yO monoxide is solely revealed by X-ray diffraction for a bias power higher than 5 W. From bibliographical data and calculated phase diagrams, it can be inferred that these phases would require very low oxygen partial pressure, high temperature and mechanical pressure, to be obtained simultaneously by a conventional ceramic process. This underlines the strong potential of radio-frequency sputtering of oxide targets to prepare original oxides or composite materials.     

Refractive indices of textured indium tin oxide and zinc oxide thin films

The refractive indices of textured indium tin oxide (ITO) and zinc oxide (ZnO) thin films were measured and compared. The ITO thin film grown on glass and ZnO buffered glass substrates by sputtering showed distinct differences; the refractive index of ITO on glass was about 0.05 higher than that of ITO on ZnO buffered glass in the whole visible spectrum. The ZnO thin film grown on glass and ITO buffered glass substrates by filtered vacuum arc also showed distinct differences; the refractive index of ZnO on glass was higher than that of ZnO on ITO buffered glass in the red and green region, but lower in the blue region. The largest refractive index difference of ZnO on glass and ITO buffered glass was about 0.1 in the visible spectrum. The refractive index variation was correlated with the crystal quality, surface morphology and conductivity of the thin films.     

Extraction of optical constants of zinc oxide thin films by ellipsometry with various models

Spectroscopic ellipsometry was used to extract the optical constants of zinc oxide (ZnO) thin films deposited on (100) silicon substrate by filtered cathodic vacuum arc technique. Three dispersion models, namely, Sellmeier dispersion model, Cauchy model and Forouhi–Bloomer model, were evaluated for determining the optical constants of ZnO thin films below the energy band gap. The study shows that the Cauchy model provides the best spectral fittings among these three models. Above the energy band gap, two ellipsometric models, namely, two-phase model and three-phase point-by-point fit, were used. This study reveals that the initial values used in the point-by-point fitting play a critical role. It also shows that the refractive index and the extinction coefficient calculated with the two-phase model can be used as the initial values for the point-by-point fitting. The spectral dependence of the refractive index and extinction coefficient obtained in this work is comparable with the data reported in the literature. In sum, a reliable methodology for determining the optical constants of ZnO thin films in the ultraviolet-visible-near infrared range (2501100 nm) has been developed.     

Application of pulsed laser deposited zinc oxide films to thin film transistor device

Transparent zinc oxide (ZnO) thin films were deposited on various substrates using a pulsed laser deposition (PLD) technique. During the PLD, oxygen pressure and substrate temperature were varied in order to find an optimal preparation condition of ZnO for thin film transistor (TFT) application. Dependence of optical, electrical and crystalline properties on the deposition conditions was investigated. The ZnO thin films were then deposited on SiN/c-Si layer structures in order to fabricate a TFT device. The pulsed laser deposited ZnO films showed a remarkable TFT performance: field effect mobility (μ_FE) of 2.4-12.85 cm²/V s and ratio of on and off current (R_on/off) in 2-6 order range. Influence of ZnO preparation conditions on the resulting TFT performance was discussed.     

Properties of nanocrystalline zinc oxide thin films prepared by thermal decomposition of electrodeposited zinc peroxide

Zinc peroxide thin films were electrodeposited from aqueous solution at room temperature using H₂O₂ as the oxidation agent. Nanocrystalline zinc oxide thin films were then obtained from thermal decomposition of zinc peroxide thin films. The grain sizes of ZnO through thermal decomposition of ZnO₂ at 200 °C, 300 °C and 400 °C were estimated from the peak width of ZnO(110) obtained from X-ray diffraction and were 6.3 nm, 9.1 nm and 12.9 nm, respectively. The optical properties of zinc oxide thin films have been studied. The photoluminescence results indicate that ZnO thin films have low Stokes blue shift (about 110 meV) and low oxygen vacancies.     

Thermal stability of indium tin oxide thin films co-sputtered with zinc oxide

The thermal stability of indium tin oxide (ITO) films and ITO co-sputtered with zinc oxide (ZnO) films at different zinc atomic ratios in various atmospheres are investigated. The resistivity of the annealed ITO films decreased with increased annealing temperatures. The improved electrical properties were attributed mainly to the increase in carrier concentration originating from the significant formation of oxygen vacancies in the ITO films. In contrast, due to the lower oxidation potential of zinc ions, the resistivity of the annealed co-sputtered films showed no significant reduction and an increase with annealing temperatures. The film decomposition due to the high degree outdiffusion of oxygen atoms and aggregation of In atoms observed from the metal-like In phase in the diffraction patterns was responsible for the drastic thermal degradation in the electrical and optical properties of the samples annealed at elevated temperatures in reducing gas atmosphere. In contrast, the superior thermal stability of the co-sputtered films, at an atomic ratio of 60% annealed in reducing gas atmospheres, was ascribed to the stable Zn₃In₂O₆ crystalline structure that appeared in the diffraction pattern. The absorption edge observed from the optical transmittance of these annealed films also showed evidence of carrier concentration evolution in various annealing atmospheres. The lower oxidation potential of the zinc atoms introduced into the ITO films was concluded to be efficient in compensating for the formation of oxygen vacancies resulting in the alleviated decomposition behavior during thermal annealing.     

Micropatterned nanocrystalline zinc oxide thin films obtained through metal-loaded hydrogels

The paper describes the preparation of micropatterned zinc oxide films through a synthetic route based on the thermal degradation of metal-loaded poly(ethylene glycol)-based hydrogels. This approach requires very simple apparatuses and involves only simple, inexpensive and environmentally friendly chemicals. Highly transparent and crack free nanocrystalline films were obtained through this route. The evolution of the films during the thermal degradation and the influence of synthesis parameters on the film characteristics were investigated by thermal analysis, X-ray grazing incidence diffraction, scanning electron microscopy, atomic force microscopy and micro-Raman. The response toward reducing gasses was tested at different temperatures. Finally, the micropatterning of ZnO films through soft lithography has been characterized.     

Investigation of thin solid ZnO films prepared by sputtering

Zinc oxide (ZnO) thin films have attracted great attention in recent years due to their unique piezoelectric and piezooptic properties, making them suitable for various microelectronics and optoelectronics applications, such as surface acoustic wave devices, optical fibers, solar cells etc. ZnO is a semiconductor with a band gap of 3.3 eV and a large exciton binding energy of 60 meV. Undoped ZnO exhibits intrinsic n-type conductivity and it enables achieving high electron concentration. However, it may be doped to obtain low resistivity p-type thin films. Among group V of the periodic table, nitrogen is used as a popular p-type dopant due to its small atomic size. However, it is difficult to achieve p-type conduction in ZnO films due to the low solubility of nitrogen and its high intensity in self compensating process upon doping.Sputtering techniques enable us to form dense and homogeneous films due to the relatively high energy of the sputtered atoms. Thus we can grow high quality ZnO films with c-axis orientation, low growth temperature, high deposition rate, large area deposition, and availability in various growths ambient. In this work, the zinc oxide films were prepared using various DC sputtering methods in an atmosphere of pure argon and an atmosphere of mixed argon with nitrogen. Optical and electrical properties of the films were investigated.     

Peculiarities of nitrogen dioxide detection with sprayed undoped and indium-doped zinc oxide thin films

Nitrogen dioxide (NO₂) sensors based on sprayed zinc oxide (ZnO) thin films have been prepared. The effect of the film thickness and the In-doping on the sensor performance (sensor response and resistance) is analyzed. By adding 3 wt.% of indium nitrate to the spraying solution it is possible to enhance the film-gas response to 5 ppm of NO₂ at 275 °C. At the same time the film resistance is sensibly reduced. The film crystallographic structure, morphology and additive content are studied by means of X-ray Diffraction, Scanning Electron Microscopy, X-ray Photoelectron Spectroscopy and Atomic Force Microscopy. The possible sensitization mechanism is discussed.     

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.     

Polycrystalline growth and recrystallization processes in sputtered ITO thin films

Indium tin oxide (ITO) thin films with various thicknesses from 170 to 700 nm have been grown onto unheated glass substrates by sputtering from ceramic target, and subsequently annealed in vacuum at temperatures ranging from 250 to 350 °C. The structure, morphology and electro-optical characteristics of the ITO samples have been analyzed by X-ray diffraction, atomic force microscopy, four-point electrical measurements and spectrophotometry. Polycrystalline ITO growth has been found varying with film thickness. The thickness also determined the recrystallization achievable by annealing and the electro-optical thin film properties.     

Thermal stability of sputtered zirconium oxide films

In this work, the effect of post-growth annealing on the structural and optical properties of sputtered zirconium oxide films has been investigated. The temperature dependence of structure, density, and optical constants has been systematically studied by X-ray diffraction, X-ray reflectometry, atomic force microscopy (AFM) and optical spectroscopy. X-ray diffraction studies show no variation in the crystalline phase upon annealing except grain growth. X-ray reflectivity measurements determine a density increase of approximately 11% and a simultaneous thickness reduction of 10% upon annealing. The surface roughness of the films increases upon annealing as determined by XRR and confirmed by AFM measurements. Optical spectroscopy measurements confirm that the refractive index n of the films decreases with increasing annealing temperature. At the same time the optical band gap E_g of the films increases from 4.58 to 4.97 eV annealing at 900°C. The surprising decrease of refractive index upon annealing is attributed to both the intermixing of Si with ZrO₂ and the increasing surface roughness of the films.     

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.