Characteristics of ZnO:In thin films prepared by RF magnetron sputtering

In-doped ZnO (ZnO:In) transparent conductive thin films were deposited on glass substrates by RF magnetron sputtering. The effect of substrate temperature on the structural, electrical and optical properties of the ZnO:In thin films was investigated. It was found that higher temperature improves the crystallinity of the films and promotes In substitution easily. ZnO:In thin films with the best crystal quality were fabricated at 300 °C, which exhibit a larger grain size of 29 nm and small tensile strain of 0.9%. The transmittance of all the films was revealed to be over 85% in the visible range independence of the substrate temperatures and the lowest resistivity of ZnO:In thin films is 2.4×10⁻³ Ω cm.     

Characterization of nitrogen-doped ZnO thin films grown by plasma-assisted pulsed laser deposition on sapphire substrates

The crystalline, optical and electrical properties of N-doped ZnO thin films were measured using X-ray diffraction, photoluminescence and Hall effect apparatus, respectively. The samples were grown using pulsed laser deposition on sapphire substrates coated priorly with ZnO buffer layers. For the purpose of acceptor doping, an electron cyclotron resonance (ECR) plasma source operated as a low-energy ion source was used for nitrogen incorporation in the samples. The X-ray diffraction analyses indicated some deterioration of the ZnO thin film with nitrogen incorporation. Temperature-dependent Van der Pauw measurements showed consistent p-type behavior over the measured temperature range of 200–450 K, with typical room temperature hole concentrations and mobilities of 5×10¹⁵ cm⁻³ and 7 cm²/V s, respectively. Low temperature photoluminescence spectra consisted of a broad emission band centered around 3.2 eV. This emission is characterized by the absence of the green deep-defect band and the presence of a band around 3.32 eV.     

Fabrication and properties of ZnO:Cu and ZnO:Ag thin films

Thin films of ZnS and ZnO:Cu were grown by an original metal–organic chemical vapour deposition (MOCVD) method under atmospheric pressure onto glass substrates. Pulse photo-assisted rapid thermal annealing of ZnO:Cu films in ambient air and at the temperature of 700–800 C was used instead of the common long-duration annealing in a vacuum furnace. ZnO:Ag thin films were prepared by oxidation and Ag doping of ZnS films. At first a closed space sublimation technique was used for Ag doping of ZnO films. The oxidation and Ag doping were carried out by a new non-vacuum method at a temperature >500 C. Crystal quality and optical properties were investigated using X-ray diffraction (XRD), atomic force microscopy (AFM), and photoluminescence (PL). It was found that the doped films have a higher degree of crystallinity than undoped films. The spectra of as-deposited ZnO:Cu films contained the bands typical for copper, i.e. the green band and the yellow band. After pulse annealing at high temperature the 410 and 435 nm photoluminescent peaks were observed. This allows changing of the emission colour from blue to white. Flat-top ZnO:Ag films were obtained with the surface roughness of 7 nm. These samples show a strong ultraviolet (UV) emission at room temperature. The 385 nm photoluminescent peak obtained is assigned to the exciton–exciton emission.     

Structural and electrical properties of zinc oxides thin films prepared by thermal oxidation

We report on zinc oxide (ZnO) thin films (d = 55-120 nm) prepared by thermal oxidation, at 623 K, of metallic zinc films, using a flash-heating method. Zinc films were deposited in vacuum by quasi-closed volume technique onto unheated glass substrates in two arrangements: horizontal and vertical positions relative to incident vapour. Depending on the preparation conditions, both quasi-amorphous and (0 0 2) textured polycrystalline ZnO films were obtained. The surface morphologies were characterized by atomic force microscopy and scanning electron microscopy. By in situ electrical measurements during two heating-cooling cycles up to a temperature of 673 K, an irreversible decrease of electrical conductivity of as flash-oxidized Zn films was revealed. The influence of deposition arrangement and oxidation conditions on the structural, morphological and electrical properties of the ZnO films is discussed.     

Influence of annealing temperature on the properties of ZnO thin films deposited by thermal evaporation

ZnO thin films were deposited by thermal evaporation of a ZnO powder. The as-deposited films are dark brown, rich zinc and present a low transmittance. Then, these films were annealed in air atmosphere at different temperatures between 100 and 400 °C. Their microstructure and composition were studied using XRD and RBS measurements respectively. By increasing the temperature, it was found that film oxidation starts at 250 °C. XRD peaks related to ZnO appear and peaks related to Zn decrease. At 300 °C, zinc was totally oxidised and the films became totally transparent. The electrical conductivity measurement that were carried out in function of the annealing temperature showed the transition from highly conductive Zn thin film to a lower conductive ZnO thin film. The optical gap (E_g) was deduced from the UV-vis transmittance, and its variation was linked to the formation of ZnO.     

Development of a novel high speed (electron-mobility) epi-n-ZnO thin films by L-MBE for III–V opto-electronic devices

Intrinsic epitaxial zinc oxide (epi-ZnO) thin films were grown by laser-molecular beam epitaxy (L-MBE), i.e., pulsed laser deposition (PLD) technique using Johnson Matthey “specpure”-grade ZnO pellets. The effects of substrate temperatures on ZnO thin film growth, electrical conductivity (σ), mobility (μ) and carrier concentration (n) were studied. As well as the feasibility of developing high quality conducting oxide thin films was also studied simultaneously. The highest conductivity was found for optimized epi-ZnO thin films is σ=0.06×10³ ohm⁻¹ cm⁻¹ (n-type) (which is almost at the edge of semiconductivity range), carrier density n=0.316×10¹⁹ cm⁻³ and mobility μ=98 cm²/V s. The electrical studies further confirmed the semiconductor characteristics of epi-n-ZnO thin films. The relationship between the optical and electrical properties were also graphically enumerated. The electrical parameter values for the films were calculated, graphically enumerated and tabulated. As a novelty point of view, we have concluded that without doping and annealing, we have obtained optimum electrical conductivity with high optical transparency (95%) for as deposited ZnO thin films using PLD. Also, this is the first time that we have applied PLD made ZnO thin films to iso-, hetero-semiconductor–insulator–semiconductor (SIS) type solar cells as transparent conducting oxide (TCO) window layer. We hope that surely these data be helpful either as a scientific or technical basis in the semiconductor processing.     

Atomic layer deposition and characterization of Ga-doped ZnO thin films

Low-resistivity n-type ZnO thin films were grown by atomic layer deposition (ALD) using diethylzinc (DEZ) and H₂O as Zn and O precursors. ZnO thin films were grown on c-plane sapphire (c- Al₂O₃) substrates at 300 C. For undoped ZnO thin films, it was found that the intensity of ZnO () reflection peak increased and the electron concentration increased from 6.8×10¹⁸ to 1.1×10²⁰ cm⁻³ with the increase of DEZ flow rate, which indicates the increase of O vacancies () and/or Zn interstitials (Zn_i). Ga-doping was performed under Zn-rich growth conditions using triethylgallium (TEG) as Ga precursor. The resistivity of 8.0×10⁻⁴ Ω cm was achieved at the TEG flow rate of 0.24 μmol/min.     

Dependences of structural and electrical properties on thickness of polycrystalline Ga-doped ZnO thin films prepared by reactive plasma deposition

Polycrystalline Ga-doped (Ga content: 4 wt%) ZnO (GZO) thin films were deposited on glass substrates at 200 C by a reactive plasma deposition with DC arc discharge technique. The dependences of structural and electrical properties of GZO films on thickness, ranging from 30 to 560 nm, were investigated. Carrier concentration, n, and Hall mobility, μ, increases with increasing film thickness below 100 nm, and then the n remains nearly constant and the μ gradually increases until the thickness reaches 560 nm. The resistivity obtained of the order of 10⁻⁴ Ω cm for these films decreases with increasing film thickness: The highest resistivity achieved is 4.4×10⁻⁴ Ω cm with n of 7.6×10²⁰ cm⁻³ and μ of 18.5 cm²/V s for GZO films with a thickness of 30 nm and the lowest one is 1.8×10⁻⁴ Ω cm with n of 1.1×10²¹ cm⁻³ and μ of 31.7 cm²/V s for the GZO film with a thickness of 560 nm. X-ray diffraction pattern for all the films shows a hexagonal wurtzite structure with its strongly preferred orientation along the c-axis. Full width at half maximum of the (002) preferred orientation diffraction peak of the films decreases with increasing film thickness below 100 nm.     

Study of structural, optical and electrical properties of ZnO and SnO2 thin films

The investigation of structure, optical and electrical properties of tin and zinc oxide films on glass substrates by using magnetron sputtering are carried out. X-ray data show the formation of textured tin oxides film during deposition and its transformation to SnO₂ polycrystalline film at low temperature (200 C) if the concentration of oxygen in the chamber is high (O₂ — 100%, Ar — 0%). Optimal conditions of SnO₂ polycrystalline film deposition (pressure of Ar–O₂ mixture in chamber — 2.7 Pa, concentration of O₂ — 10%) are determined. Low resistivity of as-deposited ZnO film and increasing ZnO crystallite sizes and phase volume at temperatures higher than the melting point of Zn (419.5 C) are explained by formation of conductive Zn and ZnO particle chains and their destruction, respectively.     

Electrical characterisation of phosphorus-doped ZnO thin films grown by pulsed laser deposition

Phosphorus-doped ZnO films were grown by pulsed laser deposition using a ZnO:P₂O₅-doped target as the phosphorus source with the aim of producing p-type ZnO material. ZnO:P layers (with phosphorus concentrations of between 0.01 to 1 wt%) were grown on a pure ZnO buffer layer. The electrical properties of the films were characterised from temperature dependent Hall-effect measurements. The samples typically showed weak n-type conduction in the dark, with a resistivity of 70 Ω cm, a Hall mobility of μ_n0.5 cm² V ⁻¹ s⁻¹ and a carrier concentration of n3×10¹⁷ cm⁻³ at room temperature. After exposure to an incandescent light source, the samples underwent a change in conduction from n- to p-type, with an increase in mobility and decrease in concentration for temperatures below 300 K.     

Growth and characterization of thin ZnO films deposited on glass substrates by electrodeposition technique

Electrodeposition technique was used in order to produce nanometric zinc oxide films on glass insulating substrates. The effect of electrolyte concentration and applied current density on the formation and growth of electrodeposited Zn thin films in aqueous solutions of ZnSO₄ were studied. After a thermal oxidation, a characterization of the structural morphology of the films deposited was carried out by optical microscopy (OM), atomic force microscopy (AFM), scanning electron microscopy (SEM) and by grazing incidence X-rays diffraction (GIXD). These characterization techniques show that the grains size of the films after oxidation at temperature 450 °C is between 5 and 15 nm, as well as the structure is polycrystalline nature with several orientations. UV/vis spectrophotometry confirms that it is possible to obtain transparent good ZnO films with an average transmittance of approximately 80% within the visible wavelength region, as well as the optical gap of obtained ZnO films is 3.17 eV.     

Ordered ultra thin ZnO films on metal substrate

Ultra thin ZnO films were prepared on metal Mo(1 1 0) substrate under ultrahigh vacuum conditions either by depositing Zn in 10⁻⁵ Pa oxygen or by oxidizing pre-deposited Zn films. The films were characterized in situ by various surface analytical techniques, including Auger electron spectroscopy, X-ray and ultraviolet photoelectron spectroscopies, low energy electron diffraction and high resolution electron energy loss spectroscopy. The results indicate that a long-range ordered and stoichiometric ZnO films are formed along its [0 0 0 1] direction. The annealing experiments show that as-prepared ZnO films are thermal stable until 800 K. This study provides constructive information to further understand the growth mechanism of ZnO films on different substrates.     

Optical and electrical characteristics of Al-doped ZnO thin films prepared by aqueous phase deposition

Transparent conducting Al-doped ZnO (AZO) thin films have been deposited by sol-gel route. Starting from an aqueous solution of zinc acetate by adding aluminum chloride as dopant, a c-axis oriented polycrystalline ZnO thin film 100 nm in thickness could be spin-coated on glass substrates via a two-step annealing process under reducing atmosphere. The effects of thermal annealing and dopant concentration on the structural, electrical and optical properties of AZO thin films were investigated. The post-treated AZO films exhibited a homogenous dense microstructure with grain sizes less than 10 nm as characterized by SEM photographs. The annealing atmosphere has prominent impact on the crystallinity of the films which will in turn influence the electrical conductivity. By varying the doping concentrations, the optical and electrical properties could be further adjusted. An optimal doping concentration of Al/Zn = 2.25 at.% was obtained with minimum resistivity of 9.90 × 10⁻³ Ω-cm whereas the carrier concentration and mobility was 1.25 × 10²⁰ cm⁻³ and 5.04 cm² V⁻¹ s⁻¹, respectively. In this case, the optical transmittance in the visible region is over 90%.     

Stable p-ZnO thin films by oxygen control using reverse spray dynamics

Semiconducting ZnO thin films were deposited on glass substrates by a modified CVD method using reverse spray of the precursor solutions. The films were characterized by X-ray diffraction (XRD) and Hall effect measurements at room temperature. The results of XRD analysis revealed polycrystalline nature of the grown films with different crystallographic orientations. The type of conductivity and the carrier concentration as determined from Hall effect measurements were dependent on the deposition temperature and annealing conditions. Oxygen control at 220 °C produced p-ZnO film with high hole mobility (193 cm²/V s). The electrical conductivity was correlated to the stoichiometry of the grown films.     

Transparent conductive ZnO:Ga films prepared by DC reactive magnetron sputtering at low temperature

Ga-doped ZnO (ZnO:Ga) transparent conductive films were deposited on glass substrates by DC reactive magnetron sputtering. The structural, electrical, and optical properties of ZnO:Ga films were investigated in a wide temperature range from room temperature up to 400 °C. The crystallinity and surface morphology of the films are strongly dependent on the growth temperatures, which in turn exert an influence on the electrical and optical properties of the ZnO:Ga films. The film deposited at 350 °C exhibited the relatively well crystallinity and the lowest resistivity of 3.4 × 10⁻⁴ Ω cm. More importantly, the low-resistance and high-transmittance ZnO:Ga films were also obtained at a low temperature of 150 °C by changing the sputtering powers, having acceptable properties for application as transparent conductive electrodes in LCDs and solar cells.     

The microstructure, optical, and electrical properties of sol–gel-derived Sc-doped and Al–Sc co-doped ZnO thin films

Transparent conductive ZnO:Al–Sc (1:0.5, 1:1, 1:1.5 at.% Al–Sc) thin films were prepared on glass substrates by sol–gel method. The microstructure, optical, and electrical properties of ZnO:Sc and ZnO:Al–Sc films were investigated. Results show that Sc-doping alone obviously decreases grain size and degrades the crystallinity; there is an amorphous phase on the surface of ZnO grains; the transmittance spectra fluctuate dramatically with a large absorption valley at about 430–600 nm. However, Al–Sc co-doping can stabilize grain size and improve the microstructure; an average visible transmittance of above 73% is obtained with no large absorption valley; the amorphous phase does not appear. The optical band gaps of ZnO:Sc and ZnO:Al–Sc films (3.30–3.32 eV) are blue-shifted relative to pure ZnO film (3.30 eV). Hall effects show that the lowest resistivity of 2.941 × 10⁻² Ω cm and the maximum Hall mobility of 24.04 cm²/V s are obtained for ZnO:Al–Sc films while ZnO:Sc films do not exhibit any electrical conductivity. Moreover, there is an optimum atomic ratio with Al to Sc of 1:0.5–1 at.%. Although the resistivities are increased compared with that of ZnO:Al film, the Hall mobilities are raised by one order of magnitude.     

Structural,electrical and optical studies on spray-deposited aluminium-doped ZnO thin films

Thin films of zinc oxide (ZnO) were deposited on cleaned glass substrates by chemical spray pyrolysis technique using Zn(CH₃COO)₂ as precursor solution. Also, aluminium-doped thin films of ZnO were prepared by using AlCl₃ as doping solution for aluminium. The dopant concentration [Al/Zn atomic percentage (at%)] was varied from 0 to 1.5 at% in thin films of ZnO prepared in different depositions. Structural characterization of the deposited films was performed with X-ray diffraction (XRD) studies. It confirmed that all the films were of zinc oxide having polycrystalline nature and possessing typical hexagonal wurtzite structure with crystallite size varying between 100.7 and 268.6 nm. The films exhibited changes in relative intensities and crystallite size with changes in the doping concentration of Al. The electrical studies established that 1 at% of Al-doping was the optimum for enhancing electrical conduction in ZnO thin films and beyond that the distortion caused in the lattice lowered the conductivity. The films also exhibited distinct changes in their optical properties at different doping concentrations, including a blue shift and slight widening of bandgap with increasing Al dopant concentration.     

Thermal oxidation of n-type ZnN films made by -sputtering from a zinc nitride target, and their conversion into p-type films

Transparent p-type thin films, containing zinc oxide phases, have been fabricated from the oxidation of n-type zinc nitride films. The zinc nitride thin films were deposited by rf-magnetron sputtering from a zinc nitride target in pure N₂ and pure Ar plasma. Films deposited in Ar plasma were conductive (resistivity 4.7×10⁻² Ω cm and carrier concentrations around 10²⁰ cm⁻³) Zn-rich Zn_xN_y films of low transmittance, whereas Zn_xN_y films deposited in N₂ plasma showed high transmittance (>80%), but five orders of magnitude lower conductivity. Thermal oxidation up to 550 C converted all films into p-type materials, exhibiting high resistivity, 10²–10³ Ω cm, and carrier concentration around 10¹³ cm⁻³. However, upon oxidation, the Zn_xN_y films did not show the zinc oxide phase, whereas Zn-rich Zn_xN_y films were converted into films containing ZnO and ZnO₂ phases. All films exhibited transmittance >85% with a characteristic excitonic dip in the transmittance curve at 365 nm. Low temperature photoluminescence revealed the existence of exciton emissions at 3.36 and 3.305 eV for the p-type zinc oxide film.     

Characteristics of ZnO:In thin films prepared by RF magnetron sputtering

In-doped ZnO (ZnO:In) transparent conductive thin films were deposited on glass substrates by RF magnetron sputtering. The effect of substrate temperature on the structural, electrical and optical properties of the ZnO:In thin films was investigated. It was found that higher temperature improves the crystallinity of the films and promotes In substitution easily. ZnO:In thin films with the best crystal quality were fabricated at 300 °C, which exhibit a larger grain size of 29 nm and small tensile strain of 0.9%. The transmittance of all the films was revealed to be over 85% in the visible range independence of the substrate temperatures and the lowest resistivity of ZnO:In thin films is 2.4×10⁻³ Ω cm.     

Investigation of p-type behavior in Ag-doped ZnO thin films by E-beam evaporation

Ag-doped ZnO (ZnO:Ag) thin films were grown on glass substrates by E-beam evaporation technique. The structural, electrical and optical properties of the films were investigated as a function of annealing temperature. The films were subjected to post annealing at different temperatures in the range of 350-650 °C in an air ambient. All the as grown and annealed films at temperature of 350 °C showed p-type conduction. The films lost p-type conduction after post annealing treatment temperature of above 350 °C, suggesting a narrow post annealing temperature window for the fabrication of p-type ZnO:Ag films. ZnO:Ag film annealed at 350 °C revealed lowest resistivity of 7.25 × 10⁻² Ω cm with hole concentration and mobility of 5.09 × 10¹⁹ cm⁻³ and 1.69 cm²/V s, respectively. Observation of a free-to-neutral-acceptor (e,A^o) and donor-acceptor-pair (DAP) emissions in the low temperature photoluminescence measurement confirms p-type conduction in the ZnO:Ag films.