Enhancement of the surface and structural properties of ZnO epitaxial films grown on Al2O3 substrates utilizing annealed ZnO buffer layers

ZnO films were grown on Al₂O₃ (1000) substrates without and with ZnO buffer layers by using radio-frequency magnetron sputtering. Atomic force microscopy images showed that the surface roughness of the ZnO films grown on ZnO buffer layers annealed in a vacuum was decreased, indicative of an improvement in the ZnO surfaces. X-ray diffraction patterns showed that the crystallinity of the ZnO thin films was enhanced by using the annealed ZnO buffer layer in comparison with the film grown on without a buffer layer. The improvement of the surface and structural properties of the ZnO films might be attributed to the formation of the Zn-face ZnO buffers due to annealing in a vacuum. These results indicate that the surface and structural properties of ZnO films grown on Al₂O₃ substrates are improved by using ZnO buffer layers annealed in a vacuum.     

Structural and electrical properties of Sb-doped p-type ZnO thin films fabricated by RF magnetron sputtering

We investigated the Sb-doping effects on ZnO thin film using RF (radio frequency) magnetron sputtering and RTA (rapid thermal annealing). The structural and electrical properties of the thin films were measured by X-ray diffraction, SEM (scanning electron microscope), and Hall effect measurement. Thin films were deposited at a high temperature of 800°C in order to improve the crystal quality and were annealed for a short time of only 3 min. The structural properties of undoped and Sb-doped films were considerably improved by increasing oxygen content in the Ar-O₂ gas mixture. Sb-doping also significantly decreased the electron concentration, making the films p-type. However, the crystallinity and surface roughness of the films degraded and the mobility decreased while increasing Sb-doping content, likely as a result of the formation of smaller grain size. From this study, we observed the transition to the p-type behavior at 1.5 at.% of Sb. The thin film deposited with this doping level showed a hole concentration of 4.412?×?10¹⁷ cm^?3 and thus is considered applicable to p-type ZnO thin film.     

Effect of a hydrogen ratio in electrical and optical properties of hydrogenated Al-doped ZnO films

This study examined the effect of the hydrogen ratio on the electrical and optical properties of hydrogenated Al-doped zinc oxide (AZO) thin films deposited by rf magnetron sputtering using a ceramic target (98 wt% ZnO, 2 wt% Al₂O₃). Various AZO films on glass were prepared by changing the H₂/(Ar?+?H₂) ratio at room temperature. The AZO/H films showed a lower resistivity and a higher carrier concentration and mobility than the AZO films. However, the resistivity and mobility of the AZO/H films increased and decreased with increasing H₂ flow ratio, respectively. As a result, the AZO/H films grown with 2% H₂ addition showed excellent electrical properties with a resistivity of 4.98?×?10⁴ Ωcm. The UV-measurements showed that the optical transmission of the AZO/H films was >85% in the visible range with a wide optical band gap. In addition, the effect of H₂ flow ratio on the structure and composition of hydrogenated AZO thin films have also been studied.     

Low temperature growth of sol-gel SrBi2Ta2O9 thin films by low-pressure annealing

A new low-temperature processing method to prepare SrBi₂Ta₂O₉ thin films is proposed. These thin films were prepared on Pt/Ta/SiO₂/Si substrates by a sol-gel method, and their structural and electrical properties were investigated. Films were annealed before and after the top Pt electrode deposition. The first annealing was performed in a 760-Torr oxygen atmosphere at 600 °C for 30 min, and the second annealing was performed in a 5-Torr oxygen atmosphere at 600 °C for 30 min. The films were well crystallized and fine-grained after the second annealing. The electrical characteristics of the 200-nm-thick film obtained by this new process were as follows: remanent polarization, P_r = 8.5 μC/cm²; coercive field, E_c = 36 kV/cm; and leakage current density, I_L = 1 × 10⁻⁷ A/cm² (at 150 kV/cm). This process is very attractive for highly integrated ferroelectric nonvolatile memory applications. © 1997 Scripta Technica, Inc. Electr Eng Jpn, 120(2): 27–33, 1997     

The annealing effect on properties of ZnO thin film transistors with Ti/Pt source-drain contact

ZnO-based thin film transistors (TFTs) with Ti/Pt contacts were fabricated on SiO₂/Si substrates. The as-deposited ZnO TFT did not work well as a TFT device but the annealed ZnO TFT showed acceptable characteristics with a mobility (μ_sat), threshold voltage (V_th), on/off ratio and subthreshold swing (SS) of 0.8 cm²/V.s, 2.5 V, over 10⁶ and 0.84 V/dec, respectively. Complete oxygen loss was observed in ZnO after annealing at 300°C under a N₂ atmosphere. The annealing process altered the crystallinity, density and composition of the ZnO active layers due to the formation of oxygen vacancies as shallow donors. This process is expected to play an important role in controlling the TFT performance of ZnO. In addition, it is expected to form the basis of the future electronic devices applications, such as transparent displays and active matrix organic lighting emitted displays (AMOLED).     

Unconventional magnetism in ZnO nanorods

ABSTRACT

We report room temperature ferromagnetism in vacuum annealed ZnO nanorods. ZnO nanorods were annealed at 600°C for 6 hours in an annealing chamber with a pressure of 10^?6 Torr. Our study indicates that ZnO nanorods develop room temperature ferromagnetism due to the presence of oxygen vacancy defects in it. Presence of large surface area of nanorods and oxygen vacancy are mainly responsible for the observed magnetic behavior.     

Electrical properties of paraelectric PLT(28) thin films deposited by dc magnetron sputtering

Abstract

Paraelectric [Pb, La]TiO₃ (PLT, La = 28 mol%) thin films were prepared by dc magnetron sputtering using a multi-element metal target. In order to crystallize the as-deposited PLT thin films into the cubic perovskite structure, a heat treatment was applied at annealing temperatures ranging between 450 and 750°C. The electrical measurements such as dielectric properties, polarization-electric field (P-E), and current-voltage (I–V) were investigated with the change of annealing temperature. The dielectric constant and dissipation factor of paraelectric PLT film annealed at 750°C were 1216 and 0.018, respectively. The charge storage density was approximately 12.5 μC/cm². The leakage current density in PLT film annealed at 650°C was around 0.1 μA/cm² at the electric field of 0.25 MV/cm.     

Annealing temperature effect on ferroelectric and magnetic properties in Mn-added polycrystalline BiFeO3 films

We fabricated 5 at.% Mn-added polycrystalline BiFeO₃ films and investigated the annealing temperature effect on structural, ferroelectric and magnetic properties. In the x-ray diffraction patterns, only the diffraction peaks due to the BiFeO₃ structure were observed and no secondary phase could be observed at annealing temperatures between 773 and 923 K. Adding Mn suppressed the leakage current density in the high electric field region when compared to pure BiFeO₃ films. The conduction mechanism of the Mn-added BiFeO₃ films was dominated by Ohmic conduction. Remanent polarization of the Mn-added polycrystalline BiFeO₃ films for an applied electric field of approximately 1.5 mV/cm was 63 μC/cm² for the specimen annealed at 773 K and 46 μC/cm² for the specimen annealed at 923 K, although the remanent polarization still exhibited a tendency to increase with an increase in the electric field. Spontaneous magnetization was obtained at high annealing specimens. This study revealed that the annealing temperature strongly affected the ferroelectric and magnetic properties in Mn-added polycrystalline BiFeO₃ films. In addition, by optimizing the annealing temperature, we realized multiferroics coexistent with spontaneous magnetization and spontaneous polarization at room temperature in the Mn-added polycrystalline BiFeO₃ film.     

Effect of heat treatment of sputter deposited ZnO films co-doped with H and Al

ZnO films co-doped with H and Al (HAZO) were prepared by sputtering ZnO targets containing Al₂O₃ dcontent of 1 (HA₁ZO series) and 2 wt.% (HA₂ZO series) on Corning glass (Eagle 2000) at substrate temperature of 150 °C with Ar and H₂/Ar gas mixtures. The effects of hydrogen addition to Al-doped ZnO (AZO) films with different Al contents on the electrical, optical and structural properties of the as-grown films as well as the vacuum- and air-annealed films were examined. For the as-deposited films, the free carrier number in both series of HAZO films increased with increasing H₂ content in sputter gas. HA₂ZO film series prepared from target containing 2 wt.% Al₂O₃ showed better crystallinity and higher carrier concentration than HA₁ZO film series deposited using target containing 1 wt.% Al₂O₃. The crystallinity and the Hall mobility of HA₂ZO film series decreased with increasing H₂ content in sputter gas, while those of HA₁ZO film series showed a reversed behavior. Although HA₂ZO film series yielded lower resistivity than HA₁ZO film series due to higher carrier concentrations, the higher figure of merit (expressed as 1?/?ρα, where ρ and α represents the resistivity and absorption coefficient, respectively) was observed for HA₁ZO film series because of substantially low absorption loss in these films. When annealed in air ambient, HA₁ZO film series showed much stronger stability than HA₂ZO film series. Vacuum-annealing resulted in drop of the carrier concentrations as well as large shrinkage in lattice constant, which indicated that the hydrogen dopants are in relatively volatile state and can be removed easily from the films upon annealing.     

The <00l>-oriented growth of Cu2S films and its switching properties

Cu₂S films have been deposited on Pt/TiO₂/SiO₂/Si(111) substrates, and annealed at different temperatures in a vacuum chamber. They were characterized by using X-ray diffraction and scanning electron microscopy. It was observed that the Cu₂S films deposited at room temperature are well crystallized and the grains are oriented along different directions. With the increase of the annealing temperature, the grains of Cu₂S films prefer the <00l>-orientations, and the average size of Cu₂S films decreases. After annealed at 400°C, the films are completely <00l>-oriented, and the grain boundaries of Cu₂S films become undistinguishable due to the possible movements of the ions at high temperature. The resistive ratio of the ‘off’ state to the ‘on’ state is about 10⁷ for the memory unit of Cu/Cu₂S/Pt structure with the Cu₂S films annealed at 400°C, about 6 orders of magnitude higher than that for the memory unit with the Cu₂S films deposited at room temperature.     

Deposition of Europium Oxide on Si and its optical properties depending on thermal annealing conditions

We investigate the influence of the ambient gas during thermal annealing on the photoluminescence (PL) properties of europium compound thin films on Si substrates. The films were deposited by radio-frequency magnetron sputtering and subsequently annealed in N₂ or O₂ ambient gas by rapid thermal annealing (RTA). The results of X-ray diffraction indicate that the resulting europium compound annealed in N₂ ambient have several silicate phases such as EuSiO₃ and Eu₂SiO₄ compared to those annealed in O₂ ambient. The spectral results revealed that a broad luminescence associated with Eu²⁺ ions, with a maximum intensity at 600 nm and a FWHM of 110 nm, was observed from the thin film annealed at 1000 °C in N₂ ambient. However, a series of narrow PL spectra from Eu³⁺ ions were observed from the film annealed in O₂ ambient.     

Preparation of TiO<Subscript>2</Subscript> thin films deposited from highly dense targets with multi-oxide glass doping

Glass doped TiO₂ (GTO) thin films were deposited by radio frequency (RF) magnetron sputter at room temperature and annealed in a reductive atmosphere containing 90 % N₂ and 10 % H₂. Highly dense TiO₂ ceramic mixed with glass consisting of multi-metal oxides (as a sintering aid) was used as the sputtering target. This sintering aid allows low temperature densification of TiO₂ target through a liquid phase wetting mechanism, and also works as a doping resource. XRD and FESEM were carried out to characterize the microstructure of the GTO films and the results reveal that the doping of multi-metal ions enhances the crystallization and increases the grain size of TiO₂ films. TEM analysis also showed that these metal ions were dissolved into TiO₂ lattices. The electrical and optical properties of TiO₂ thin films at different glass concentrations were evaluated and compared to the films merely doped with MoO₃. The electrical resistivity of the GTO films reaches 9.1 × 10^–4 Ω·cm at 2 wt% glass doping, corresponding to a carrier density of 8.9 x 10²⁰ cm^-3 and a mobility of 7.1 cm²/Vs. Meanwhile, the electrical resistivity of the TiO₂ film doped with glass was found to be lower than that of MoO₃-doped film. This was mainly attributed to the increase in carrier concentration by double doping effect of glass. The optical band gap of the GTO films ranged from 3.34 to 3.42 eV, which is greater than that of the un-doped TiO₂ film. This blue shift of approximately 0.18 eV was due to the Burstein-Moss effect.     

EFFECT OF ANNEALING ON THE ELECTRICAL PROPERTIES OF SrTiO3 THIN FILMS PRODUCED BY ION BEAM SPUTTERING

ABSTRACT

Thin film capacitors with SrTiO₃ (STO) as dielectric and Pt as electrode material have been prepared by ion beam sputtering. The as-deposited film is amorphous and exhibits a crystallization temperature around 321°C as proved by X-ray diffraction. The effect of post annealing on the crystalline quality of the films was systematically studied by x-ray diffraction and Atomic Force microscopy (AFM). The temperature and frequency dependent dielectric properties were measured from 30°C to 200°C and 0.01 Hz to 10⁵ Hz, respectively. The influence of the microstructure of SrTiO₃ thin films on their electrical properties was investigated through an extensive characterization. The electrical properties of SrTiO₃ films appear to be strongly depending on the annealing temperatures. The capacitance voltage (C-V) characteristics reveal an improvement of capacitance density with increasing the annealing temperature.     

A study on the characteristics of hydrated La2O3 thin films with different oxidation gases on the various annealing temperature

In order to investigate the structural and electrical properties of La₂O₃ films deposited by O₂ and O₃, films were hydrated in DI-water and annealed at 600 and 900 °C. La₂O₃ films deposited by O₃ showed better hydration resistance than those deposited by O₂. The thickness of both hydrated films decreased after annealing at 600 °C and increased after annealing at 900 °C. The dielectric constants of the La₂O₃ films deposited by O₃ were greater than films deposited by O₂ after annealing at 600 °C and slightly less after annealing at 900 °C. The leakage current density of the La₂O₃ films deposited by O₃ was lower than those by O₂ after annealing at 900 °C. To this end, La₂O₃ films deposited by O₃ showed better dissolution resistance than O₂ for hydration experiment as a function of dipping time.     

Properties of (001)-textured Pb(Mg1/3Nb2/3)O3–PbTiO3 thin films

Relaxor ferroelectric Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ (PMN–PT) thin films with [001] preferential orientation were deposited on platinized silicon wafers by a sol–gel method, in which a PbO seeding layer was involved. The influences of annealing temperature on the crystal phase, microstructure, and electrical properties of the PMN–PT films were investigated. Pyrochlore-free perovskite PMN–PT films could be formed on PbO-seeded Pt(111)/Ti/SiO₂/Si wafers at 800 °C, which was also the optimal annealing temperature for endowing the film with the best ferroelectric and dielectric properties. The enhanced properties were attributed to the improved crystallinity and microstructure. The leakage behaviors of the PMN–PT films annealed at different temperatures were also measured and discussed.     

Preparation and electrical properties of 0.4Pb(Zn1/3Nb2/3)O3-0.6Pb(Zr0.4Ti0.6)O3 thin films by 2-step annealing method

Films of (1−x)Pb(Zn_1/3Nb_2/3)O₃-xPb(Zr_0.4Ti_0.6) O₃ (x = 0.6, 40PZN-60PZT) were deposited on Pt/TiO₂/ SiO₂/Si substrate through spin coating. Using a combination of homogeneous precursor solution preparation and two-step pyrolysis process, we were able to obtain the 40PZN-60PZT thin films of perovskite phase virtually without pyrochlore phase precipitation after annealing above 650^∘C. But since annealing done at the high temperatures for extended time can cause diffusion of Pt, TiO₂ and Si, and precipitation of nonstoichiometric PbO, we adopted 2-step annealing method to circumvent these problems. The 2-step annealed films show dense microstructure than the 1-step films annealed at higher temperature. Furthermore, the root-mean-square surface roughness of 220 nm thick films which are annealed at 720^∘C for 1 min and then annealed at 650^∘C for 5 min was found to be 3.9 nm by atomic force microscopy as compared to the 12 nm surface roughness of the film annealed only at 720^∘C for 5 min. The electrical properties of 2-step annealed films are virtually same and those of the 1-step annealed films annealed at high temperature. The film 2-step annealed at 720^∘C for brief 1 min and with subsequent annealing at 650^∘C for 5 min showed a saturated hysteresis loop at an applied voltage of 5 V with remanent polarization (P _r) and coercive voltage (V _c) of 25.3 μC/cm² and 0.66 V respectively. The leakage current density was lower than 10⁻⁵A/cm² at an applied voltage of 5 V.     

Preparation and Ferroelectric Properties of K0.5Na0.5NbO3 Thin Films Derived from Non-alcohol Niobium Salt Sol-gel Process

Lead-free K_0.5Na_0.5NbO₃ (KNN) thin films were prepared on Pt (111) /Ti/SiO₂/Si (100) substrates by a polyvinylpyrrolidone (PVP)-modified sol-gel method without any metal alkoxides. The effects of PVP on the crystallization, surface morphology and electrical properties were investigated. It was found that the introduction of PVP into the sol could reduce the annealing temperature, enhance the surface quality and improve the KNN film of (100) oriented growth. Compared with the pure non-PVP-modified KNN thin films, the dielectric and ferroelectric properties of the KNN films were significantly enhanced by adding PVP into the sol. In particular, the PVP-modified KNN films which were annealed at 550°C exhibited relatively saturated polarization-electric field (P-E) hysteresis loops with high remnant polarization P_r of 22 μC/cm², dielectric constant of 280 and dielectric loss of 0.09, respectively, indicating promising lead-free piezoelectric film candidate for future applications.     

Effect of fluorine doping on the properties of ZnO films deposited by radio frequency magnetron sputtering

ZnO films with varying fluorine content were prepared on Corning glass by radio frequency magnetron sputtering of ZnO target containing ZnF₂ at room temperature, and the compositional, electrical, optical, and structural properties of the as-grown films together with the vacuum-annealed films were investigated. The fluorine content in the fluorine doped ZnO (FZO) films increased almost linearly with increasing ZnF₂ content in sputter target, and the highest atomic concentration was 7.3%. Vacuum-annealing caused a slight reduction of fluorine content in the films. The resistivity of the as-grown FZO films deposited showed a typical valley-like behavior with respect to the fluorine content in film, i.e. having minimum resistivity at intermediate fluorine content. Despite high fluorine content in the FZO films, the carrier concentration remained below 1.2?×?10²⁰ cm^?3, leading to very low doping efficiency level. Upon vacuum-annealing, the resistivity of FZO films decreased substantially due to increase in both the carrier concentration and the Hall mobility. From the structural analysis made by X-ray diffraction study, it was shown that addition of small amount of fluorine enhanced the crystallinity of FZO films with (002) preferred orientation, and that large amount of fluorine addition yielded disruption of preferred orientation. It was also shown that doping of fluorine rendered a beneficial effect in reducing the absorption loss of ZnO films in visible range, thereby substantially enhancing the figure of merit.     

The dependence of ferroelectric and fatigue behaviors of PZT films on annealing conditions

Films of PZT about 0.2 μm thick with the composition PbZr_0.53Ti_0.47O₃ were prepared using the metalloorganic decomposition (MOD) process. The amorphous films produced by pyrolysis at 350°C were annealed at 550, 575, 600 and 650°C for 10 minutes, 1 hour or 4 hours. Films annealed at temperatures below 550°C showed no ferroelectric behavior while others annealed above 650°C showed signs of loss of ferroelectric behavior. Most films demonstrated satisfactory ferroelectric properties such as low switching voltage and high polarization values. Some PZT films also demonstrated fatigue life-time of more than 10⁹ switching reversals. The performance of the films was dependent on the annealing time and temperature. It was found that films with better initial polarization values did not necessarily demonstrate better fatigue behavior. The causes of film degradation as a result of switching based on the pinning of domains at grain boundaries triggered by the migration of pores is discussed.     

The Rutile Phase of TiO2/Graphene Films: Sol–Gel Method,Phase Transition,Photocatalytic Properties

Abstract

TiO₂ materials are of great interest in different applications because of the controllable preparation of different structures. In this paper, the TiO₂ and TiO₂/graphene films with different phase structure and inserted graphene layer between Cu substrate and TiO₂ film were prepared by sol–gel method at different annealing temperatures, and then used as catalysts for photo-degradation of methylene blue (MB) dye solution under ultraviolet irradiation using 15?W of ultraviolet lamp. The effects of annealing temperature and graphene layer on the phase structure, morphology, chemical composition, binding energy level, and photocatalytic performance of TiO₂ films were studied in details. XRD results reveal that the anatase phase of TiO₂ films transfers to rutile phase with the increase in annealing temperature, and the introducing of graphene film layer can accelerate the phase transformation of anatase to rutile and improve the crystallization quality of TiO₂ films. It is found that the MB degradation efficiency of TiO₂ and TiO₂/graphene films is enhanced with the increasing annealed temperature, which shows that the existence of rutile phase, well crystalline quality and the better dispersion of the TiO₂ particles are helpful in photocatalytic behavior. In addition, compared to the rutile phase TiO₂ film, the rutile phase TiO₂/graphene films at annealed temperatures of 900?°C exhibit much higher photocatalytic activity due to the introduction of graphene films.