Preparation and rapid thermal annealing of AlN thin films grown by molecular beam epitaxy

AlN films were grown at 785 ^°C on (0001) sapphire substrates by radio-frequency assisted molecular beam epitaxy. Post-growth rapid thermal annealing (RTA) was carried out from 900 to 1200 ^°C for 10 s in flowing N₂. The morphological and structural properties of the AlN epilayers before and after the RTA were studied by atomic force microscopy, x-ray diffraction and transmission electron microscopy. It is found that the threading dislocations can be decreased to an order of magnitude by using an interlayer growth method. The surface roughness (RMS) of the AlN thin films becomes larger with the increase of annealing temperature. The full width at half maximum of AlN (0002) rocking curve reaches its minimum after the RTA at 1000 ^°C.     

Physical and dispersive optical characteristics of ZrON/Si thin-film system

To date, the complex evaluation of physical and dispersive optical characteristics of the ZrON/Si film system has yet been reported. Hence, ZrON thin films have been formed on Si(100) substrates through oxidation/nitridation of sputtered metallic Zr in N₂O environment at 500, 700, and 900 ^°C. Physical properties of the deposited films have been characterized by X-ray diffractometry (XRD), Fourier transform infrared (FTIR) spectroscopy, reflection high-energy electron diffraction (RHEED), and spectroscopic ellipsometry (SE). It has been shown that ZrON/Si thin films without optical absorption can be prepared by oxidation/nitridation reaction in N₂O environment at 700–900 ^°C.     

Structural study of TiO2 thin films by micro-Raman spectroscopy

The Raman spectroscopy method was used for structural characterization of TiO₂ thin films prepared by atomic layer deposition (ALD) and pulsed laser deposition (PLD) on fused silica and single-crystal silicon and sapphire substrates. Using ALD, anatase thin films were grown on silica and silicon substrates at temperatures 125–425 °C. At higher deposition temperatures, mixed anatase and rutile phases grew on these substrates. Post-growth annealing resulted in anatase-to-rutile phase transitions at 750 °C in the case of pure anatase films. The films that contained chlorine residues and were amorphous in their as-grown stage transformed into anatase phase at 400 °C and retained this phase even after annealing at 900 °C. On single crystal sapphire substrates, phase-pure rutile films were obtained by ALD at 425 °C and higher temperatures without additional annealing. Thin films that predominantly contained brookite phase were grown by PLD on silica substrates using rutile as a starting material.     

Annealing effects of sapphire substrate on properties of ZnO films grown by magnetron sputtering

The annealing effects of sapphire substrates on the quality of epitaxial ZnO films grown by dc reactive magnetron sputtering were studied. The atomic steps formed on (0001) sapphire (α-Al₂O₃) substrates surface by annealing at high temperature were analyzed by atomic force microscopy. Their influence on the growth of ZnO films was examined by X-ray diffraction and photoluminescence measurements. Experimental results indicate that the film quality is strongly affected by annealing treatment of the sapphire substrate surface. The optimum annealing temperature of sapphire substrates for ZnO grown by magnetron sputtering is 1400 °C for 1 h in air. PACS 81.40.Ef; 68.55.Jk; 81.05.Dz; 81.15.Cd     

Effect of annealing time on the structural and ferromagnetic properties of the GaMnN thin films

GaMnN thin films were deposited on a sapphire (0001) substrate by using laser assisted molecular beam epitaxy. Subsequently, the samples were annealed in the ammonia ambience at 1000 °C for different time lengths. The crystalline quality was improved gradually, and the room temperature ferromagnetism of our samples becomes stronger with the increase of the annealing time within 25 min. The X-ray photoelectron spectra analysis confirmed that the Mn³⁺ concentration in the GaMnN films increased after annealing. The stronger ferromagnetism was observed in the sample with the higher Mn³⁺ concentration. However, too long annealing time, such as 35 min, will lead to the degradation of the crystalline quality and the decrease of Mn³⁺ concentration, which results in the weakened ferromagnetism. The optimal annealing time is 25 min at 1000 °C in our experiments. Finally, the origin of the room temperature ferromagnetism in our samples was discussed preliminarily.     

In situ RHEED analysis of epitaxial Gd2O3 thin films grown on Si (001)

Epitaxial Gd₂O₃ thin films were successfully grown on Si (001) substrates using a two-step approach by laser molecular-beam epitaxy. At the first step, a ～0.8 nm thin layer was deposited at the temperature of 200 ^°C as the buffer layer. Then the substrate temperature was increased to 650 ^°C and in situ annealing for 5 min, and a second Gd₂O₃ layer with a desired thickness was deposited. The whole growth process is monitored by in situ reflection high-energy electron diffraction (RHEED). In situ RHEED analysis of the growing film has revealed that the first Gd₂O₃ layer deposition and in situ annealing are the critical processes for the epitaxial growth of Gd₂O₃ film. The Gd₂O₃ film has a monoclinic phase characterized by X-ray diffraction. The high-resolution transmission electron microscopy image showed all the Gd₂O₃ layers have a little bending because of the stress. In addition, a 5–6 nm amorphous interfacial layer between the Gd₂O₃ film and Si substrate is due to the in situ high temperature annealing for a long time. The successful Gd₂O₃/Si epitaxial growth predicted a possibility to develop the new functional microelectronics devices.     

Ultrathin amorphous Ti–Al film used as a diffusion barrier for copper metallization

The viability of ultrathin amorphous Ti–Al film (～4 nm) as a diffusion barrier layer between Cu and Si for the application in Si-based ultra-large scale integration (ULSI) has been investigated. The Cu/Ti–Al/Si heterostructures are annealed in a high vacuum at various temperatures. There is no impurity peaks in the X-ray diffraction patterns for the samples up to annealing temperature of 800 ^°C, although the island-like grains were observed on the surface of the 800 ^°C annealed sample due to dewetting and agglomeration of the Cu film. No inter-reactions can be found from the images of transmission electron microscopy and Ti–Al is still amorphous after high-temperature annealing. These results indicate that Ti–Al film can effectively separate Cu from Si at high temperatures, and that the amorphous ultrathin Ti–Al film can be a very good barrier layer for Cu metallization.     

Oxidation of bismuth nanodroplets deposit on GaAs substrate

Bismuth nanodroplets on GaAs substrate were obtained by metalorganic vapor phase epitaxy (MOVPE). New products have been synthesized when Bi nanodroplets are heated under oxygen atmosphere. The oxidation process of Bi nanodroplets consists of a heating from the room temperature to different oxidation temperatures (350, 500, 600 ^°C) with a temperature rate of 14 ^°C/min. The annealing duration was fixed to 30 min. The presence of oxygen in the products was confirmed by energy dispersive X-ray (EDX) measurements using a scanning electron microscope (SEM). SEM images show that Bi microcomposites density decrease and their size increases with increasing annealing temperature. After X-ray diffraction analysis of the products no obvious peaks could be observed. The reflectance spectra of the products were studied in spectral domains ranged from 200 nm to 1100 nm. By fitting the reflectivity signal, we extracted the thickness of the products and their refractive index variation versus wavelength. The results show that the thickness of the samples increases with increasing annealing temperature. The photoluminescence (PL) spectra under excitation at 325 nm shows a broad emission centered at around 1.92 eV.     

Thermally activated crystallization of Nb2O5 grown on Pt electrode

The influence of the local crystallographic orientation of the polycrystalline bottom platinum electrode on the crystallization of niobium pentoxide thin films during their rapid thermal annealing was investigated by X-ray diffraction, X-ray reflectivity and transmission electron microscopy. The Nb₂O₅ thin films under study were reactively sputtered in a mixed O₂/Ar atmosphere and subsequently subjected to the annealing in argon atmosphere at temperatures ranging from 500 ^°C to 700 ^°C. The X-ray diffraction confirmed a transition from the amorphous niobium oxide to the crystalline orthorhombic Nb₂O₅ for temperatures between 500 ^°C and 600 ^°C. The X-ray reflectivity measurements showed that the crystallization process was accompanied by a continuous increase of the electron density in Nb₂O₅ and by a rapid increase of the surface roughness at 700 ^°C. It was further observed by transmission electron microscopy that Nb₂O₅ crystallizes selectively and that the crystalline domains of Nb₂O₅ possess a strong orientation relationship to the platinum from the bottom electrode. The orientation relationship $(\bar{1} 1 1)_{\mathrm{Pt}}\,{\parallel}\, (\bar{1} \bar{6}0)_{\mathrm{Nb}_{2}\mathrm{O}_{5}}$ was identified as the most beneficial one for crystallization of Nb₂O₅.     

Aluminium-induced crystallization of amorphous silicon films deposited by DC magnetron sputtering on glasses

Amorphous silicon (a-Si) and hydrogenated amorphous silicon (a-Si:H) films were deposited by DC magnetron sputtering technique with argon and hydrogen plasma mixture on Al deposited by thermal evaporation on glass substrates. The a-Si/Al and a-Si:H/Al thin films were annealed at different temperatures ranging from 250 to 550 °C during 4 h in vacuum-sealed bulb. The effects of annealing temperature on optical, structural and morphological properties of as-grown as well as the vacuum-annealed a-Si/Al and a-Si:H/Al thin films are presented in this contribution. The averaged transmittance of a-Si:H/Al film increases upon increasing the annealing temperature. XRD measurements clearly evidence that crystallization is initiated at 450 °C. The number and intensity of diffraction peaks appearing in the diffraction patterns are more important in a-Si:H/Al than that in a-Si/Al layers. Results show that a-Si:H films deposited on Al/glass crystallize above 450 °C and present better crystallization than the a-Si layers. The presence of hydrogen induces an improvement of structural properties of poly-Si prepared by aluminium-induced crystallization (AIC).     

Study of structural and electrical properties of thin NiO<Subscript>x</Subscript> films prepared by ion beam sputtering of Ni and subsequent thermo-oxidation

Nickel oxide thin films were prepared by thermal annealing of thin Ni films (thickness ca 47?nm) deposited by ion beam sputtering. The thermal annealing was performed at 350 °C and 400 °C with elected time (1–7 hours) in a quartz furnace opened to air. During annealing the samples underwent structural changes, as well as changes of their electrical properties. The structural properties (surface morphology and occurrence of crystalline phases) were analyzed by the AFM and XRD methods, O and Ni depth concentration profiles by the NRA method, and electrical properties (sheet resistance) by the van der Pauw 4-point technique. The sheet resistance (R _S ) of the as-deposited sample was found to be 12.03 Ω/□; after open air thermal annealing at 350 °C for 1 h the value was found to be almost the same, 11.67 Ω/□. After 2 h of annealing, however, a sharp increase in the sheet resistance (R _S = 1.46 MΩ/□) was observed. At this stage the deposit formed largely oxidized Ni layer with a distinct polycrystalline structure. The sharp increase of sheet resistance was ascribed to the oxidation of the Ni layer, leaving only a smaller amount of isolated Ni particles unoxidized. Almost complete oxidation was found after 7 h of annealing at 350 °C. At 400 °C was almost complete oxidation recorded already after 1 h of annealing.     

Correlation of plume dynamics and oxygen pressure with VO2 stoichiometry during pulsed laser deposition

Vanadium dioxide thin films have been deposited on Corning glass substrates by a KrF laser ablation of V₂O₅ target at the laser fluence of 2 J?cm^?2. The substrate temperature and the target-substrate distance were set to 500 ^°C and 4 cm, respectively. X-ray diffraction analysis showed that pure VO₂ is only obtained at an oxygen pressure range of 4×10^?3–2×10^?2 mbar. A higher optical switching contrast was obtained for the VO₂ films deposited at 4×10^?3–10^?2 mbar. The films properties were correlated to the plume-oxygen gas interaction monitored by fast imaging of the plume.     

Investigation of threshold switching mechanism based on Mn-doped ZnO/GaN heterojunction by photogenerated carrier injection

Highly c-axis oriented ZnO thin films have been prepared on n-type GaN-coated sapphire substrates by radio frequency reactive magnetron sputtering at 100 °C followed by thermal annealing at 740 °C for 2 h. The ZnO/GaN heterojunction devices show a steady threshold switching (TS) characteristic. In addition, Mn-doped ZnO (MZO)/GaN heterojunction has been prepared and it shows lower threshold voltage and higher on/off ratio than those of ZnO/GaN heterojunction. The formation of TS characteristic may be attributed to trapping and detrapping of electrons in heterojunction device. Furthermore, the devices are investigated by the injection of photogenerated carriers, it is illustrated that the external carrier injection may affect the rate of the trapping of electrons and results in the decrease of the threshold voltage.     

Texture control and its impact on the properties of SrBi2Ta2O9 thin films prepared by pulsed laser deposition

SrBi₂Ta₂O₉ (SBT) ferroelectric thin films with different preferred orientations were deposited by pulsed laser deposition (PLD). Several methods have been developed to control the preferred orientation of SBT thin films. For SBT films deposited directly on Pt/TiO₂/SiO₂/Si substrates and in situ crystallized at the deposition temperature, the substrate temperature has a significant impact on the orientation and the remnant polarization (Pr) of the films; a higher substrate temperature benefits the formation of (115) texture and larger grain size. The films deposited on Pt/TiO₂/SiO₂/Si substrates at 830 °C are (115)-oriented and exhibit 2Pr of 6 μC/cm². (115)- and (200)-predominant films can be formed by using a La_0.85Sr_0.15CoO₃ (LSCO) buffer layer or by annealing amorphous SBT films deposited on Pt/TiO₂/SiO₂/Si substrates at 450 °C using rapid thermal annealing (RTA). These films exhibit good electric properties; 2Pr of the films are up to 12 μC/cm² and 17 μC/cm², respectively. The much larger 2Pr of the films deposited on the LSCO buffer layer and of the films obtained by RTA than 2Pr of the films deposited on Pt/TiO₂/SiO₂/Si substrates at 830 °C is attributed to a stronger (200) texture. Received: 30 January 2001 / Accepted: 30 May 2001 / Published online: 25 July 2001     

The microstructures and the electrical and optical properties of ZnO:N films prepared by thermal oxidation of Zn3N2 precursor

Samples of p-type ZnO:N films were prepared on glass substrates by thermal oxidation of Zn₃N₂ precursor, which was produced by reactive magnetron sputtering with a metallic zinc target in Ar/N₂ working gas. The microstructures and the electrical and optical properties of the samples were systematically investigated as a function of the annealing temperature. The results indicate that the annealing temperature has strong effects on the conductivity and photoluminescence (PL) properties of the obtained ZnO:N films. With an annealing temperature of 500 ^°C in oxygen flux, ZnO:N samples show the best p-type characteristics. The doping mechanism and the doping efficiency are briefly discussed based on the experimental results.     

Formation of superconductive supersaturated TaZr solid solutions by pulsed electron beam treatment

Amorphous TaZr films were prepared by simultaneous evaporation onto sapphire substrates. Pulsed electron beam treatment with deposited energy densities above a threshold of about 2 J cm^?2 led to a crystallization of the films and to the formation of supersaturated TaZr solid solutions with a bcc structure up to Zr concentrations of 54 at %. The crystalline alloys were superconducting with a maximum transition temperature T_c of 7.7 K. The films decomposed totally at a temperature of 1100°C during furnace annealing.     

Swift heavy ion provoked structural, optical and electrical properties in SnO2 thin films

SnO₂ thin films grown on glass substrates at 300 ^°C by reactive thermal evaporation and annealed at 600 ^°C were irradiated by 120 MeV Ag⁹⁺ ions. Though irradiation is known to induce lattice disorder and suppression of crystallinity, we observe grain growth at a certain fluence of irradiation. X-ray diffraction (XRD) revealed the crystalline nature of the films. The particle size estimated by Scherrer’s formula for the irradiated films was in the range 10–25 nm. The crystallite size increases with increase in fluence up to 1×10¹² ions?cm^?2, whereas after that the size starts decreasing. Atomic force microscope (AFM) results showed the surface modification of nanostructures for films irradiated with fluences of 1×10¹¹ ions?cm^?2 to 1×10¹³ ions?cm^?2. The UV–visible spectrum showed the band gap of the irradiated films in the range of 3.56 eV–3.95 eV. The resistivity decreases with fluence up to 5×10¹² ions?cm^?2 and starts increasing after that. Rutherford Backscattering (RBS) reveals the composition of the films and sputtering of ions due to irradiation at higher fluence.     

Preparation of p-type ZnO:(Al, N) by a combination of sol--gel and ion-implantation techniques

We report the preparation of p-type ZnO thin films on (0001) sapphire substrates by a combination of sol--gel and ion-implantation techniques. The results of the Hall-effect measurements carried out at room temperature indicate that the N-implanted ZnO:Al films annealed at 600\du\ have converted to p-type conduction with a hole concentration of $1.6\times10¹⁸cm^-3, a hole mobility of 3.67cm²/V.s and a minimum resistivity of 4.80cm.\Omega$. Ion-beam induced damage recovery has been investigated by x-ray diffraction (XRD), photoluminescence (PL) and optical transmittance measurements. Results show that diffraction peaks and PL intensities are decreased by N ion implantation, but they nearly recover after annealing at 600\du. Our results demonstrate a promising approach to fabricate p-type ZnO at a low cost.     

Studies on highly resistive ZnO thin films grown by DC-discharge-assisted pulsed laser deposition

It was found that by changing the substrate temperature from room temperature to ～850 °C, ZnO thin films with widely varying resistivity values could be grown on sapphire substrates using DC-discharge-assisted pulsed laser deposition (PLD) in oxygen ambient. The resistivity of the film grown at room temperature was too high to measure using our existing setup. However, as the growth temperature was increased from 550 °C to 750 °C, the resistivity first decreased slowly from ～14.0 to 4.4 Ω?m and then dropped suddenly to get saturated at ～2.0×10^?3 Ω?m as the growth temperature was further increased. In contrast to these, when there was no DC-discharge, the variation of resistivity for ZnO thin films grown by PLD was marginal up to the substrate temperature of ～850 °C. The reason for these observations was found to be the combined effects of reduction in donor defect densities like oxygen vacancies and zinc interstitials, introduction of acceptor type defects like interstitial oxygen and zinc vacancies, and the resultant poor carrier mobility at lower growth temperatures. At higher growth temperatures (800 °C and above), the appearance of oxygen vacancies and increase in mobility due to better crystalline quality were found to be responsible for reducing the resistivity. The PL of these films had significant emission in the green and red regions of the spectrum due to the aforesaid defect related transitions. Such highly resistive and luminescent films might be suited for applications such as resistive RAM, UV-photo detector, TFT, piezoelectric, transparent phosphor, and broadband LED applications.     

Effect of Al doping on structural,optical and electrical properties of SnO2 thin films synthesized by pulsed laser deposition

Aluminium-doped (Al = 0–5?wt.%) SnO₂ thin films with low-electrical resistivity and high optical transparency have been successfully synthesized by pulsed laser deposition technique at 500 °C. Structural, optical and electrical properties of the as-deposited and post-annealed thin films were investigated. X-ray diffraction patterns suggest that the films transform from crystalline to amorphous state with increasing aluminium content. The root mean square (R_q) surface roughness parameter, determined by atomic force microscopy decreases upon annealing of the as-deposited film. While resistivity of the film is the lowest (9.49 × 10^?4 Ω-cm) at a critical doping level of 1?wt.% Al, optical transparency is the highest (nearly 90%) in the as-deposited condition. Temperature dependence of the electrical resistivity suggests that the Mott’s variable range hopping process is the dominant carrier transport mechanism in the lower temperature range (40–135 K) for all the films whereas, thermally activated band conduction mechanism seems to account for conduction in the higher temperature region (200–300 K).