Observation of ferromagnetism at room temperature for Cr ions implanted ZnO thin films

Single crystalline ZnO films were grown on c-plane GaN/sapphire (0 0 0 1) substrates by molecular beam epitaxy. Cr⁺ ions were implanted into the ZnO films with three different doses, i.e., 1 × 10¹⁴, 5 × 10¹⁵, and 3 × 10¹⁶ cm⁻². The implantation energy was 150 keV. Thermal treatment was carried out at 800 °C for 30 s in a rapid thermal annealing oven in flowing nitrogen. X-ray diffraction (XRD), atomic force microscopy, Raman measurements, transmission electron microscopy and superconducting quantum interference device were used to characterize the ZnO films. The results showed that thermal annealing relaxed the stress in the Cr⁺ ions implanted samples and the implantation-induced damage was partly recovered by means of the proper annealing treatment. Transmission electron microscopy measurements indicated that the first five monolayers of ZnO rotated an angle off the [0 0 0 1]-axis of the GaN in the interfacial layer. The magnetic-field dependence of magnetization of annealed ZnO:Cr showed ferromagnetic behavior at room temperature.     

Processing for optically active erbium in silicon by film co-deposition and ion-beam mixing

Techniques of film deposition by co-evaporation, ion-beam assisted mixing, oxygen ion implantation, and thermal annealing were been combined in a novel way to study processing of erbium-in-silicon thin-film materials for optoelectronics applications. Structures with erbium concentrations above atomic solubility in silicon and below that of silicide compounds were prepared by vacuum co-evaporation from two elemental sources to deposit 200-270 nm films on crystalline silicon substrates. Ar⁺ ions were implanted at 300 keV. Oxygen was incorporated by O⁺-ion implantation at 130 keV. Samples were annealed at 600 °C in vacuum. Concentration profiles of the constituent elements were obtained by Rutherford backscattering spectrometry. Results show that diffusion induced by ion-beam mixing and activated by thermal annealing depends on the deposited Si-Er profile and reaction with implanted oxygen. Room temperature photoluminescence spectra show Er³⁺ transitions in a 1480-1550 nm band and integrated intensities that increase with the oxygen-to-erbium ratio.     

Optical study of implantation damage recovery from Si-implanted GaN

Comprehensive and systematic optical activation studies of Si-implanted GaN grown on sapphire substrates have been made as a function of ion dose and anneal temperature. Silicon ions were implanted at 200 keV with doses ranging from 1×10¹³ to 5×10¹⁵ cm⁻² at room temperature. The samples were proximity cap annealed from 1250 to 1350 °C with a 500-Å-thick AlN cap in a nitrogen environment. The results of photoluminescence measurements made at 3 K show a very sharp neutral-donor-bound exciton peak along with a sharp donor-acceptor pair peak after annealing at 1350 °C for 20 s, indicating excellent implantation damage recovery. The results also indicate the AlN cap protected the implanted GaN layer very well during high temperature annealing without creating any significant anneal-induced damage. This observation is consistent with the electrical activation results for these samples.     

Effects of carbonization and substrate temperature on the growth of 3C-SiC on Si(1 1 1) by SSMBE

The growth of 3C-SiC on Si(1 1 1) substrate was performed at different carbonization temperatures and substrate temperatures by solid-source molecular beam epitaxy (SSMBE). The properties of SiC film were analyzed with in situ reflection high energy electron diffraction (RHEED), X-ray diffraction (XRD), atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The best carbonization temperature of 810 °C was found to be optimal for the surface carbonization. The quality of SiC film grown on Si at substrate temperature of 1000 °C is best. The worse crystalline quality for the sample grown at higher temperature was attributed to the large mismatch of thermal expansion coefficient between SiC and Si which caused more dislocation when sample was cooled down to room temperature from higher substrate temperature. Furthermore, the larger size of single pit and the total area of the pits make the quality of SiC films grown at higher temperature worse. More Si atoms for the sample grown at lower temperature were responsible for the degradation of crystalline quality for the sample grown at lower temperature.     

Synthesis of GaN phase by ion implantation

GaN phase is synthesized using systemic implantation of nitrogen ions of multiple energies (290, 130 and 50 keV) into Zn-doped GaAs (1 0 0) at room temperature and subsequent annealing at 850 °C for 30 min in Ar + H₂ atmosphere. The implanted doses of nitrogen ions are 5 × 10¹⁶ and 1 × 10¹⁷ ions-cm⁻². Glancing angle X-ray diffraction studies show that hexagonal phase of GaN were formed. The photoluminescence studies show the emission from the band edge as well as from point defects.     

Microstructural evolution upon annealing in Ar-implanted Si

The annealing effects of crystalline silicon (Si) implanted with argon (Ar) ions at a dose of 2 × 10¹⁶ Ar⁺/cm² at room temperature and subsequently annealed at 400-1100 °C for 30 min were investigated. The samples were analyzed by transmission electron microscopy and Raman spectroscopy. Before and after annealing up to 600 °C, an amorphous layer is formed but Ar bubbles are not observed in the damage layer. After annealing at 800 °C, argon bubbles are observed together with extended defects. The damage layer evolves into a polycrystalline structure. After annealing at 1100 °C; exfoliation occurs on the sample surface, and microtwin lamellas form in the damage layer. Raman scattering revealed that a strong recrystallization occurs from 600 °C to 800 °C. The results were compared with the case of helium implantation, with particular focus on bubble formation mechanisms.     

Synthesis of silicon carbide films by combined implantation with sputtering techniques

Silicon carbide (SiC) films were synthesized by combined metal vapor vacuum arc (MEVVA) ion implantation with ion beam assisted deposition (IBAD) techniques. Carbon ions with 40 keV energy were implanted into Si(1 0 0) substrates at ion fluence of 5 × 10¹⁶ ions/cm². Then silicon and carbon atoms were co-sputtered on the Si(1 0 0) substrate surface, at the same time the samples underwent assistant Ar-ion irradiation at 20 keV energy. A group of samples with substrate temperatures ranging from 400 to 600 °C were used to analyze the effect of temperature on formation of the SiC film. Influence of the assistant Ar-ion irradiation was also investigated. The structure, morphology and mechanical properties of the deposited films were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and nanoindentation, respectively. The bond configurations were obtained from IR absorption and Raman spectroscopy. The experimental results indicate that microcrystalline SiC films were synthesized at 600 °C. The substrate temperature and assistant Ar-ion irradiation played a key role in the process. The assistant Ar-ion irradiation also helps increasing the nanohardness and bulk modulus of the SiC films. The best values of nanohardness and bulk modulus were 24.1 and 282.6 GPa, respectively.     

Amorphous to crystalline phase transition in pulsed laser deposited silicon carbide

SiC thin films were grown on Si (1 0 0) substrates by excimer laser ablation of a SiC target in vacuum. The effect of deposition temperature (up to 950 °C), post-deposition annealing and laser energy on the nanostructure, bonding and crystalline properties of the films was studied, in order to elucidate their transition from an amorphous to a crystalline phase. Infra-red spectroscopy shows that growth at temperatures greater than 600 °C produces layers with increasingly uniform environment of the Si-C bonds, while the appearance of large crystallites is detected, by X-ray diffraction, at 800 °C. Electron paramagnetic resonance confirms the presence of clustered paramagnetic centers within the sp² carbon domains. Increasing deposition temperature leads to a decrease of the spin density and to a temperature-dependent component of the EPR linewidth induced by spin hopping. For films grown below 650 °C, post-deposition annealing at 1100 °C reduces the spin density as a result of a more uniform Si-C nanostructure, though large scale crystallization is not observed. For greater deposition temperatures, annealing leads to little changes in the bonding properties, but suppresses the temperature dependent component of the EPR linewidth. These findings are explained by a relaxation of the stress in the layers, through the annealing of the bond angle disorder that inhibits spin hopping processes.     

Annealing temperature dependence of Raman scattering in Si/SiO2 superlattice prepared by magnetron sputtering

Si/SiO₂ superlattices were prepared by magnetron sputtering, and the deposition temperature and annealing temperature had a great influence on the superlattice structure. In terms of SEM images, the mean size of Si nanocrystals annealed at 1100 °C is larger than that of nanocrystals annealed at 850 °C. It was found that the films deposited at room temperature are amorphous. With increasing deposition temperature, the amorphous and crystalline phases coexist. With increasing annealing temperature, the Raman intensity of the peak near 470 cm⁻¹ decreases, and the intensity of that at 520 cm⁻¹ increases. Also, on increasing the annealing temperature, the Raman peak near 520 cm⁻¹ shifts and narrows, and asymmetry emerges. A spherical cluster is used to model the nanocrystals in Si/SiO₂ superlattices, and the observed Raman spectra are analyzed by combining the effects of confinement on the phonon frequencies. Raman spectra from a variety of nanocrystalline silicon structures were successfully explained in terms of the phonon confinement effect. The fitted results agreed well with the experimental observations from SEM images.     

The important role of Mn in the room-temperature ferromagnetism of Mn-doped GaN films

Mn-doped GaN films (Ga_1−xMn_xN) were grown on sapphire (0 0 0 1) using Laser assisted Molecular Beam Epitaxy (LMBE). High-quality nanocrystalline Ga_1−xMn_xN films with different Mn concentration were then obtained by thermal annealing treatment for 30 min in the ammonia atmosphere. Mn ions were incorporated into the wurtzite structure of the host lattice by substituting the Ga sites with Mn³⁺ due to the thermal treatment. Mn³⁺, which is confirmed by XPS analysis, is believed to be the decisive factor in the origin of room-temperature ferromagnetism. The better room-temperature ferromagnetism is given with the higher Mn³⁺ concentration. The bound magnetic polarons (BMP) theory can be used to prove our room-temperature ferromagnetic properties. The film with the maximum concentration of Mn³⁺ presents strongest ferromagnetic signal at annealing temperature 950 °C. Higher annealing temperature (such as 1150 °C) is not proper because of the second phase Mn_xGa_y formation.     

Annealing behaviour of high-dose-implanted nitrogen in InP

Concentration profiles of nitrogen in vacuum-annealed p- and n-type single-crystal (1 0 0) InP implanted with 1 × 10¹⁶ 30 keV¹⁵N⁺ ions cm^–2 have been studied by Secondary Ion Mass Spectrometry (SIMS) and Nuclear Resonance Broadening (NRB) techniques. Damage induced by the nitrogen implantation was studied by Rutherford Backscattering Spectrometry (RBS) and channeling. Annealing the samples led to loss and redistribution of nitrogen in the temperature range from 575 to 675 °C. At temperatures from 575 to 600 °C, rapid migration of nitrogen towards the sample surface was observed. The n-type InP material had a very dominant tendency for surface nitrogen build-up, whereas the p-type material had a markedly smaller surface peak in the nitrogen distribution. The surface peak in n-type material is due to sulphur acting partly as a diffusion barrier. SIMS analyses showed sulphur build-up on the surface in the course of annealing. At temperatures from 600 to 675 °C, the nitrogen profiles of n- and p-type InP were similar. A small loss of nitrogen was observed at 625–675 °C. Two different recovery stages were observed at 575–600°C and at 625–650 °C. The corresponding activation energies for nitrogen loss are 2.9 and 3.0 eV, respectively.     

Influence of surface morphology on the field emission properties of planar SiC/Si heterostructures formed by ion beam synthesis

The electron field emission properties of planar SiC/Si heterostructures with various surface morphology formed by high dose C⁺ implantation into Si using a metal vapor vacuum arc ion source were investigated. An implant energy of 35 keV was used with doses of 8×10¹⁷, 1×10¹⁸ and 1.2×10¹⁸ ions/cm⁻² with subsequent annealing in Ar at 1200 °C for various times. X-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy showed that a thin stoichiometric SiC surface layer is formed and the surface work function is about 4.5 eV. Atomic force microscopy indicated that the size and density of the densely distributed small protrusions formed on the surface vary with preparation conditions. Results showed that there is an optimum annealing time for the corresponding implant dose at which a remarkably low turn-on field of about 1 V/μm is observed. The density and size of the small protrusions on the surface are believed to be the main factors affecting the field emission properties.     

High-dose carbon implantations into silicon: fundamental studies for new technological tricks

Depending on the implantation temperature, the implantation of carbon ions into silicon at high doses results in the formation of either amorphous SiC_x or crystalline 3C-SiC precipitates. Various aspects of the precipitation behaviour observed, such as the impeded nucleation, the limited growth and the resulting sensitivity to ballistic destruction are attributed to the large interfacial energy between crystalline silicon and 3C-SiC. Periodically arranged amorphous SiC_x nanoclusters, which are formed at lower temperatures, are shown to promote amorphisation by their surrounding stress field and to represent sinks for silicon self-interstitials, which can be activated by annealing at 900 °C. By control of the depth distribution of equally sized, oriented 3C-SiC precipitates formed at higher implantation temperatures, it is possible to establish suitable starting conditions for the formation of buried homogeneous, single-crystalline 3C-SiC layers during a post-implantation anneal. The properties of these ion-beam-synthesised SiC layers are described and attempts to combine them with insulating and metallic layers are reviewed. A survey is given of the emerging applications of ion-beam-synthesised buried SiC layers and microstructures in electronic, optical and micromechanical devices and as large-area SiC pseudosubstrates. Received: 11 November 2002 / Accepted: 12 November 2002 / Published online: 4 April 2003 RID="*" ID="*"Corresponding author. Fax: +49-821/598-3425, E-mail: lindner@physik.uni-augsburg.de     

Recrystallization behavior of high-fluence N-implanted GaAs studied by Raman spectroscopy

Raman spectroscopy was used to study the evolution of host lattice recrystallization in high-fluence N⁺-implanted GaAs. A high-fluence of N⁺ ions (>10¹⁵ cm⁻²) was introduced into semi-insulating GaAs by the combinatorial implantation method. Subsequent thermal annealing at 800 °C was carried out to re-grow the implantation-induced amorphous layers. The dependence of Raman parameters on N contents was systematically observed for each recrystallized cell. The volume of the newly formed crystallites with original orientation decreases with increasing fluences, whereas that of crystallites of other orientations increases after high-fluence implantation and annealing. The correlation length L, representing the size of crystalline regions with preserved translational symmetry, was determined by fitting the LO phonon signal with spatial correlation model. For 10¹⁶ cm⁻² implantation, the recrystallized layer consists of nano-meter-sized crystallites (∼30 nm). The dimension of the recrystallized crystallites decreases with increasing N⁺ fluences, in good agreement with the model.     

Luminescence properties of Ge implanted SiO2:Ge and GeO2:Ge films

We have investigated cathodeluminescence (CL) of Ge implanted SiO₂:Ge and GeO₂:Ge films. The GeO₂ films were grown by oxidation of Ge substrate at 550 °C for 3 h in O₂ gas flow. The GeO₂ films on Ge substrate and SiO₂ films on Si substrate were implanted with Ge-negative ions. The implanted Ge atom concentrations in the films were ranging from 0.1 to 6.0 at%. To produce Ge nanoparticles the SiO₂:Ge films were thermally annealed at various temperatures of 600-900 °C for 1 h in N₂ gas flow. An XPS analysis has shown that the implanted Ge atoms were partly oxidized. CL was observed at wavelengths around 400 nm from the GeO₂ films before and after Ge⁻-implantation as well as from SiO₂:Ge films. After Ge⁻-implantation of about 0.5 at% the CL intensity has increased by about four times. However, the CL intensity from the GeO₂:Ge films was several orders of magnitude smaller than the intensity from the 800 °C-annealed SiO₂:Ge films with 0.5 at% of Ge atomic concentration. These results suggested that the luminescence was generated due to oxidation of Ge nanoparticles in the SiO₂:Ge films.     

Effect of isochronal annealing on photoluminescence properties of Mn-implanted GaN

Mn ions were implanted into metal organic chemical vapour deposition (MOCVD)-grown GaN with dose ranging from 10¹⁴ to 5×10¹⁶ cm⁻². Isochronal annealing at 800 and 850 °C has been carried out after implantation of the samples. Photoluminescence measurements were carried out on the implanted samples before and after annealing. A peak found at 3.34 eV in the spectra of implanted samples after annealing at 850 °C is attributed to the stacking faults. Blue and green luminescence bands have been observed suppressed and an oxygen-related peak appeared at 3.44 eV in the PL spectra. The suppression of blue and green luminescence bands has been assigned to dissociation of V_GaO_N complex. Near-band-edge (NBE) peak exhibited a blue shift after 800 °C anneal and then red shift to restore its original energy position when annealed at 850 °C.     

Synthesis of crystalline SiC nanofiber through the pyrolysis of polycarbomethylsilane coated platelet carbon nanofiber

SiC nanofiber with high crystallinity was synthesized through the pyrolysis of polycarbomethylsilane (PS) coated platelet carbon nanofiber (PCNF) over 700 °C and burning PCNF under the oxidative atmosphere. The as-prepared β-SiC nanofiber exhibited a diameter less than 100 nm and a medium surface area of 50 m²/g. The crystallinity of silicon carbide (SiC) nanofiber increases with increasing heat-treatment temperature, showing the formation of high crystalline SiC nanofiber at 1400 °C. PCNF can be used as a unique template to govern the shape, crystallinity and morphology of SiC.     

Preparation and characterization of pulsed laser deposition (PLD) SiC films

Si K-edge XAFS was used to characterize a stoichiometric SiC film prepared by pulsed KrF laser deposition. The film was deposited on a p-type Si(1 0 0) wafer at a substrate temperature of 250 °C in high vacuum with a laser fluence of ∼5 J/cm². The results reveal that the film contains mainly a SiC phase with an amorphous structure in which the Si atoms are bonded to C atoms in its first shell similar to that of crystalline SiC powder but with significant disorder.     

Damage formation in Ge during Ar and He implantation at 15 K

Ar⁺ and He⁺ ions were implanted into Ge samples with (1 0 0), (1 1 0), (1 1 1) and (1 1 2) orientations at 15 K with fluences ranging from 1×10¹¹ to 1×10¹⁴ cm⁻² for the Ar⁺ ions and fluences ranging from 1×10¹² to 6×10¹⁵ cm⁻² for the He⁺ ions. The Rutherford backscattering (RBS) technique in the channelling orientation was used to study the damage built-up in situ. Implantation and RBS measurements were performed without changing the target temperature. The samples were mounted on a four axis goniometer cooled by a close cycle He cryostat. The implantations were performed with the surface being tilt 7° off the ion beam direction to prevent channelling effects. After each 300 keV Ar⁺ and 40 keV He⁺ implantation, RBS analysis was performed with 1.4 MeV He⁺ ions.For both the implantation ions, there is about no difference between the values found for the damage efficiency per ion for the four different orientations. This together with the high value (around 5 times higher than that found in Si), gives rise to the assumption of amorphous pocket formation per incident ion, i.e. direct impact amorphization, already at low implantation fluences. At higher fluences, when collision cascades overlap, there is a growth of the already amorphized regions.