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.     

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.     

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.     

Defects formation in the dual B+ and N+ ions implanted silicon

Silicon wafers were implanted with 40 keV B⁺ ions (to doses of 1.2×10¹⁴ or 1.2×10¹⁵ cm^–2) and 50 or 100 keV N⁺ ions (to doses from 1.2×10¹⁴ to 1.2×10¹⁵ cm^–2). After implantations, the samples were furnace annealed at temperatures from 100 to 450 °C. The depth profiles of the radiation damages before and after annealing were obtained from random and channeled RBS spectra using standard procedures. Two damaged regions with different annealing behaviour were found for the silicon implanted with boron ions. Present investigations show that surface disordered layer conserves at the annealing temperatures up to 450 °C. The influence of preliminary boron implantation on the concentration of radiation defects created in subsequent nitrogen implantation was studied. It was shown that the annealing behaviour of the dual implanted silicon layers depends on the nitrogen implantation dose.The authors would like to thank the members of the INP accelerator staff for the help during the experiments. The work of two authors (V.H. and J.K.) was partially supported by the Internal Grant Agency of Academy of Science of Czech Republic under grant No. 14805.     

Slow positron beam study of nitrogen implanted CZ-Si subjected to rapid thermal processing

In this experiment, nitrogen ions were implanted into CZ-silicon wafer at 100 keV at room temperature with the fluence of 5 × 10¹⁵ N₂⁺/cm², followed by rapid thermal processing (RTP) at different temperatures. The single detector Doppler broadening and coincidence Doppler broadening measurements on slow positron beam were carried out to characterize the defects in the as-implanted silicon and RTP-treated samples. It is found that both nitrogen-vacancy complexes (N-Vsi) and oxygen-vacancy complexes (O-Vsi) produced by nitrogen implantation diffuse back to the sample surface upon annealing. But the N-Vsi and the O-Vsi complete with each other and give a summed effect on positron annihilation characteristics. It is shown that the N-Vsi win out the O-Vsi in as-implanted sample and by RTP at 650 °C, 750 °C, which make the S-parameter increase; O-Vsi plays a dominant role after annealing above 850 °C, which makes the S parameter decrease.     

Crystalline quality of 3C-SiC formed by high-fluence C-implanted Si

Carbon ions at 40 keV were implanted into (1 0 0) high-purity p-type silicon wafers at 400 °C to a fluence of 6.5 × 10¹⁷ ions/cm². Subsequent thermal annealing of the implanted samples was performed in a diffusion furnace at atmospheric pressure with inert nitrogen ambient at 1100 °C. Time-of-flight energy elastic recoil detection analysis (ToF-E ERDA) was used to investigate depth distributions of the implanted ions. Infrared transmittance (IR) and Raman scattering measurements were used to characterize the formation of SiC in the implanted Si substrate. X-ray diffraction analysis (XRD) was used to characterize the crystalline quality in the surface layer of the sample. The formation of 3C-SiC and its crystalline structure obtained from the above mentioned techniques was finally confirmed by transmission electron microscopy (TEM). The results show that 3C-SiC is directly formed during implantation, and that the subsequent high-temperature annealing enhances the quality of the poly-crystalline SiC.     

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.     

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.     

Investigations of He implantation and subsequent annealing effects in InP

The influence of 70 keV He⁺ ion implantation and subsequent annealing of Cz-indium phosphide (InP) samples has been investigated using a slow positron beam-based Doppler broadening spectrometer. Three samples with ion fluences of 1 × 10¹⁶, 5 × 10¹⁶ and 1 × 10¹⁷ cm⁻² were studied in the as-implanted condition as well as after annealing at 640 °C for times between 5 and 40 min. It was found that the line-shape parameter of the positron-electron annihilation peak in the implanted layer increases after 5 min annealing, then after longer annealing times it starts to decline gradually until it reaches a value close to the value of the as-grown sample. This implies that vacancy-like defects can be created in InP by He implantation followed by short-thermal annealing at T > 600 °C. Comparison of the results with a study where cavities were observed in He-implanted InP has been carried out.     

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.     

Analysis of the effect of annealing on the photoluminescence spectra of Cu ion implanted ZnS nanoparticles

In the present study, we report the photoluminescence (PL) study of nanoparticles of ZnS implanted with Cu⁺ ions at the doses of 5×10¹⁴, 1×10¹⁵ and 5×10¹⁵ ions/cm² and annealed at 200 and 300 °C. The photoluminescence spectra of the samples implanted at lower doses of 5×10¹⁴ and 1×10¹⁵ ions/cm² and annealed at 200 and 300 °C showed peaks at around 406, 418 and 485 nm. The PL emission peak at 485 nm was attributed to the transition of electrons from conduction band of ZnS to the impurity level formed by the implanted Cu⁺ ions. In the PL spectrum of the sample implanted at the highest dose of 5×10¹⁵ ions/cm², in addition to the emission peaks observed in the PL spectra of the samples implanted at lower doses, a peak at around 525 nm, the intensity of which decreased with increase in the annealing temperature, was observed. The emission peak at 525 nm was attributed to the transitions between sulfur and zinc vacancy levels. The full width at half maximum (FWHM) of the emission peak at 406 nm was observed to decrease with increase in annealing temperature, indicating lattice reconstruction. The observation of copper ion impurity related peak at 485 nm in the PL spectra of samples of the present study indicated that the doping of copper ions into the ZnS lattice is achievable by implanting Cu⁺ ions followed by annealing.     

Characterization of BCN films synthesized by radiofrequency plasma enhanced chemical vapor deposition

Boron carbonitride (BCN) films have been synthesized on Si(1 0 0) substrate by radio frequency plasma enhanced chemical vapor deposition using tris-(dimethylamino)borane (TDMAB) as a precursor. The deposition was performed at the different RF powers of 400-800 W, at the working pressure of 2×10⁻¹ Torr. The formation of the sp²-bonded BCN phase was confirmed by Fourier transform infrared spectroscopy. X-ray photoelectron spectroscopy measurements showed that B atoms were bonded to C and N atoms to form the BCN atomic hybrid configurations with the chemical compositions of B₅₂C₁₂N₃₆ (sample 1; prepared at the RF power of 400 W), B₅₂C₁₀N₃₈ (sample 2; at 500 W) and B₄₆C₁₈N₃₆ (sample 3; at 800 W), respectively. Near-edge X-ray absorption fine structure (NEXAFS) measurements indicated that B atoms were bonded not only to N atoms but also to C atoms to form various configurations of sp²-BCN atomic hybrids. The polarization dependence of NEXAFS suggested that the predominant hybrid configuration of sp²-BCN films oriented in the direction perpendicular to the Si substrate.     

Boron electrical activation in dual B+ + N+ + and B+ + Ar+ ion-implanted silicon

Silicon wafers were implanted with 40 keV B⁺ ions and then with 50 keV N⁺ or 100 keV Ar+ ions to doses from 1.2 x 1014 to 1.2 x 1015 cm^–2. The implanted samples were studied using the Hall effect and standard van der Pauw methods. The dependences of the sheet resistivity and the sheet concentration of charge carriers on the annealing temperature in the range from 700 to 1300 K were obtained. Models describing the influence of additional implantation of nitrogen and argon ions on the process of boron electrical activation during annealing are proposed.     

Photoluminescence from C ion-implanted and electrochemical etched Si layers

The microstructural and optical analysis of Si layers emitting blue luminescence at about 431 nm is reported. These structures have been synthesized by C⁺ ion implantation and high-temperature annealing in hydrogen atmosphere and electrochemical etching sequentially. With the increasing etching time, the intensity of the blue peak increases at first, decreases then and is substituted by a new red peak at 716 nm at last, which shows characteristics of the emission of porous silicon. CO compounds are induced during C⁺ implantation and nanometer silicon with embedded structure is formed during annealing, which contributes to the blue emission. The possible mechanism of photoluminescence is presented.     

Structural and photoluminescence properties of Si nanoclusters obtained by ion implantation into Si3N4 films

In the present paper we report structural and photoluminescence (PL) results from samples obtained by Si implantation into stoichiometric silicon nitride (Si₃N₄) films. The Si excess was introduced in the matrix by 170 keV Si implantation performed at different temperatures with a fluence of Φ=1×10¹⁷ Si/cm². The annealing temperature was varied between 350 and 900 °C in order to form the Si precipitates. PL measurements, with a 488 nm Ar laser as an excitation source, show two superimposed broad PL bands centered around 760 and 900 nm. The maximum PL yield is achieved for the samples annealed at 475 °C. Transmission electron microscopy (TEM) measurements show the formation of amorphous nanoclusters and their evolution with the annealing temperature.     

Structural and optical properties of Au-implanted ZnO films

The structural and luminescence related optical behaviours of Au ion implanted ZnO films grown by magnetic sputtering and their post implantation annealing behaviours in the temperature range of 100-700 °C have been investigated. Optical absorption and transmittance spectra of the films indicate that band edge of Au-implanted ZnO has shifted to high energy range and optical band gap has increased, because the sharp difference of thermal expansion induces the lattice mismatch between ZnO and SiO₂. PL spectra reveal that UV and visible luminescence bands of ZnO films can be improved after thermal annealing due to recovery of defects and Au ions incorporation. Importantly, green luminescence band of 530 nm has been only observed in the Au-implanted and subsequently annealed ZnO films and it enhances with the increasing annealing temperature, which can be related to Au atoms or clusters in ZnO films. Furthermore, X-ray photoelectron spectroscopy measurements reveal that the Au⁰ is dominant state in Au implanted and annealed ZnO films. Possible mechanisms, such as optical transitions of Au atoms or clusters and deep level luminescence of ZnO, have been proposed for green emission.     

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.     

Estimation of diffusion coefficient by photoemission electron microscopy in ion-implanted nanostructures

We have fabricated parallel stripes of nanostructures in an n-type Si substrate by implanting 30 keV Ga⁺ ions from a focused ion beam (FIB) source. Two sets of implantation were carried out. In one case, during implantation the substrate was held at room temperature and in the other case at 400 °C. Photoemission electron microscopy (PEEM) was carried out on these samples. The implanted parallel stripes, each with a nominal dimension of 4000 nm × 100 nm, appear as bright regions in the PEEM image. Line scans of the intensities from the PEEM image were recorded along and across these stripes. The intensity profile at the edges of a line scan is broader for the implantation carried out at 400 °C compared to room temperature. From the analysis of this intensity profile, the lateral diffusion coefficient of Ga in silicon was estimated assuming that the PEEM intensity is proportional to Ga concentration. The diffusion coefficient at 400 °C has been estimated to be ∼1.3 × 10⁻¹⁵ m²/s. Across the stripes an asymmetric diffusion profile has been observed, which has been related to the sequence of implantation of these stripes and the associated defect distribution due to lateral straggling of the implanted ions.     

Influence of nitrogen ion implantation fluences on surface structure and tribological properties of SiC ceramics in water-lubrication

Nitrogen ions were implanted into SiC ceramics by using ion implantation technology (N⁺-SiC). The surface structure and chemical bonds of N⁺-SiC ceramics were determined by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), and their nanohardness was measured by nanoindenter. The friction and wear properties of the N⁺-SiC/SiC tribo-pairs were investigated and compared with those of SiC/SiC tribo-pairs in water using ball-on-disk tribo-meters. The wear tracks on the N⁺-SiC ceramics were observed by non-contact surface profilometer and scanning electron microscope (SEM) and their wear volumes were determined by non-contact surface profilometer. The results show that the N⁺-SiC ceramics were mainly composed of SiC and SiCN phase and SiN, CC, CN and CN bonds were formed in the implantation layer. The highest hardness of 22.3 GPa was obtained as the N⁺-SiC ceramics implanted at 50 keV and 1 × 10¹⁷ ions/cm². With an increase in nitrogen ion fluence, the running-in period of N⁺-SiC/SiC tribo-pairs decreased, and the mean stable friction coefficient decreased from 0.049 to 0.024. The N⁺-SiC ceramics implanted at 50 keV and 5 × 10¹⁷ ions/cm² exhibited the excellent tribological properties in water. In comparison of SiC/SiC ceramic tribo-pairs, the lower friction coefficient and lower wear rate for the N⁺-SiC/SiC tribo-pairs were acquired.