Effects of annealing on the damage morphologies in BF 2 + ion implanted (1 0 0) silicon

The effects of annealing on the damage morphologies and impurity redistributions in BF ₂ ⁺ ion implanted (1 0 0) silicon were studied using secondary ion mass spectrometry (SIMS), transmission electron microscopy (TEM) and Rutherford backscattering (RBS) ion beam channelling technique. An amorphized silicon layer and a heavily-damaged crystal layer containing a high density of point-defect clusters, are formed on the silicon wafer by the ion implantation. SIMS depth profiles of both boron and fluorine are almost Gaussian distribution. Both furnace annealing and rapid thermal annealing cause recrystallization of the amorphized layer and formation of dislocation loop bands out of the point defects. SIMS depth profiles for both impurities show anomalous double peaks at the same depths. These facts suggest that the primary peak is due to the peak of the Gaussian distribution and the secondary peak due to the gettering effects of residual dislocation loop band.     

Characterization of cobalt annealed on silicon-germanium epilayers

Cobalt-coated single-crystal Si-Ge layers grown epitaxially by ultrahigh vacuum chemical vapor deposition on silicon substrates were annealed by rapid thermal annealing in the temperature range from 450 °C to 800 °C for periods ranging from 1 to 3 min. The measured sheet resistivities of the films exhibit strong dependence on the annealing conditions. The Co-SiGe film annealed at 700 °C for 3 min had the lowest sheet resistivity (3Ω/p). Structural studies using cross-sectional transmission electron microscopy showed that the cobalt films reacted with the SiGe layer and the thickness of the resulting film increases with increasing annealing temperature or time. Electron diffraction and X-ray microanalysis using energy-dispersive spectrometry showed that CoSi₂ was formed during initial annealing. The detection of germanium in the reacted layer and the deviation of the reacted layer's lattice constant from that of CoSi₂ indicated that germanium diffused into the CoSi₂ and formed ternary compounds (Co_xSi_yGe_z) during further annealing.     

Improvement of Ta-based thin film barriers on copper by ion implantation of nitrogen and oxygen

Magnetron sputtered polycrystalline Ta and Ta(Si) barriers for copper metallization schemes were modified by nitrogen as well as oxygen high dose ion implantation to improve their thermo-mechanical stability. Ion bombardment changed the initial polycrystalline microstructure to amorphous-like. In contrast to pure Ta, Ta(Si) layers were already amorphous or nanocrystalline after deposition. In this case, the annealing temperature at which formation of a well crystallized structure occurs increased by approximately 100 K as a result of the implantation. In order to demonstrate the improvement in the barrier properties of the implanted Ta films, the intermixing of Ta and Cu at the interface of corresponding layer structures was measured as a function of the annealing temperature by depth profiling using Auger electron spectroscopy (AES). The thermal stability of Ta and Ta(Si) barriers increased from 600 °C/1 h for the non-implanted layers up to 750 °C/1 h after implantation of nitrogen or oxygen.     

Silicide formation and phase separation from Cu/Nb and Nb/Cu bilayers on silicon

Electron beam evaporation was used to produce Nb/Cu and Cu/Nb bilayers on silicon. The phase sequence and morphology were investigated as a function of annealing temperature in the temperature range between 200 °C and 800 °C, using Auger electron spectroscopy, Rutherford backscattering spectrometry, X-ray diffraction, and transmission electron microscopy. Independently of the sequence of deposition, the phases Nb₃Si and Nb₅Si₃ are the two first niobium phases to be formed as a very thin layer at the Nb---Si interface. However, there is evidence that the reaction between niobium and silicon depends strongly on the presence of copper at the Nb---Si interface. The unusual coexistence of Nb₅Si₃, NbSi₂ and niobium phases was also observed. The formation of the ternary phase Nb₅Cu₄Si₄ was detected after annealing Cu/Nb at 700 °C and Nb/Cu at 800 °C. In the latter case the NbSi₂ and Cu₃Si+Cu₄Si phases were formed through a layered growth process.     

Structural and optical characterization of β-FeSi2 layers on Si formed by ion beam synthesis

Structural and optical properties have been investigated for surface β-FeSi₂ layers on Si(100) and Si(111) formed by ion beam synthesis using ⁵⁶Fe ion implantations with three different energies (140–50 keV) and subsequent two-step annealing at 600 °C and up to 915 °C. Rutherford backscattering spectrometry analyses have revealed Fe redistribution in the samples after the annealing procedure, which resulting in a Fe-deficient composition in the formed layers. X-ray diffraction experiments confirmed the existence of /gb-FeSi₂ by annealing up to 915 °C, whereas the phase transformation from the β to phase has been induced at 930 °C. In photoluminescence measurements at 2 K, both β-FeSi₂/Si(100) and β-FeSi₂/Si(111) samples, after annealing at 900–915 °C for 2 h, have shown two dominant emissions peaked around 0.836 eV and 0.80 eV, which nearly coincided with previously reported PL emissions from the sample prepared by electron beam deposition. Another β-FeSi₂/Si(100) sample has shown sharp emissions peaked at 0.873 eV and 0.807 eV. Optical absorption measurements at room temperature have revealed the allowed direct bandgap of 0.868–0.885 eV as well as an absorption coefficient of the order of 10⁴ cm⁻¹ near the absorption edge for all samples.     

Amorphous Ni---N---W film as a diffusion barrier between aluminum and silicon

The influence of nitrogen on the diffusion barrier properties of amorphous Ni---W films was studied. Nitrogen was introduced into the amorphous Ni---W film by co-sputtering nickel and tungsten in a premixed gas mixture of 90% Ar and 10% N₂, resulting in the formation of amorphous Ni₃₀N₂₁W₄₉ film. X-ray analysis indicates a detectable crystallization of the amorphous film after 30 min annealing in vacuum at 600°C, accompanied by the formation of W₂N, but backscattering spectrometry (BS) reveals a reaction with silicon only at about 725°C. The Schottky barrier height of this amorphous film on n-Si is stable for 30 min annealing up to at least 550°C. With an aluminum overlayer, BS indicates that an amorphous Ni₃₀N₂₁W₄₉ film effectively prevents the metallurgical interaction between aluminum and silicon for 30 min up to 600°C. The Schottky barrier height of that contact configuration is also stable up to at least 550°C, suggesting that amorphous Ni---N---W films have attractive features as diffusion barriers.     

Evolution of microstructure during annealing of low-dose SIMOX wafers implanted at 65 keV

The microstructural changes that occur during annealing of ultra-thin oxygen-implanted silicon-on-insulator have been studied using transmission electron microscopy (TEM), Rutherford backscattering spectrometry (RBS), and Auger electron spectroscopy (AES). Silicon substrates were implanted at 65 keV with a dose of 4.5×10¹⁷ O⁺ cm^–2, followed by annealing at various temperatures. TEM results show that the defects observed in the as-implanted material (stacking faults and {1 1 3} defects) were reduced after annealing at 900 °C for 2 h and were eliminated after annealing at 1100 °C for 2 h. A continuous buried oxide (BOX) layer was formed after annealing at 1300 °C for 6 h. Numerous silicon islands were present in the BOX layer. The silicon islands can be traced to a precursor structure that developed at the implantation step. RBS results indicate that the crystallinity of the top Si layer is significantly restored after annealing at 1100 °C for 2 h and is completely restored after annealing at 1300 °C for 6 h. It was also found through AES analysis that the redistribution of oxygen during annealing is initiated at 1100 °C.     

Gettering of iron in silicon by boron implantation

In this work we studied, both experimentally and theoretically the iron gettering by boron implantation. Sample material was p-type bulk silicon with resistivity of 21 Ωcm. Samples were iron contaminated and boron was implanted into the wafers using two different implantation doses of 4 × 10¹⁵ and 8 × 10¹⁵ cm^?2. After that various gettering annealings were performed. The results indicate that gettering cannot be explained by electronic interactions between interstitial iron and boron ions alone i.e. segregation gettering to heavily doped implantation region. It was found out that better agreement between experimental and simulation results is achieved if heterogeneous precipitation of iron to ion implantation induced damage is included in the simulations. Finally, the effects of high boron doping and gettering site morphology on iron precipitation are discussed.     

Redistribution of indium implanted in silicon due to thermal treatment and swift heavy ion irradiation

Silicon layers of 150 nm thickness supersaturated with indium up to ≈5 at% were prepared by multiple energy ion implantation. A redistribution of the implanted impurities caused by post-implantation annealing and following irradiation with swift Bi ions has been observed by means of Rutherford backscattering spectrometry in channelling configuration (RBS/C). It is demonstrated by TEM that the thermal decomposition of the supersaturated Si〈In〉 solution is accompanied by polycrystalline recrystallisation of amorphous silicon, precipitation of the second phase (In) both within the implanted layer and on the surface, as well as by impurity redistribution. The main features of the structure transformation under the influence of the Bi ion irradiation are discussed.     

HI-ERDA, Micro-Raman and HRXRD studies of buried silicon oxynitride layers synthesized by dual ion implantation

Silicon oxynitride (Si_xO_yN_z) buried insulating layers were synthesized by dual implantation of nitrogen (¹⁴N⁺) and oxygen (¹⁶O⁺) ions sequentially into single crystal silicon in the ratio 1:1 at 150 keV to ion-fluences ranging from 1 × 10¹⁷ to 5 × 10¹⁷ cm⁻². Heavy ion elastic recoil analysis (HI-ERDA) studies of as implanted samples show Gaussian like distributions of nitrogen and oxygen. After annealing at 800 °C, both the nitrogen and oxygen distributions appear as flat plateau like regions near projected range showing the formation of a continuous buried oxynitride layer. Micro-Raman study of as implanted samples shows a broad peak at 480 cm⁻¹ for all fluences. It signifies a complete amorphization of silicon due to high fluence implantation. The annealing at 800 °C results in the reduction of the intensity of the broad peak observed at 480 cm⁻¹ and also gives rise to an additional peak at 517 cm⁻¹. It shows partial recrystallization of damaged silicon due to annealing. The X-ray rocking curves studies from high-resolution X-ray diffraction (HRXRD) of the samples implanted with different fluences have also further confirmed partial recrystallization of damaged silicon on annealing.     

Radical-Beam Gettering Epitaxy of ZnO Films under UV Irradiation

Single-crystal ZnO films are grown by radical-beam gettering epitaxy: annealing of single-crystal zinc chalcogenide (ZnS, ZnSe, or ZnTe) substrates in a flow of oxygen atoms (radicals) and gettering of zinc atoms from the substrate bulk. The effect of UV irradiation during film growth on the structure and quality of the resulting ZnO films and the effect of ion implantation into the substrate on the growth of ZnO/ZnSe heterostructures are studied. The conditions are established for the growth of p-type ZnO films.__________Translated from Neorganicheskie Materialy, Vol. 41, No. 6, 2005, pp. 696–701.Original Russian Text Copyright © 2005 by Georgobiani, Kotlyarevsky, Rogozin, Marakhovskii.     

Large-grain polycrystalline silicon thin films obtained by low-temperature stepwise annealing of hydrogenated amorphous silicon

Large grained polycrystalline silicon thin films have been prepared by low-temperature solid phase crystallisation of sputter-deposited hydrogenated amorphous silicon (a-Si:H), with relatively short processing times, and a considerably low thermal budget. Various a-Si:H samples, deposited under different conditions and with varying hydrogen concentrations and hydrogen bonding configurations, were simultaneously annealed. Only a particular set of deposition conditions led to crystallisation. The a-Si:H thin film which was successfully crystallised was prepared in an argon-hydrogen mixture, in which the last few minutes of film deposition occurred in a hydrogen-rich atmosphere. For that film, the hydrogen concentration profile resulted in a much higher hydrogen content on the sample surface than in the bulk, and H-Si bonds were predominantly of the weak type. Crystallisation was accomplished by low-temperature stepwise annealing from 200°C to 600°C at 100°C steps, with samples being cooled down to room-temperature between each annealing step. This resulted in large grained (> 10 μm range) polycrystalline silicon after the 600°C annealing step for a 1.1 μm thick sample. Fourier transform infrared (FTIR) spectroscopy, elastic recoil detection analysis (ERDA) and scanning electron microscopy (SEM) techniques were used to analyse samples before and after crystallisation.     

Microstructure modification of amorphous titanium oxide thin films during annealing treatment

Thin films of titanium oxide have been deposited on (100) silicon wafers and on quartz substrates by reactive r.f. magnetron sputtering from a 99.6% pure Titanium target. Amorphous and overoxidised coatings (TiO_2.2) have been obtained from this technique. The influence of the post-deposition annealing between 300 °C and 1100 °C on the structural and optical properties and on the surface morphology has been investigated. The results of X-ray diffraction showed that films annealed from 300 to 500 °C have an anatase crystalline structure whereas those annealed at 1100 °C have a rutile crystalline structure. Optical analyses showed that UV-Vis transmission spectra are strongly modified by the annealing temperature and refractive index of TiO_x layers also changes. Atomic force microscopy measurements corroborate optical and structural analyses and showed that the surface of the coatings can have various appearances and morphologies for the annealing temperatures investigated.     

Susceptor-assisted microwave annealing for activation of arsenic dopants in silicon

Microwave annealing of arsenic-doped silicon was employed to achieve nearly complete dopant activation and repair of damage caused by ion implantation. Analysis of Rutherford backscattering spectra suggested that volumetric heating from microwaves can repair ion-implantation damage. Secondary ion mass spectroscopy depth profiling revealed that even with high damage due to implanted arsenic, microwave annealing achieves repair of lattice damage, and electrical activation of dopants without allowing any significant dopant diffusion into the silicon substrate. Surface temperatures greater than 700 °C were achieved within ~ 100 s with assisted microwave heating, marking this as a quick annealing technique when compared to un-assisted annealing. This temperature was sufficient for solid phase epitaxial growth in Si. The temperature profile recorded by a thermocouple-calibarated IR pyrometer was explained based upon the type of losses the sample undergoes while heating. The mechanism for susceptor-assisted microwave heating was dominated by dipole polarization losses in the initial stages of anneal and by Ohmic conduction losses at higher temperatures. Cross-section transmission electron microscopy, along with ion channeling spectra indicated that the silicon lattice regained nearly all of its crystallinity during the microwave anneal. Hall measurement and sheet resistance characterization were used to assess the extent of dopant activation.     

Low-temperature, direct synthesis of β-SiC by metal vapor vacuum arc ion source implantation

Crystalline β-SiC surface layers with strong (111) preferred orientation were synthesized by direct ion implantation into Si(111) substrates at a low temperature of 400°C using a metal vapor vacuum arc ion source. Both X-ray diffraction and Fourier transform infrared spectroscopy reveal an augment in the amount of β-SiC with increasing implantation doses at 400°C. Scanning electron microscopy shows the formation of an almost continuous SiC surface layer after implantation at 400°C with a dose of 7×10¹⁷/cm². The full width at half maximum of the X-ray rocking curve of β-SiC(111) was measured to be 1.4° for the sample implanted at a dose of 2×10¹⁷/cm² at 700°C, revealing a good alignment of β-SiC with the Si matrix.     

Thin SiO2 films formed by oxygen ion implantation in silicon: Electron microscope investigations of the Si-SiO2 interface structures and their c-v characteristics

Electron microscope reflection diffraction studies were carried out for silicon wafers implanted with different doses of oxygen ions. Structural changes were monitored both with increasing ion dose and with annealing temperature. The structural properties of the silicon substrate underlying the SiO₂ layers that were formed with the highest implant doses were also investigated and changes caused by annealing are reported. An anneal at 800 °C was found to re-establish good structural properties of the silicon underneath the SiO₂. C-V studies of MOS structures based on such SiO₂ layers indicated good interface properties for samples annealed at 800 °C.     

Optical and nuclear characterization of Xe-induced nanoporosity in SiO2

We performed RBS, infrared (IR) and C-V measurements in order to follow the evolution of Xe, bubbles/cavities and other defects (with a focus on NBOHC: non-bridging oxygen hole center) and dielectric constant (k), in high dose Xe implantation in SiO₂. As-implanted sample provides the lowest value of k which increases with post thermal annealing. In the meantime, the concentration of negatively charged defects decreases with annealing while Xe out-diffuses after annealing at 1100 °C leaving Xe free cavities in the sample. By combining these results one can determine the contribution of nanoporosity in dielectric constant evolution.     

Visible light emission from silicon dioxide with silicon nanocrystals

An electroluminescent MOS structure was developed using silicon wafers covered by thermal silicon dioxide containing silicon nanocrystals. Efficiency of the structure was sufficient for observation to be possible with the naked eye in daylight conditions under DC polarization. Silicon nanocrystals were produced using silicon ion implantation followed by subsequent annealing at 1100 °C in a nitrogen atmosphere. Three separate bands of emitted light at wavelengths of ∼400-500 nm (blue), ∼500-600 nm (green), and ∼650-850 nm (red) were observed and found to be related to specific regions of the implanted silicon concentration profile. For a single energy implant, each of the emitted light bands originated from a separate depth region of the silicon dioxide layer containing silicon nanocrystals. The spectrum of the emitted light was found to depend on the excess silicon concentration profile. For practical applications, the color of the emitted light can be controlled by adjustment of the implantation parameters and MOS structuring process.     

Annealing effects on microstructure and mechanical properties of chromium oxide coatings

Reactive radio frequency magnetron sputter-deposited chromium oxide coatings were annealed at different temperatures and times. The influence of annealing temperature on the microstructure, surface morphology and mechanical properties was examined by X-ray diffraction, nanoindentation, pin-on-disc wear and scratch tests, respectively. X-ray results show that the chromium oxide sputtered at room temperature in low oxygen flux is primarily amorphous. Annealing below 400 °C did not cause much change, while annealing at higher temperature of 500 °C caused a significant change in microstructure and mechanical properties. Hardness increased from 12.3 GPa to 26 GPa, and the wearability improved with higher annealing temperature due to the formation of crystalline Cr₂O₃ phase, which occurs at 470 °C. Annealing time had little effect on mechanical properties and microstructure, although coating surface roughness increased with a longer annealing time. Coating adhesion was improved by annealing, due to residual stress relief and possible interfacial interdiffusion.     

Characteristics of aluminum-implanted 6H-SiC samples after different thermal treatments

Multiple energy aluminum (Al) implantations were performed at room temperature in n-type epitaxial 6H-SiC layers, aiming at amorphizing the material from the surface up to a depth inferior to 0.5 μm. Annealings were then carried out in an induction furnace. The goal of this paper is to optimize the furnace geometrical configuration, in order to reduce the surface degradation and improve the crystal reordering. This optimization was established for one-side amorphized wafers, which need restricting annealing parameters, and is therefore supposed to be valid for less crystal damaging implantations. Two types of geometrical parameters were essentially studied: the internal configuration, which tends to increase the silicon partial pressure inside the reactor, and the position of the sample, which has a direct influence on the recrystallization and on the dopant electrical activation. The annealings are compared for the same thermal parameters: the plateau temperature (1700 °C), the annealing duration (30 min), and the heating rate (60 °C s⁻¹). The surface roughness was evaluated by using atomic force microscopy. Two final configurations were retained, leading to satisfactory results with respect to the as-implanted material: (i) Rutherford backscattering spectrometry in channeling geometry revealed a very good recrystallization in both cases, giving a signal level similar to the virgin crystal one; (ii) secondary ion mass spectrometry showed two distinct results depending on the sample position: one position led to some material etching, especially the SiC part which was amorphized by the implantation, and the second position gave rise to the deposition of a crudely monocrystalline SiC layer on the surface of the sample implanted side. This coating was found to prevent from any dopant loss by exodiffusion or material etching. Electrical measurements (four-point probe at 300 K) proved an Al substitutional ratio of 97 and 78% depending on the configuration, giving room temperature sheet resistances of about 2×10⁴ and 4×10⁴ Ω sq.⁻¹, respectively, for 4×10¹⁹ cm⁻³ Al implanted samples.