Defects in carbon and oxygen implanted p-type silicon

Both oxygen and carbon ion implantation are frequently used to form either insulating buried SiO₂ or SiC layer for various purposes. This creates a renewal of the interest in defects produced during such implantation processes. In the present paper we report on deep level transient spectroscopy studies of defect states occurring in boron-doped p-type silicon after high dose C⁺ and CO⁺ ion implantation and subsequent thermal annealing. It is shown that the predominant defect created during the implantation is in both cases related to silicon selfinterstitial clusters, which upon annealing at higher temperatures evolve to extended structural defects.     

Epitaxial 3C-SiC nanocrystal formation at the SiO2/Si interface after carbon implantation and subsequent annealing in CO atmosphere

3C-SiC nanocrystallites were epitaxially formed on a single crystalline Si surface covered by a 150 nm thick SiO₂ capping layer after low dose carbon implantation and subsequent high temperature annealing in CO atmosphere. Carbon implantation is used to introduce nucleation sites by forming silicon–carbon clusters at the SiO₂/Si interface facilitating the growth of 3C-SiC nanocrystallites.     

Structure and strain measurements on SiC formed by carbon ion implantation

Thin buried silicon carbide layers have been formed by high-dose carbon ion implantation into silicon and subsequent annealing. The formation of SiC during implantation and the structure of carbide layers after annealing are investigated by X-ray diffraction measurements using a four-circle goniometer. A detailed stress analysis of the epitaxially aligned 3C---SiC precipitates formed during implantation is presented. The three-dimensional strain and stress tensors are calculated for different doses. With increasing dose, stress relaxation accompanied by a transition from isotropic to anisotropic strain/stress states is observed. The dose dependence of the peak intensities of 3C---SiC present in the as-implanted state is studied. Stress tensors show a further relaxation in the annealed state.     

Formation of Si/SiC multilayers by low-energy ion implantation and thermal annealing

Si/SiC multilayer systems for XUV reflection optics with a periodicity of 10-20 nm were produced by sequential deposition of Si and implantation of 1 keV ions. Only about 3% of the implanted carbon was transferred into the SiC, with a thin, 0.5-1 nm, buried SiC layer being formed. We investigated the effect of thermal annealing on further completion of the carbide layer. For the annealing we used a vacuum furnace, a rapid thermal annealing system in argon atmosphere, and a scanning e-beam, for different temperatures, heating rates, and annealing durations. Annealing to a temperature as low as 600 °C resulted in the formation of a 4.5 nm smooth, amorphous carbide layer in the carbon-implanted region. However, annealing at a higher temperature, 1000 °C, lead to the formation of a rough poly-crystalline carbide layer. The multilayers were characterized by grazing incidence X-ray reflectometry and cross section TEM.     

Nanometer-thick SGOI structures produced by Ge+ ion implantation of SiO2 films and subsequent hydrogen transfer of Si layers

Nanometer-thick silicon-germanium-on-insulator (SGOI) structures have been produced by the implantation of Ge⁺ ions into thermally grown SiO₂ layer and subsequent hydrogen transfer of silicon film on the Ge⁺ ion implanted substrate. The intermediate nanometer-thick Ge layer has been formed as a result of the germanium atom segregation at the Si/SiO₂ bonding interface during annealing at temperatures 800–1100 ^оС. From a thermodynamic analysis of Si/Ge/SiO₂ system, it has been suggested that the growth of the epitaxial Ge layer is provided by the formation of a molten layer at the Si/SiO₂ interface due to the Ge accumulation. The effect of germanium on the hole mobility in modulation-doped heterostructures grown over the 3–20 nm thick SGOI layers was studied. An increase in the Hall hole mobility in SGOI-based structures by a factor of 3–5 was obtained in comparison with that in respective Ge-free SOI structures.     

Controlling the density distribution of SiC nanocrystals for the ion beam synthesis of buried SiC layers in silicon

The depth distribution of SiC nanocrystals formed during high-dose implantation of carbon ions into silicon at conditions suitable for the ion beam synthesis of buried SiC layers in silicon is studied in this paper. For implantation temperatures of 400–600°C and dose rates of 10¹² − 10¹³ C⁺/cm²s, SiC precipitates in crystalline silicon are observed to be of approximately equal size, independent of the depth position beneath the surface. Ballistic destruction of small precipitates and difficulties in precipitate growth are thought to be responsible for the observed narrow size distribution. The destruction of precipitates may lead to the simultaneous release of a superthreshold concentration of carbon atoms resulting in a carbon-induced amorphization of the silicon host lattice. The local reduction of the number density of SiC nanocrystals involved with this amorphization can be used to tailor discontinuous depth distributions of oriented SiC precipitates providing ideal starting conditions for the synthesis of well-defined single-crystalline SiC layers in silicon.     

Extended defects in Si wafers implanted with ions of rare-earth elements

Structural defects arising in Cz–Si wafers after implantation with high-energy ions of rare-earth elements (Er, Ho, Dy) and annealing in a chlorine-containing ambience were studied by transmission electron microscopy and chemical etching/Nomarski microscopy. Regularities of extended defect formation in dependence on implant and annealing conditions as well as evolution of structural defect patterns during thermal annealing have been established.     

Ion beam induced amorphization and recrystallization of Si/SiC/Si layer systems

Epitaxial, buried silicon carbide (SiC) layers have been fabricated in (100) and (111) silicon by ion beam synthesis (IBS). In order to study the ion beam induced epitaxial crystallization (IBIEC) of buried SiC layers, the resulting Si/SiC/Si layer systems were amorphized using 2 MeV Si²⁺ ion irradiation at 300 K. An unexpected high critical dose for the amorphization of the buried layers is observed. Buried, amorphous SiC layers were irradiated with 800 keV Si⁺ ions at 320 and 600°C, respectively, in order to achieve ion beam induced epitaxial crystallisation. It is demonstrated that IBIEC works well on buried layers and results in epitaxial recrystallization at considerably lower target temperatures than necessary for thermal annealing. The IBIEC process starts from both SiC/Si interfaces and may be accompanied by heterogenous nucleation of poly-SiC as well as interfacial layer-by-layer amorphization, depending on irradiation conditions. The structure of the recrystallized regions in dependence of dose, dose rate, temperature and crystal orientation is presented by means of TEM investigations.     

Gettering layer for oxygen accumulation in the initial stage of SIMOX processing

A cavity layer or nano-bubble layer introduced by He implantation before the oxygen implantation collects the implanted oxygen and increases the oxygen concentration. The average size and density of the oxygen precipitates formed in the initial stage of the separation-by-implanted-oxygen (SIMOX) process is conform with the size and density of the cavities pre-formed by He implantation and annealing. The gettering ability of the cavity layer for oxygen is directly related to the area of the internal surface of the cavities. A nano-bubble layer accumulates oxygen in a very narrow range occurring between the damage maximum, D_P, and the mean projected ion range, R_P. Such a nano-bubble layer is most efficient in oxygen gettering due to their larger area of the internal surface and the small size of the oxide precipitates initially formed at the bubbles.     

The formation and evolution of vacancy-type defects in Ar-implanted silicon studied by slow-positron annihilation spectroscopy

The Doppler broadening spectrum of a silicon wafer was measured using a variable-energy positron beam to investigate the effects of vacancy-type defects induced by 180 keV Ar ion implantation. The S-parameter in the damaged layer decreases with annealing temperature up to 673 K, and then increases with annealing temperature from 673 to 1373 K. At low annealing temperatures ranging from room temperature to 673 K, argon-decorated vacancies are formed by argon atoms combining with open-volume defects at inactive positron sites. With further increase of annealing temperature, argon-decorated vacancies dissociate and subsequently migrate and coalesce, leading to an increase of S-parameter. Furthermore, the buried vacancy-layer becomes narrow with increasing annealing temperature. At 1373 K, the buried vacancy-layer moved towards the sample surface.     

The formation of compound layers in silicon by ion beam synthesis

The technique of ion beam synthesis (IBS) using high doses of energetic ions has been successfully implemented to produce a variety of compounds, the physical properties of which are dependent on the implanted species and range from insulators, e.g. SiO₂, through semiconductors, e.g. SiC, to conductors, e.g. CoSi₂. In this paper we study the evolution of these compounds and compare and contrast their methods of formation. To demonstrate the versatility of the technique we look at three examples of IBS layers: (1) To date most of the interest in IBS has concentrated on the production of buried oxide layers for silicon-on-insulator (SOI) device applications. Recently it has been shown that by using a series of sequential implants and high-temperature anneals the defect density in the silicon overlayer can be dramatically reduced. To study how this process occurs, we followed the redistribution of the implanted species during implantation and annealing using both ¹⁶O⁺ and ¹⁸O⁺. (2) Buried CoSi₂ layers can be fabricated in (100) single-crystal silicon by implanting high doses of energetic cobalt ions at elevated temperatures. For the higher doses (≥ 4 × 10¹⁷ O⁺/cm² at 350 keV), a continuous coherent layer of CoSi₂ grows epitaxially during implantation. For lower doses, precipitates of both A- and B-type CoSi₂ are observed. After annealing at 1000° C for 30 min, single-crystal aligned layers are produced for the higher doses, while for lower doses discrete octahedral A-type precipitates are formed. (3) The microstructures of synthesized SiC layers are more complex than analogous synthesized oxide or silicide layers. Unlike buried oxide layers, the carbon concentration at the peak of the implanted distribution does not saturate at a value equivalent to that in the stoichiometric compound, but continues to rise, reflecting the lower diffusivity of the C in the synthesized compound layer. To achieve chemical segregation of the implanted carbon, very-high-temperature (≥ 1300°C), long-time (typically 20 h) anneals are required. At the interface with the silicon substrate the synthesized layer grows with a degree of epitaxy. This is also found to occur during implantation if the temperature is ≥ 650° C.     

Surface exfoliation and defect structures in Si induced by 160 keV He and 110 keV H ion implantation

Cz n-type Si(100) wafers were implanted at room temperature with 160 keV He ions at a fluence of 5 × 10¹⁶/cm² and 110 keV H ions at a fluence of 1 × 10¹⁶/cm², singly or in combination. Surface phenomena and defect microstructures have been studied by various techniques, including scanning electron microscopy (SEM), atomic force microscopy (AFM) and cross-sectional transmission electron microscopy (XTEM). Surface exfoliation and flaking phenomena were only observed on silicon by successive implantation of He and H ions after subsequent annealing at temperatures above 400 °C. The surface phenomena show strong dependence on the thermal budget. At annealing temperatures ranging from 500 to 700 °C, craters with size of about 10 μm were produced throughout the silicon surface. As increasing temperature to 800 °C, most of the implanted layer was sheared, leaving structures like islands on the surface. AFM observations have demonstrated that the implanted layer is mainly transfered at the depth around 960 nm, which is quite consistent with the range of the ions. XTEM observations have revealed that the additional low fluence H ion implantation could significantly influence thermal growth of He-cavities, which gives rise to a monolayer of cavities surrounded by a large amount of dislocations and strain. The surface exfoliation effects have been tentatively interpreted in combination of AFM and XTEM results.     

Post-annealing effect on the microstructure and photoluminescence properties of the ion beam synthesized FeSi2 precipitates in Si

FeSi₂ precipitates with various structural properties embedded within silicon matrix were formed by iron ion implantation using a metal vapor vacuum arc ion source followed by thermal annealing at various conditions. The microstructure and phase properties of the implanted samples were studied by transmission electron microscopy. The orientation relationships and thus the interfacial coherence between the FeSi₂ precipitates and the Si matrix were observed to change with the annealing conditions. A good correlation is identified in-between the structural properties and the photoluminescence properties of these samples.     

Temperature effect study of silicon-on-insulator structures prepared by high dose implantation of nitrogen

The temperature effect on the microstructure of the N⁺-ion implantation-induced Si₃N₄ buried layer was investigated. The underlying silicon nitride layers were formed in a Si (1 1 1) wafer after implantation of 50 keV nitrogen ions (fluence: 1 × 10¹⁷, 2 × 10¹⁷ and 5 × 10¹⁷ ions/cm²). It was observed that a continuous amorphous layer of about 200 nm thickness was formed in all implanted samples due to the irradiation damage. After 30 min annealing at 900 °C, poly-crystalline Si₃N₄ products were found by TEM examination in the specimen implanted with 5 × 10¹⁷ ions/cm² dose. In the case of annealing at 1200 °C a continuous single-crystalline α-Si₃N₄ buried layer was formed indicating that the amorphous layer in the implanted samples could be transformed into three successive layers, which are amorphous SiO₂, single-crystal α-Si₃N₄ and retained defects from surface to inner substrate, respectively.     

Endotaxial growth of InSb nanocrystals at the bonding interface of the In+ and Sb+ ion implanted SOI structure

Growth of InSb nanocrystals at the Si/SiO₂ bonding interface of silicon-on-insulator (SOI) structures has been studied as a function of the annealing temperature. SOI structures with the ion implanted regions above and below the bonding interface were produced as a result of the hydrogen transfer of the Sb⁺ ion implanted silicon layer from first silicon substrate to the In⁺ ion implanted SiO₂ layer thermally-grown on the second silicon substrate. Rutherford backscattering spectrometry and high-resolution transmission electron microscopy (XTEM) were used to study the properties of the prepared structures. Up-hill diffusion of In and Sb atoms from the implantation regions toward the bonding interface as well as subsequent interface-mediated growth of InSb nanocrystals were observed as the annealing temperature achieved 1100 °C. The strain minimizing orientations of the Si and InSb lattice heteropairs were obtained from XTEM analysis of the grown nanocrystals.     

Raman scattering and SEM studies of graphite and silicon carbide surfaces bombarded with energetic protons,deuterons and helium ions

Experimental investigations on the chemical and physical effects of 10–15 keV H₁⁺, D₁⁺ and He⁺ ion bombardments to fluences up to 10¹⁹ ions/cm² on graphite and SiC have been conducted using the techniques of Raman scattering and scanning electron microscopy (SEM). Raman scattering data for ion bombarded graphite reveal the formation of an amorphous surface layer as indicated by the appearance of a broad band in the spectrum centered at 1525 cm which replaces the bands due to microcrystalline carbon at 1585 cm^?1 and 1360 cm^?1. The microcrystalline structure could be partially restored upon vacuum annealing at 1040°C for several hours. A weak, broad band centered at 2150 cm also appears after bombardment which is indicative of the formation of ?C = C? bonds. Surfaces of “KT” SiC were also amorphized on ion bombardment as indicated by changes in the Raman spectra. Chemical trapping of the incident h₁⁺ and D₁⁺ ions to form bulk C-H, C-D and Si-H species was observed. Preferential sputtering of Si leaving a carbon rich surface region also occurred. Blister formation was observed in the SEM studies.     

Formation of thin silicon nitride layers on Si by low energy N2+ ion bombardment

The formation of nitride layers in silicon due to low-energy implantation of nitrogen in a wide range of ion bombardment parameters (energy E and angle of incidence θ) and for different temperatures of subsequent annealing (T) has been studied using Auger Electron Spectroscopy (AES), Secondary Ion Mass Spectrometry (SIMS) and Fourier Transform InfraRed Spectroscopy (FTIRS). Bombardment at angles θ < 40° produces an amorphous layer of stoichiometric Si₃N₄ the thickness of which depends on implantation energy and incidence angle. Annealing of the samples at 1000°C produces layers with rather sharp interfaces.     

Positron annihilation on the surfaces of SiO2 films thermally grown on single crystal of Cz-Si

Two-detector coincidence system and mono-energetic slow positron beam has been applied to measure the Doppler broadening spectra for single crystals of SiO₂, SiO₂ films with different thickness thermally grown on single crystal of Cz-Si, and single crystal of Si without oxide film. Oxygen is recognized as a peak at about 11.85 × 10⁻³m₀c on the ratio curves. The S parameters decrease with the increase of positron implantation energy for the single crystal of SiO₂ and Si without oxide film. However, for the thermally grown SiO₂-Si sample, the S parameters in near surface of the sample increase with positron implantation energy. It is due to the formation of silicon oxide at the surface, which lead to lower S value. S and W parameters vary with positron implantation depth indicate that the SiO₂-Si system consist of a surface layer, a SiO₂ layer, a SiO₂-Si interface layer and a semi-infinite Si substrate.     

Spatial distribution of defects in ion-implanted and annealed Si: The RP/2 effect

Gettering of metal impurities in ion-implanted Si occurs midway between the surface and the projected ion range, R_P, after annealing at temperatures in the range of 700–1000°C and vanishes at higher temperatures. This phenomenon, called the R_P/2 effect, seems to be a common feature of ion-implanted and annealed Si. The gettering ability of the damage at R_P/2 is commensurate with or may exceed that of the damage at R_P. The defects around R_P/2 acting as gettering sites have not yet been identified by other analysis techniques. They are formed after ion implantation in the process of defect evolution during annealing and, probably, consist of small complexes of intrinsic defects (vacancies or/and self-interstitials).     

FTIR and RBS study of ion-beam synthesized buried silicon oxide layers

Single crystal silicon samples were implanted at 140 keV by oxygen (¹⁶O⁺) ion beam to fluence levels of 1.0 × 10¹⁷, 2.5 × 10¹⁷ and 5.0 × 10¹⁷ cm⁻² to synthesize buried silicon oxide insulating layers by SIMOX (separation by implanted oxygen) process at room temperature and at high temperature (325 °C). The structure and composition of the ion-beam synthesized buried silicon oxide layers were investigated by Fourier transform infrared (FTIR) and Rutherford backscattering spectroscopy (RBS) techniques. The FTIR spectra of implanted samples reveal absorption in the wavenumber range 1250-750 cm⁻¹ corresponding to the stretching vibration of Si-O bonds indicating the formation of silicon oxide. The integrated absorption band intensity is found to increase with increase in the ion fluence. The absorption peak was rather board for 325 °C implanted sample. The FTIR studies show that the structures of ion-beam synthesized buried oxide layers are strongly dependent on total ion fluence. The RBS measurements show that the thickness of the buried oxide layer increases with increase in the oxygen fluence. However, the thickness of the top silicon layer was found to decrease with increase in the ion fluence. The total oxygen fluence estimated from the RBS data is found to be in good agreement with the implanted oxygen fluence. The high temperature implantation leads to increase in the concentration of the oxide formation compared to room temperature implantation.