Correlation between surface damage and micro-defects in Si covered with insulating layer by implantation of He and H ions

Cz n-type Si (100) wafers covered with a 220 nm SiO₂ layer or a 170 nm Si₃N₄ layer were singly implanted with 160 keV He ions at a dose of 5 × 10¹⁶/cm² or successively implanted with 160 keV He ions at a dose of 5 × 10¹⁶/cm² and 110 keV H ions at a dose of 1 × 10¹⁶/cm². Surface morphologies together with defect microstructures have been studied by means of several techniques, including optical microscopy, atomic force microscopy, and cross-sectional transmission electron microscopy (XTEM). Only surface blistering has been observed for He and H sequentially implanted SiO₂/Si samples after annealing in temperature range up to 1000 °C. However, as for the He and H implanted Si₃N₄/Si samples, surface features including blistering and the localized exfoliation of both the top Si₃N₄ layer and the implanted Si layer have been well demonstrated during subsequent annealing. XTEM observations reveal quite different defect morphologies in two kinds of materials under the same implantation and annealing conditions. The possible mechanisms of surface damage in two kinds of materials have been discussed and presented based on the XTEM results.     

Transfer of thin Si layers by cold and thermal ion cutting

We have used the crack-opening method to study the mechanical exfoliation behavior in hydrogen-implanted and bonded Cz Si. We found that the crystal orientation and boron doping influence the temperature required for mechanical layer transfer. Boron implantation at doses >10¹³ cm^–2 reduces the annealing temperature needed for mechanical exfoliation. The boron-doped epilayers followed similar exfoliation behavior as the boron-implanted samples. No lowering of the exfoliation temperature was observed for compensated and arsenic-doped Si layers. The hydrogen implantation converted the silicon wafer surface from p-type to n-type. The as-transferred Si layer was also found to be n-type after annealing at 200–450 °C. The p-type conductivity was restored upon annealing at around 600 °C. We believe that this conductivity conversion is due to the combined effect of ion-enhanced thermal donors and the presence of H-related shallow donors in the implanted layer. The p-type conductivity is restored at higher temperatures following the dissociation of the thermal donors and the out-diffusion of hydrogen. We also report that a good-quality silicon on glass layer can be obtained by the bonding and ion-cutting processes.     

LBIC measurement optimization to detect laser annealing induced defects in Si

Because of the short penetration depth of ultraviolet (UV) in semiconductor, the realization of UV sensors requires the reduction of the junction thickness. Excimer laser annealing (ELA) is a new annealing technical allowing to achieve a thin layer (<30 nm) heavily boron doped (R_sq < 350 Ω/sq) on n-type silicon substrate together with a good profile abruptness (<3 nm/dec).     

Structured ZnO-based contacts deposited by non-reactive rf magnetron sputtering on ultra-thin SiO2/Si through a stencil mask

In this paper, we study the localized deposition of ZnO micro and nanostructures deposited by non-reactive rf-magnetron sputtering through a stencil mask on ultra-thin (10 nm) SiO₂ layers containing a single plane of silicon nanocrystals (NCs), synthetized by ultra-low energy ion implantation followed by thermal annealing. The localized ZnO-deposited areas are reproducing the exact stencil mask patterns. A resistivity of around 5 × 10^− 3 Ω cm is measured on ZnO layer. The as-deposited ZnO material is 97% transparent above the wavelength at 400 nm. ZnO nanostructures can thus be used as transparent electrodes for Si NCs embedded in the gate-oxide of MOS devices.     

Diffusion of Pb in carbon ion-implanted silicon: Discovery of a new crystalline phase after electron beam annealing

A novel phase has been discovered by dual low-energy ion implantation and high vacuum electron beam annealing. (100) p-type Si was implanted with (a) 20 keV ¹²C⁺ ions to the fluence of 6 × 10¹⁶ cm⁻² and (b) 7 keV Pb⁺ ions to the fluence of 4 × 10¹⁵ cm⁻². The ¹²C ion implantation results in an understoichiometric shallow SiC_x layer that intersects with the surface. The implanted Pb ions decorate a shallow subsurface region. High vacuum electron beam annealing at 1000 °C for 15 s using a temperature gradient of 5 °C s⁻¹ leads to the formation of large SiC nanocrystals on the surface with RBS measurements showing Pb has diffused into the deeper region affected by the ¹²C implantation. In this region, a new crystalline phase has been discovered by XRD measurements.     

Effects of annealing temperature on buried oxide precipitates in He and O co-implanted Si

The effects of the processing conditions on the formation of buried oxide precipitates in He and O co-implanted Si were investigated by the combination of Fourier transform infrared (FTIR) absorption spectroscopy, depth-resolved positron annihilation Doppler spectroscopy, and transmission electron microscopy (TEM). Silicon wafers were implanted with 50 keV He ions at a fluence of 2 × 10¹⁶ cm⁻² and subsequent 150 keV O ions at a fluence of 2 × 10¹⁷ cm⁻². For comparison, reference Si wafers were only implanted with 150 keV O ions. The Si–O–Si stretching frequency increases while the peak width of the Si–O–Si stretching absorption band decreases with an increase in annealing temperature. After the same annealing, the peak width of the Si–O–Si stretching absorption band in the He and O co-implanted sample is significantly larger than that in the reference sample. Two kinds of vacancy-type defects are observed by positrons, i.e., vacancy-type defects and vacancy-oxygen complexes. The characteristic S values of vacancy-type defects and vacancy-type complexes in the He and O co-implanted sample are smaller than those of the reference sample. In addition, the thickness of the buried oxide layer in the He and O co-implanted sample is smaller than that in the reference sample. After annealing at 1473 K, the O content is larger in the He and O co-implanted sample compared to that in the reference sample.     

Significance of the interface regarding magnetic properties of manganese nanosilicide in silicon

Magnetic properties of manganese (Mn) nanosilicide embedded in thin silicon-on-insulator (SOI) layers are investigated. Mn nanosilicide formed by Mn⁺ ion implantation into a thin SOI layer followed by a thermal annealing at 600-900 °C shows soft ferromagnetism or superparamagnetism at 5 K. A monotonic decrease of the saturation magnetization is observed with increasing temperature for post implantation annealing and consequently with increasing mean particle size of nanosilicide. In addition, the magnetization is found to be enhanced when the Si surrounding the Mn nanosilicide is selectively removed. These results indicate that the magnetic moment indeed arises from the nanosilicide and is sensitive to the interface conditions.     

Fabrication of nitrogen-doped mesoporous TiO2 layer with higher visible photocatalytic activity by plasma-based ion implantation

Nitrogen-doped porous TiO₂ layers were fabricated on the titanium substrate by plasma-based ion implantation sequentially using He, O₂ or N₂ atmospheres. Post implantation annealing at 570 °C generates a mixture of anatase with a small fraction of rutile in the implanted layer. In order to enlarge the specific surface area, a mesoporous surface structure was produced by exposing the helium bubbles at the sub-surface after removing the surface compact layer using argon ion sputtering. Nitrogen doping extends the photoresponse into the visible light region. Moreover, a lower dose of 4 × 10¹⁵ N/cm² induces a stronger visible light absorption. The photodegradation of Rhodamine B solution with visible light sources indicates that the mesopores at the fresh surfaces and nitrogen doping, both individually and in combination, contribute to an apparent increase in the photodegradation rate.     

Effect of layer thickness on structural quality of Ge epilayers grown directly on Si(001)

A study of Ge epilayer growth directly on a Si(001) substrate is presented, following the two temperature Ge layer method. In an attempt to minimize the overall thickness while maintaining a good quality Ge epilayer, we have investigated the effect of varying the thickness of both the low and high temperature Ge layers, grown at 400 °C and 670 °C, respectively, by reduced pressure chemical vapor deposition. We find that the surface of the low temperature (LT) seed layer has a threading dislocation density (TDD) to the order of 10¹¹ cm^− 2. On increasing the LT layer thickness from 30 nm to 150 nm this TDD decreases by a factor of 2, while its roughness doubles and degree of relaxation increases from 82% to 96%. Growth of the high temperature (HT) layer reduces the TDD level to around 10⁸ cm^− 2, which is also shown to decrease with increasing layer thickness. Both the surface roughness and degree of relaxation reach stable values for which increasing the thickness beyond about 700 nm has no effect. Finally, annealing the HT layer is shown to reduce the TDD, without affecting the degree of relaxation. However, unless a thick structure is used the surface roughness increases significantly on annealing.     

Interfacial reactions in Nb/NbSi2 and Nb/NbSi2-B systems

For the use of Nb-based alloys at high temperatures, a high oxidation resistant coating such as NbSi₂ coating is required. In the present study, to clarify the physico-chemical compatibility between Nb and NbSi₂, the extent of the interfacial reaction and the reaction products were studied at temperatures ranging from 1573 to 1773 K. Growth of the reaction layer formed in the interfacial reactions was caused by the preferential diffusion of Si toward to the Nb side, leading to the formation of a Nb₅Si₃ layer. The growth followed a parabolic rate law, and the growth rate constant was expressed by k_p (m² s⁻¹) = 7.98 × 10⁻¹⁰ exp(−131.84 kJ mol⁻¹/RT). In addition, behavior of boron in the Nb/NbSi₂ interfacial reaction was clarified.     

Stable p-type conductivity and enhanced photoconductivity from nitrogen-doped annealed ZnO thin film

We report on the growth of p-type ZnO thin films with improved stability on various substrates and study the photoconductive property of the p-type ZnO films. The nitrogen doped ZnO (N:ZnO) thin films were grown on Si, quartz and alumina substrates by radio frequency magnetron sputtering followed by thermal annealing. Structural studies show that the N:ZnO films possess high crystallinity with c-axis orientation. The as-grown films possess higher lattice constants compared to the undoped films. Besides the high crystallinity, the Raman spectra show clear evidence of nitrogen incorporation in the doped ZnO lattice. A strong UV photoluminescence emission at ~ 380 nm is observed from all the N:ZnO thin films. Prior to post-deposition annealing, p-type conductivity was found to be unstable at room temperature. Post-growth annealing of N:ZnO film on Si substrate shows a relatively stable p-type ZnO with room temperature resistivity of 0.2 Ω cm, Hall mobility of 58 cm²/V s and hole concentration of 1.95 × 10¹⁷ cm^− 3. A homo-junction p-n diode fabricated on the annealed p-type ZnO layer showed rectification behavior in the current-voltage characteristics demonstrating the p-type conduction of the doped layer. Doped ZnO films (annealed) show more than two orders of magnitude enhancement in the photoconductivity as compared to that of the undoped film. The transient photoconductivity measurement with UV light illumination on the doped ZnO film shows a slow photoresponse with bi-exponential growth and bi-exponential decay behaviors. Mechanism of improved photoconductivity and slow photoresponse is discussed based on high mobility of carriers and photodesorption of oxygen molecules in the N:ZnO film, respectively.     

Modelling boron diffusion in heavily implanted low-pressure chemical vapor deposited silicon thin films during thermal post-implantation annealing

We have investigated and modelled boron (B) diffusion in heavily implanted silicon (Si) thin films deposited from disilane (Si₂H₆) by low pressure chemical vapor deposition (LPCVD) at low temperatures. A comprehensive one-dimensional two-stream diffusion model adapted to the particular structure of deposited Si films and to the effects of high B concentrations has been developed. This model includes B clustering in grains as well as in grain boundaries. In addition, the effects of Si-films crystallization, during thermal post-implantation annealing, on B diffusion as well as on B clusters formation and dissolution were considered. The effects of clustering, growth of grains, dopant-enhanced grains growth and the driving force for grains growth were coupled with the dopant diffusion coefficients and the process temperature based on thermodynamic concepts. To investigate complex B diffusion in heavily implanted Si films deposited by LPCVD, we have used experimental profiles obtained by secondary ion mass spectroscopy (SIMS) for B implantation with doses of 1 × 10¹⁵ at./cm², 4 × 10¹⁵ at./cm² and 5 × 10¹⁵ at./cm² at an energy of 15 keV. Thermal post-implantation anneals were carried out at relatively low-temperatures (700 °C and 850 °C) for various short-times of 1 min to 15 min. The good adjustment of the simulated profiles with the experimental SIMS profiles allowed the validation of this model. It was found that the simulation well reproduces the experimental SIMS profiles when the growth of grains and immobile B clusters are considered.     

Preparation and dielectric properties of B-doped SiC powders by combustion synthesis

The SiC(B) solid solution powders were synthesized via combustion reaction of Si/C system in Ar atmosphere, using boron powder as the dopant and polytetrafluoroethylene as the chemical activator, which were investigated by X-ray diffraction (XRD), scanning electronic microscope (SEM) and Raman spectra. Results show that the prepared powders are C-enriched SiC with C antisites and sp² carbon defects in which the sp² carbon is transformed to the sp³ carbon due to boron doping. The electric permittivities of the prepared powders were determined in the frequency range of 8.2-12.4 GHz. The dielectric real part ?′ and dielectric loss tan δ of undoped powder have maximum values (?′ = 5.5-5.3, tan δ = 0.23-0.20), and decrease with increasing boron content. The mechanism of dielectric loss by doping has been discussed.     

Electrical properties of Sm-doped bismuth titanate thin films prepared on Si (100) by metalorganic decomposition

Samarium-doped bismuth titanate [Bi_4−xSm_xTi₃O₁₂ (BSmT)] thin films have been grown on n-type Si (100) substrates using metalorganic decomposition and subsequent annealing at 700 °C for 1 h. X-ray diffraction analysis showed layered perovskite structures with a single phase in the films. The current-voltage characteristics displayed ohmic conductivity in the lower voltage range and space-charge-limited conductivity in the higher voltage range. The capacitance-voltage characteristics of Au/BSmT/Si (100) exhibited hysteresis loops due to the ferroelectricity and did not show large carrier injections. The fixed charge density and the surface state density of BSmT films on Si substrate were calculated to be in the range of 10¹¹ cm⁻² and 10¹² cm⁻² eV⁻¹, respectively.     

Self-forming AlOx layer as Cu diffusion barrier on porous low-k film

The copper diffusion barrier properties of an ultrathin self-forming AlO_x layer on a porous low-k film have been investigated. Cu-3 at.% Al alloy films were directly deposited onto porous low-k films by co-sputtering, followed by annealing at various temperatures. Transmission electron microscopy micrographs showed that a ∼ 5 nm layer self-formed at the interface after annealing. X-ray photoelectron spectroscopy analysis showed that this self-formed layer was Al₂O₃. Sharp declines of the Cu and Si concentrations at the interface indicated a lack of interdiffusion between Cu and the porous low-k film for annealing up to 600 °C for 30 min. The leakage currents from Cu(Al)/porous low-k/Si structures were similar to as-deposited films even after a 700 °C, 5 min anneal while a Cu sample without Al doping failed at lower temperatures. Adding small amounts of Al to bulk Cu is an effective way to self-form copper diffusion layer for advanced copper interconnects.     

New semiconducting silicides assembled from transition-metal-encapsulating Si clusters

We synthesized amorphous films composed of transition-metal-encapsulating Si clusters (MSi_n: M = Zr, Nb, Mo and W) by deposition of hydrogenated MSi_nH_x clusters onto solid substrates followed by annealing at 400-500 °C for dehydrogenation. The MSi_n (n = 7-20) cluster films are amorphous semiconductors with an optical gap > 0.4 eV and have larger electron and hole mobility than that of the hydrogenated amorphous Si (a-Si:H) film. In these films, while Si atoms form amorphous networks similar to those in a-Si:H films, the thermal stability is enhanced and the electronic disorder is reduced by the use of MSi_n clusters as the unit structures. Structure modeling by ab initio calculations for MSi_n films suggests that the encapsulated M atom works as a terminator of dangling bonds of the Si network.     

Interdiffusion and growth of chromium silicide at the interface of Cr/Si(As) system during rapid thermal annealing

In this work, the solid-state reaction between a thin film of chromium and silicon has been studied using Rutherford backscattering spectroscopy, X-ray diffraction and the sheet resistance measurements. The thickness of 100 nm chromium layer has been deposited by electronic bombardment on Si (100) substrates, part of them had previously been implanted with arsenic ions of 10¹⁵ at/cm² doses and an energy of 100 keV. The samples were heat treated under rapid thermal annealing at 500 °C for time intervals ranging from 15 to 60 s. The rapid thermal annealing leads to a reaction at the interface Cr/Si inducing the formation and the growth of the unique silicide CrSi₂, but no other phase can be detected. For samples implanted with arsenic, the saturation value of the sheet resistance is approximately 1.5 times higher than for the non-implanted case.     

Formation and structural characterization of nanocrystalline Si/SiC multilayers grown by hot filament assisted chemical vapor deposition using CH3SiH3 gas jets

We report on the formation and the structural characterization of nanocrystalline Si/SiC (nc-Si/SiC) multilayers on Si(100) by hot filament assisted chemical vapor deposition using CH₃SiH₃ gas pulse jets. Si rich amorphous SiC (a-Si_1 − xC_x, x ~ 0.33) was initially grown at the substrate temperature (T_s) of 600 °C with heating a hot filament at ~ 2000 °C. The following crystalline SiC layers were grown at T_s = 850 °C without utilizing a hot filament. When the a-Si_1 − xC_x layer was ultrathin (< 2 nm) on Si(100), this a-Si_1 − xC_x layer was transformed to a single epitaxial SiC layer during the subsequent SiC growth process. The Si{111} faceted pits were formed at the SiC/Si(100) interface due to Si diffusion processes from the substrate. When the thickness of the initial a-Si_1 − xC_x layer was increased to ~ 5 nm, a double layer structure was formed in which this amorphous layer was changed to nc-Si and nc-SiC was grown on the top resulting in the considerable reduction of the {111} faceted pits. It was found that nc-SiC was formed by consuming the Si atoms uniformly diffused from the a-Si_1 − xC_x layer below and that Si nanocrystals were generated in the a-Si_1 − xC_x layers due to the annealing effect during further multilayer growths.     

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.