Low temperature formation of luminescent Si nanocrystals with combined process of excimer UV-light irradiation and RTA

Si ion implantation was widely used to synthesize specimens of SiO₂ containing supersaturated Si and subsequent high temperature annealing induces the formation of embedded luminescent Si nanocrystals. In this work, the potentialities of excimer UV-light (172 nm, 7.2 eV) irradiation and rapid thermal annealing (RTA) to achieve low temperature (below 1000 °C) formation of luminescent Si nanocrystals in SiO₂ have been investigated. The Si ions were introduced at acceleration energy of 180 keV to fluences of 7.5 × 10¹⁶ and 1.5 × 10¹⁷ ions/cm². The implanted samples were subsequently irradiated with an excimer-UV lamp for 2 h. After the process, the samples were rapidly thermal annealed at 1050 °C for 5 min before furnace annealing (FA) at 900 °C. Photoluminescence spectra were measured at various stages at the process. Effective visible photoluminescence is found to be observed even after FA at 900 °C, only for specimens treated with excimer-UV lamp and RTA, prior to a low temperature FA process. Based on our experimental results, we discuss the mechanism for the initial formation process of the luminescent Si nanocrystals in SiO₂, together with the effects with excimer lamp irradiation and RTA process on the luminescence.     

Photoluminescence induced by Si implantation into Si3N4 matrix

Up to the present, photoluminescence (PL) was obtained from near stoichiometric or amorphous Si nitride films (SiN_x) after annealing at high temperatures. As a consequence, the existence of PL bands has been reported in the 400–900 nm range. In the present contribution, we report the first PL results obtained by Si implantation into a stoichiometric 380 nm Si₃N₄ film. The Si excess is obtained by a 170 keV Si implantation at different temperatures with a fluence of Φ = 10¹⁷ Si/cm². Further, we have annealed the samples in a temperature range between 350 and 900 °C in order to form the Si precipitates. PL measurements were done using an Ar laser as an excitation source, and a broad PL band basically centered at 910 nm was obtained. We show that the best annealing condition is obtained at T_a = 475 °C for the samples implanted at 200 °C, with a PL yield 20% higher than the obtained at room temperature implantation. Finally, we have varied the implantation fluence and, consequently, the Si nanocrystals size. However, no variation was observed nor in the position neither in the intensity of the PL band. We concluded that the PL emission is due to radiative states at the matrix and the Si nanocrystals interface, as previously suggested in the literature.     

Effect of implanted Si concentration on the Si nanocrystal size and emitted PL spectrum

Implantation of Si⁺ in excess into SiO₂ followed by annealing produces Si nanocrystals (Si-nc) embedded in the SiO₂ layer, which can emit a strong photoluminescence (PL) signal. Several samples have been characterized by means of ellipsometry and transmission electron microscopy (TEM). For local Si concentrations in excess of ∼2.4 × 10²² Si⁺/cm³, the Si-nc diameter ranges from ∼2 to ∼22 nm in the whole sample, the Si-nc in the middle region of the implanted layer being bigger than those near the surface or the bottom of the layer. The depth distribution of the Si-nc agrees relatively well with the SRIM simulation as well as with the depth distribution of the n and k components of the complex refractive index. For SiO₂ layers thermally grown on a Si wafer, the PL spectrum is modulated by optical interference of the pump laser and of the light emitted by the Si-nc in this layer. The good agreement between the results of the model calculations and experimental measurements indicates that for low and moderate Si concentration in excess (<8 × 10²¹ cm⁻³) the PL light emitters are localized in a layer situated at the same depth as the Si-nc depth distribution. However, for a Si concentration in excess of ∼2.3 × 10²² cm⁻³, the depth distribution of light emitters is narrow and situated mostly in the first half (relative to the surface) of the Si-nc depth distribution. This observation indicates that the recombination of the electron–hole pair at the interfaces could be responsible for the emitted PL spectrum.     

SHI induced re-crystallization of Ge implanted SiO2 films

Ge nanocrystals embedded in SiO₂ matrix have been synthesized by swift heavy ion irradiation of Ge implanted SiO₂ films. In the present study, 400 keV Ge⁺ ions were implanted into SiO₂ films at dose of 3 × 10¹⁶ ions/cm² at room temperature. The as-implanted samples were irradiated with 150 MeV Ag¹²⁺ ions with various fluences. Similarly 400 keV Ge⁺ ions implanted into Silicon substrate at higher fluence at 573 K have been irradiated with 100 MeV Au⁸⁺ ions at room temperature (RT). These samples were subsequently characterized by XRD and Raman to understand the re-crystallization behavior. The XRD results confirm the presence of Ge crystallites in the irradiated samples. Rutherford backscattering spectrometry (RBS) was used to quantify the concentration of Ge in the SiO₂ matrix. Variation in the nanocrystal size as a function of ion fluence is presented. The basic mechanism of ion beam induced re-crystallization has been discussed.     

Homogeneously size distributed Ge nanoclusters embedded in SiO2 layers produced by ion beam synthesis

500 nm SiO₂ layers were implanted with 450 keV (F=3 × 10¹⁶ at./cm²) and 230 keV (F=1.8 × 10¹⁶ at./cm²) Ge ions at room temperature to obtain an almost constant Ge concentration of about 2.5 at.% in the insulating layer. Subsequently, the specimens were annealed at temperatures between 500°C and 1200°C for 30 min in a dry N₂ ambient atmosphere. Cross-sectional TEM analysis reveal homogeneously distributed Ge nanoclusters arranged in a broad band within the SiO₂ layer. Their mean cluster size varies between 2.0 and 6.5 nm depending on the annealing conditions. Cluster-free regions are always observed close to the surface of the specimens independent of the annealing process, whereas a narrow Ge nanocluster band appears at the SiO₂/Si interface at high annealing temperatures, e.g. ⩾1000°C. The atomic Ge redistribution due to the annealing treatment was investigated with a scanning TEM energy dispersive X-ray system and Rutherford back scattering (RBS).     

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.     

Photoluminescence induced from hot Ge implantation into SiO2

Up to the present, by using the ion implantation technique, photoluminescence (PL) from Ge nanocrystals (Ge NCs) was obtained by room temperature (RT) Ge implantation into a SiO₂ matrix followed by a high temperature anneal. In this way two PL bands were observed, one at 310 nm and the second, with much higher yield at 390 nm. In the present work we have used another experimental approach. We have performed the Si implantation at high temperature (T_i) and then, we have done a higher temperature anneal (T_a) in order to nucleate the Ge NCs. With this aim we have changed T_i between RT and 600 °C. By performing the implantation at T_i = 350 °C we found a PL yield four times higher than the one obtained from the usual RT implantation at the same fluence. Moreover, by changing the implantation fluence between Φ = 0.25 × 10¹⁶ and 2.2 × 10¹⁶ Ge/cm² we observed that Φ = 0.5 × 10¹⁶ Ge/cm² induces a PL yield three times higher as compared to the usual RT implantation fluence. In conclusion, using a hot Ge implantation plus an optimal Ge atomic concentration, we were able to gain more than one order of magnitude in the 390 nm PL yield as compared with previous ion implantation results.     

Impact of Ni co-implantation on Si nanocrystals formation and luminescence

We investigate the Si nanocrystals (Si-nc) growth and photoluminescence (PL) obtained by Si and Ni co-implantation. After 1 h of annealing at 1000 °C, PL emission between 600 and 1000 nm is observed to be five times higher for samples containing 0.04–0.21 at.% Ni than for samples without Ni. For samples annealed at 1100 °C, a small increase in PL intensity is observed followed by a decrease for Ni contents above 0.3 at.%. Our results are well described by a simple model which assumes that Ni atoms act both as a nucleation center for amorphous Si (a-Si) clusters crystallisation and as a non-radiative recombination site when more than one atom is included in a Si-nc. The nucleation effect is supported by the increase in PL intensity, the increase of PL decay time and the decrease of the a-Si Raman peak intensity at 480 cm^?1 for samples annealed at 1000 °C in presence of ～0.1 at.% Ni. Time-resolved PL shows that Ni mainly affects two emission bands. The first band, around 730 nm, is related to an oxygen surface state, suggesting that Ni enhances oxygen bonding with Si-nc. The second band, around 880 nm, is associated to the crystallisation effect induced by Ni at lower annealing temperature.     

Depth-profiling of implanted 28Si by (α,α) and (α,p0) reactions

Silicon nanocrystals enclosed in thin films (Si quantum dots or Si QDs) are regarded to be the cornerstone of future developments in new memory, photovoltaic and optoelectronic products. One way to synthesize these Si QDs is ion implantation in SiO₂ layers followed by thermal annealing post-treatment.Depth-profiling of these implanted Si ions can be performed by reactions induced by α-particles on ²⁸Si. Indeed, for high incident energy, nuclear levels of ³²S and ³¹P can be reached, and cross-sections for (α,α) and (α,p₀) reactions are more intense. This can help to increase the signal for surface silicon, and therefore make distinguishing more easy between implanted Si and Si coming from the SiO₂, even for low fluences.In this work, (α,α) and (α,p₀) reactions are applied to study depth distributions of 70 keV ²⁸Si⁺ ions implanted in 200 nm SiO₂ layers with fluences of 1 × 10¹⁷ and 2 × 10¹⁷ cm^?2. Analysis is performed above E_R = 3864 keV to take advantage of resonances in both (α,α) and (α,p₀) cross-sections. We show how (α,p₀) reactions can complement results provided by resonant backscattering measurements in this complex case.     

Damage accumulation and annealing in 6H–SiC irradiated with Si+

Damage accumulation and annealing in 6H-silicon carbide (α-SiC) single crystals have been studied in situ using 2.0 MeV He⁺ RBS in a 〈0 0 0 1〉-axial channeling geometry (RBS/C). The damage was induced by 550 keV Si⁺ ion implantation (30° off normal) at a temperature of −110°C, and the damage recovery was investigated by subsequent isochronal annealing (20 min) over the temperature range from −110°C to 900°C. At ion fluences below 7.5 × 10¹³ Si⁺/cm² (0.04 dpa in the damage peak), only point defects appear to be created. Furthermore, the defects on the Si sublattice can be completely recovered by thermal annealing at room temperature (RT), and recovery of defects on the C sublattice is suggested. At higher fluences, amorphization occurs; however, partial damage recovery at RT is still observed, even at a fluence of 6.6 × 10¹⁴ Si⁺/cm² (0.35 dpa in the damage peak) where a buried amorphous layer is produced. At an ion fluence of 6.0 × 10¹⁵ Si⁺/cm² (−90°C), an amorphous layer is created from the surface to a depth of 0.6 μm. Because of recovery processes at the buried crystalline–amorphous interface, the apparent thickness of this amorphous layer decreases slightly (<10%) with increasing temperature over the range from −90°C to 600°C.     

Effects of BF2+ implantation on the strain-relaxation of pseudomorphic metastable Ge0.06Si0.94 alloy layers

Metastable pseudomorphic Ge_0.06Si_0.94 alloy layers grown by molecular beam epitaxy (MBE) on Si (1 0 0) substrates were implanted at room temperature by 70 keV BF₂⁺ ions with three different doses of 3 × 10¹³, 1 × 10¹⁴, and 2.5 × 10¹⁴ cm⁻². The implanted samples were subsequently annealed at 800°C and 900°C for 30 min in a vacuum tube furnace. Observed by MeV ⁴He channeling spectrometry, the sample implanted at a dose of 2.5 × 10¹⁴ BF₂⁺ cm⁻² is amorphized from surface to a depth of about 90 nm among all as-implanted samples. Crystalline degradation and strain-relaxation of post-annealed Ge_0.06Si_0.94 samples become pronounced as the dose increases. Only the samples implanted at 3 × 10¹³ cm⁻² do not visibly degrade nor relax during anneal at 800°C . In the leakage current measurements, no serious leakage is found in most of the samples except for one which is annealed at 800°C for 30 min after implantation to a dose of 2.5 × 10¹⁴ cm⁻². It is concluded that such a low dose of 3 × 10¹³ BF₂⁺ cm⁻² can be doped by implantation to conserve intrinsic strain of the pseudomorphic GeSi, while for high dose regime to meet the strain-relaxation, annealing at high temperatures over 900°C is necessary to prevent serious leakages from occuring near relaxed GeSi/Si interfaces.     

Early stage of the crystallization in amorphous Fe–Si layers: Formation and growth of metastable α-FeSi2

Crystallization processes of amorphous Fe–Si layers have been investigated using transmission electron microscopy (TEM). Si(1 1 1) substrates were irradiated with 120 keV Fe ions at ?150 °C to a fluence of 1.0 × 10¹⁷ cm². An Fe-rich amorphous layer embedded in an amorphous Si was formed in the as-irradiated sample. Plan-view TEM observations revealed that a part of the amorphous Fe–Si layer crystallized to the metastable α-FeSi₂ after thermal annealing at 350 °C for 8 h. The lattice parameter of c-axis decreased with thermal annealing. It was considered that the change in the lattice parameter originates from the decrease of the Fe occupancy at (0, 0, 1/2) and its equivalent positions in the unit cell of the metastable α-FeSi₂.     

Er+ implantation in SnO2:SiO2 layers: Structure changes and light emission

Structure changes and light emission behavior in Er⁺ implanted SnO₂:SiO₂ layers are studied, using transmission electron microscopy (TEM), Rutherford backscattering (RBS) and cathodoluminescence (CL). SnO₂:SiO₂ layers of different composition deposited with RF magnetron sputtering on Si wafers were implanted with 200 keV Er⁺ to a fluence of 3 × 10¹⁵ cm^?2 at room temperature. The implanted structures were then annealed at 600–1000 °C for 30 min, resulting in the formation of crystalline SnO₂ nanoclusters. Cross-section TEM revealed a strong reduction of the SnO₂ crystallite size down to several nanometers in the implanted area of the SnO₂:SiO₂ layer as compared to the undoped layer. In addition, a very narrow layer of SnO₂ nanocrystals appears at the SiO₂/Si interface. Several narrow CL emission peaks and wide bands were found which could be related to the decay of SnO₂ free excitons, to oxygen deficiency centers in SiO₂ and to transitions between the energy levels in the Er ions, apparently located at nanoclusters. The mechanisms of nanostructuring as well as the emission process are discussed.     

Annealing of ion implanted 4H–SiC in the temperature range of 100–800 °C analysed by ion beam techniques

Ion implantation induced damage formation and subsequent annealing in 4H–SiC in the temperature range of 100–800 °C has been investigated. Silicon Carbide was implanted at room temperature with 200 keV ⁴⁰Ar ions with two implantation fluences of 4 × 10¹⁴ and 2 × 10¹⁵ ions/cm². The samples were characterized by Rutherford backscattering and nuclear reaction analysis techniques in channeling mode using 2.00 and 4.30 MeV ⁴He ion beams for damage buildup and recovery in the Si and C sublattices, respectively. At low ion fluence, the restoration of the Si sublattice is evident already at 200 °C and a considerable annealing step occurs between 300 and 400 °C. Similar results have been obtained for the C sublattice using the nuclear resonance reaction for carbon, ¹²C(α,α)¹²C at 4.26 MeV. For samples implanted with the higher ion fluence, no significant recovery is observed at these temperatures.     

Photoluminescence studies of neutron-transmutation-doped InP:Fe

Neutron-irradiated InP:Fe semi-insulating crystals have been investigated by photoluminescence (PL) and Hall effect. The evolution of the different PL transitions was studied as a function of the thermal neutron dose, annealing temperature and excitation power. Hall effect measurements confirm the success of the doping technique in semi-insulating InP:Fe. For tin concentration higher than 6 × 10¹⁵ cm⁻³ the InP:Fe samples annealed at 550°C are clearly n-type with a free carrier concentration slightly lower than the calculated tin concentration.     

High-speed processing with Cl2 cluster ion beam

Cluster ion beam processes can produce high rate sputtering with low damage compared with monomer ion beam processes. Cl₂ cluster ion beams with different size distributions were generated with controlling the ionization conditions. Size distributions were measured using the time-of-flight (TOF) method. Si substrates and SiO₂ films were irradiated with the Cl₂ cluster ions at acceleration energies of 10–30 keV and the etching ratio of Si/SiO₂ was investigated. The sputtering yield increased with acceleration energy and was a few thousand times higher than that of Ar monomer ions. The sputtering yield of Cl₂ cluster ions was about 4400 atoms/ion at 30 keV acceleration energy. The etching ratio of Si/SiO₂ was above eight at acceleration energies in the range 10–30 keV. Thus, SiO₂ can be used as a mask for irradiation with Cl₂ cluster ion beam, which is an advantage for semiconductor processing. In order to keep high sputtering yield and high etching ratio, the cluster size needs to be sufficiently large and size control is important.     

Ion beam synthesis of SiC by C implantation into SIMOX(1 1 1)

We report the conversion of a 65 nm Si(1 1 1) overlayer of a SIMOX(1 1 1) into 30–45 nm SiC by 40 keV carbon implantation into it. High temperature implantation (600 °C) through a SiO₂ cap, 1250 °C post-implantation annealing under Ar ambient (with 1% of O₂), and etching are the base for the present synthesis. Sequential C implantations (fluence steps of about 5 × 10¹⁶ cm^?2), followed by 1250 °C annealing, has allowed to estimate the minimum C fluence to reach the stoichiometric composition as ～2.3 ×  10¹⁷ cm^?2. Rutherford Backscattering Spectrometry was employed to measure layer composition evolution. A two-sublayers structure is observed in the synthesized SiC, being the superficial one richer in Si. Transmission electron microscopy has shown that a single-step implantation up to the same minimum fluence results in better structural quality. For a much higher C fluence (4 × 10¹⁷ cm^?2), a whole stoichiometric layer is obtained, with reduction of structural quality.     

Soft X-ray fluorescence measurements of irradiated polymer films

Fluorescent soft X-ray carbon Kα emission spectra (XES) have been used to characterize the bonding of carbon atoms in polyimide (PI) and polycarbosilane (PCS) films. The PI films have been irradiated with 40 keV nitrogen or argon ions, at fluences ranging from 1 × 10¹⁴ to 1 × 10¹⁶ cm⁻². The PCS films have been irradiated with 5 × 10¹⁵ carbon ions cm⁻² of 500 keV and/or annealed at 1000°C. We find that the fine structure of the carbon XES of the PI films changes with implanted ion fluence above 1 × 10¹⁴ cm⁻² which we believe is due to the degradation of the PI into amorphous C:N:O. The width of the forbidden band as determined from the high-energy cut-off of the C Kα X-ray excitation decreases with the ion fluence. The bonding configuration of free carbon precipitates embedded in amorphous SiC which are formed in PCS after irradiation with C ions or combined treatments (irradiation and subsequent annealing) is close to either to that in diamond-like films or in silicidated graphite, respectively.     

Ohmic contacts on n-type layers formed in GaN/AlGaN/GaN by dual-energy Si ion implantation

Electrical properties of Si-implanted n-type GaN/AlGaN/GaN layers and contact resistances of ohmic electrodes (TiAl) formed on these layers have been examined. Experimental results have clearly shown that ohmic electrodes with a low specific-contact resistance of 1.4 × 10^?7 Ω cm² can be fabricated on the n-type layer having a low sheet resistance of 145 Ω/sq, which has been formed by the dual-energy Si ion implantation (80 keV:1.01 × 10¹⁵/cm² + 30 keV:1.6 × 10¹⁴/cm²) and subsequent annealing at 1200 °C for 2 min using a Si₃N₄ layer as an encapsulant.     

Dwell-time dependence of the defect accumulation in focused ion beam synthesis of CoSi2

Cobalt disilicide microstructures were formed by 70 keV Co²⁺ focused ion beam implantation into Si(1 1 1) at substrate temperatures of about 400°C and a subsequent two step annealing (600°C, 60 min and 1000°C, 30 min in N₂). It was found that the CoSi₂ layer quality strongly depends on the pixel dwell time and the implantation temperature. Only for properly chosen parameters continuous CoSi₂ layers could be obtained. Scanning electron microscopy and Rutherford backscattering/channelling investigations were carried out combined with a special preparation technique for structures which are smaller than the analysing beam. The quality of the CoSi₂ layers which is correlated to the damage was investigated as a function of dwell-time (1–250 μs) and target temperature (355–415°C). The results show that the irradiation damage increases with the dwell-time. The Si top layer was amorphized for longer dwell-times although the substrate temperature was always above the critical temperature for amorphization of about 270°C according to the model of Morehead and Crowder. For the high current density of a focused ion beam (1–10 A/cm²) the damage creation rate is higher than the rate of dynamic annealing.