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.     

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.     

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.     

Formation of germanium nanoparticles in silica glass studied by optical absorption and X-ray absorption fine structure analysis

We examined the relation between the 3.1 eV emission band and local structure for Ge⁺ implanted silica glass by means of photoluminescence, optical and X-ray absorption spectroscopies. In the 2 × 10¹⁵ cm^?2 implanted sample, a new emission band around 2.7 eV was observed, the origin of which was assigned to the B_2α oxygen deficient center and/or small Si clusters in silica. When the Ge⁺ fluence exceeded 2 × 10¹⁶ cm^?2, a sharp and intense 3.1 eV emission band replaced the 2.7 eV band. We found that the intense 3.1 eV PL occurred by the prolonged X-ray irradiation onto the 2 × 10¹⁵ cm^?2 implanted sample. UV–vis absorption and XAFS spectroscopies suggested that the aggregation of atomically dispersed tetravalent (Ge(IV)) atoms into Ge(0) clusters of ～1 nm exhibit strongly correlation with the generation of the 3.1 eV PL. Such nano- and/or subnano-size Ge(0) clusters formed by the X-ray radiation were oxidized and decomposed again to the isolated Ge(IV) atoms, while those produced by the higher Ge⁺ fluence were stable against the exposure to air.     

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.     

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).     

Defect engineering in the MOSLED structure by ion implantation

When amorphous SiO₂ films are bombarded with energetic ions, various types of defects are created as a consequence of ion-solid interaction (peroxy radicals POR, oxygen deficient centres (ODC), non-bridging oxygen hole centres (NBOHC), E′ centres, etc.). The intensity of the electroluminescence (EL) from oxygen deficiency centres at 2.7 eV, non-bridging oxygen hole centres at 1.9 eV and defect centres with emission at 2.07 eV can be easily modified by the ion implantation of the different elements (H, N, O) into the completely processed MOSLED structure. Nitrogen implanted into the SiO₂:Gd layer reduces the concentration of the ODC and NBOHC while the doping of the oxygen increases the EL intensity observed from POR defect and NBOHC. Moreover, after oxygen or hydrogen implantation into the SiO₂:Ge structure fourfold or fifth fold increase of the germanium related EL intensity was observed.     

Swift-heavy-ion-induced shaping of spherical Ge nanoparticles into disks and rods

The work reports on experimental features and theoretical studies of swift-heavy-ion-induced shaping of Ge nanospheres into disks. A stack of alternating Ge and SiO₂ layers was sputtered on an oxidized Si wafer. The Ge layer thicknesses varied from 2.5 to 7.5 nm. Thermal treatment above the melting temperature of Ge transformed each Ge layer into a layer of Ge nanospheres. With growing Ge layer thickness the mean diameter increases from 8 to 37 nm. Irradiation with low fluences (～10¹⁴ cm^?2) of 38 MeV I⁷⁺ shaped medium-sized Ge nanospheres into disks, whereas smaller ones became rod-like and larger ones remained unchanged. At higher fluences, the larger Ge nanospheres shrink due to Ge loss and shape into disks too. A new model is presented and atomistic Monte-Carlo simulations are shown which describe the shaping evolution and the size thresholds for shaping quantitatively. The volume change of Ge upon melting has been identified as driving force.     

Light particle irradiation effects in Si nanocrystals

Si nanocrystals, formed by Si ion implantation into SiO₂ layers and subsequent annealing at 1150°C, were irradiated at room temperature either with He⁺ions at energies of 30 or 130 keV, or with 400 keV electrons. Transmission electron microscopy (TEM) and photoluminescence (PL) studies were performed. TEM experiments revealed that the Si nanocrystals were ultimately amorphized (for example at ion doses ∼10¹⁶ He cm⁻²) and could not be recrystallized by annealing up to 775°C. This contrasts with previous results on bulk Si, in which electron- and very light ion-irradiation never led to amorphization. Visible photoluminescence, usually ascribed to quantum-size effects in the Si nanocrystals, was found to decrease and vanish after He⁺ ion doses as low as 3 × 10¹²–3 × 10¹³ He cm⁻² (which produce about 1 displacement per nanocrystal). This PL decrease is due to defect-induced non-radiative recombination centers, possibly situated at the Si nanocrystal/SiO₂ interface, and the pre-irradiation PL is restored by a 600°C anneal.     

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.     

High energy Si ions bombardment effects on the properties of nano-layers of SiO2/SiO2 + Ag

We grew 50 periodic SiO₂/SiO₂ + Ag multi-layers by electron beam deposition technique. The co-deposited SiO₂ + Ag layers are 7.26 nm, SiO₂ buffer layers are 4 nm, and total thickness of film was determined as 563 nm. We measured the thickness of the layers using in situ thickness monitoring during deposition, and optical interferometry afterwards. The concentration and distribution of Ag in SiO₂ were determined using Rutherford backscattering spectrometry (RBS). In order to calculate the dimensionless figure of merit, ZT, the electrical conductivity, thermal conductivity and the Seebeck coefficient of the layered structure were measured at room temperature before and after bombardment with 5 MeV Si ions. The energy of the Si ions was chosen such that the ions are stopped deep inside the silicon substrate and only electronic energy due to ionization is deposited in the layered structure. Optical absorption (OA) spectra were taken in the range 200–900 nm to monitor the Ag nanocluster formation in the thin layers.     

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.     

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.     

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.     

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.     

Surface oxidation of Si assisted by irradiation with large gas cluster ion beam in an oxygen atmosphere

Surface oxidation of Si assisted by Ar cluster impact with a current density of a few μA/cm² under O₂ atmosphere was investigated. Thin-film formation by cluster ion beam presents a number of advantages such as atomic-scale surface smoothing, high density and precise stoichiometry. We used an Ar cluster ion beam with 20 keV and a mean size of 1000 atoms per cluster and measured the emission yields of Si⁺ and SiO⁺ after Ar cluster ion irradiation in O₂ atmosphere using a quadrupole mass spectrometer to investigate the dependence of Si surface oxidation on oxygen partial pressure. It was found that the Si surface was oxidized by Ar cluster ion irradiation in O₂ atmosphere.     

Relaxation of strain during solid phase epitaxial growth of Ge+ ion implanted layers in silicon

Formation of Si_1−xGe_x-alloy layers by solid phase epitaxial growth (SPEG) of Ge⁺ ion implanted silicon has been studied. The ion implantations were performed with 40, 100, 150, 200 and 300 keV ⁷⁴Ge⁺ ions and various ion doses. The SPEG of the ion implanted layers was carried out in a conventional furnace at 850°C for 20 min under a flow of nitrogen gas. The Si_1−xGe_x-alloy layers were characterised by Rutherford backscattering spectrometry and transmission electron microscopy (TEM). For a given ion energy, a Si_1−xGe_x-alloy layer with no observable extended defects can be manufactured if the ion dose is below a critical value and strain-induced defects are formed in the alloy layer when the ion dose is equal to or above this value. The critical Ge⁺ ion dose increases with ion energy, while the critical maximum Ge concentration decreases. For ion energies ⩽150 keV, the defects observed in the alloy layers are mostly stacking faults parallel to the {1 1 1} planes. For higher ion energies, 200 keV and above, the majority of defects in the alloy layer are hairpin dislocations. In the whole ion energy range, the critical ion dose and the depth position of the nucleation site for the stacking faults obtained from the measurements are in good agreement with theoretical predictions. Extended defects are formed in the alloy layer during the SPEG when the regrowth of the crystalline/amorphous interface has reached the depth position in the crystal where the accumulated strain energy density is equal to the critical value of 235 mJ/m².     

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.     

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.     

MeV Si ions bombardment effects on the thermoelectric properties of Co0.1SbxGey thin films

We have grown three different monolayer Co_0.1Sb_xGe_y (x = 2, 4, 11 and y = 15, 7, 15) thin films on silica substrates with varying thickness between 100 and 200 nm using electron beam deposition. The high-energy (in the order of 5 MeV) Si ion bombardments have been performed on samples with varying fluencies of 1 × 10¹², 1 × 10¹³, 1 × 10¹⁴ and 1 × 10¹⁵ ions/cm². The thermopower, electrical and thermal conductivity measurements were carried out before and after the bombardment on samples to calculate the figure of merit, ZT. The Si ions bombardment caused changes on the thermoelectric properties of films. The fluence and temperature dependence of cross plane thermoelectric parameters were also reported. Rutherford backscattering spectrometry (RBS) was used to analyze the elemental composition of the deposited materials and to determine the layer thickness of each film.