RBS analysis of ions implanted in light substrates exposed to hot plasmas laser-generated at PALS

Ge and Ta ion implantation of silicon and carbon substrates has been obtained at PALS Research Laboratory in Prague by using laser pulses of 400 ps duration, 438 nm wavelength, 10^14?16 W/cm² intensity. Substrates were exposed in vacuum at different distances from the target and at different angles with respect to the normal to the target surface. ‘On line’ measurements of ion energy were obtained with time-of-flight techniques by using an electrostatic deflector as ion energy analyzer. ‘Off line’ measurements of ion energy were obtained by Rutherford backscattering spectrometry (RBS) of 2.25 MeV He²⁺ beam at CEDAD Laboratory of Lecce University. The RBS spectra have given the depth profiles of the ion-implanted species and the implanted doses as a function of the laser intensity, angular position and target distance. A spectra deconvolution method based on the ion stopping power in the substrate matrix was applied in order to evidence the energy of the implanted ions. Measurements indicate that ions with energy ranging between 100 keV and 10 MeV and dose of the order of 10^14?16/cm² are implanted and that the process of ion implantation occurs mainly in substrates placed at little angles with respect to the normal to the target surface. Only a thin film deposition occurs for substrates placed at large angles with respect to the normal direction. Results indicate that the ion energies measured with the ‘on line’ and the ‘off line’ techniques are in good agreement.     

Modification of semiconductor materials using laser-produced ion streams additionally accelerated in the electric fields

The laser-produced ion stream may be attractive for direct ultra-low-energy ion implantation in thin layer of semiconductor for modification of electrical and optical properties of semiconductor devices. Application of electrostatic fields for acceleration and formation of laser-generated ion stream enables to control the ion stream parameters in broad energy and current density ranges. It also permits to remove the useless laser-produced ions from the ion stream designed for implantation.For acceleration of ions produced with the use of a low fluence repetitive laser system (Nd:glass: 2 Hz, pulse duration: 3.5 ns, pulse energy:∼0.5 J, power density: 10¹⁰ W/cm²) in IPPLM the special electrostatic system has been prepared. The laser-produced ions passing through the diaphragm (a ring-shaped slit in the HV box) have been accelerated in the system of electrodes. The accelerating voltage up to 40 kV, the distance of the diaphragm from the target, the diaphragm diameter and the gap width were changed for choosing the desired parameters (namely the energy band of the implanted ions) of the ion stream. The characteristics of laser-produced Ge ion streams were determined with the use of precise ion diagnostic methods, namely: electrostatic ion energy analyser and various ion collectors. The laser-produced and post-accelerated Ge ions have been used for implantation into semiconductor materials for nanocrystal fabrication. The characteristics of implanted samples were measured using AES.     

Temperature measurements in plasmas generated by using lasers at different intensities

The temperature of laser-generated pulsed plasmas is an important property that depends on many parameters, such as the particle species and the time elapsed from the laser interaction with the matter and the surface characteristics.

Laser-generated plasmas with low intensity (<10¹⁰ W/cm²) at INFN-LNS of Catania and with high intensity (>10¹⁴ W/cm²) in PALS laboratory in Prague have been investigated in terms of temperatures relative to ions, electrons, and neutral species. Time-of-flight (ToF) measurements have been performed with an electrostatic ion energy analyzer (IEA) and with different Faraday cups, in order to measure the ion and electron average velocities. The IEA was also used to measure the ion energy, the ion charge state, and the ion energy distribution.

The Maxwell–Boltzmann function permitted to fit the experimental data and to extrapolate the ion temperature of the plasma core.

The velocity of the neutrals was measured with a special mass quadrupole spectrometer. The Nd:Yag laser operating at low intensity produced an ion temperature core of the order of 400 eV and a neutral temperature of the order of 100 eV for many ablated materials. The ToF of electrons indicates the presence of hot electron emission with an energy of ～1 keV.     

Mechanism and enhancement of photoluminescence from silicon nanocrystals implanted in SiO2 matrix

Photoluminescence (PL) spectra of Si nanocrystals (NCs) prepared by 130 keV Si ions implantation onto SiO2 matrix were investigated as a function of annealing temperature and implanted ion dose. PL spectra consist of two PL peaks, originated from smaller Si NCs due to quantum confinement effect (QCE) and the interface states located at the surface of larger Si NCs. The evolution of number of dangling bonds (DBs) on Si NCs was also investigated. For hydrogen-passivated samples, a monotonic increase in PL peak intensity with the dose of implanted Si ions up to 3×1017 ions /cm2 is observed. The number of DBs on individual Si NC, the interaction between DBs at the surface of neighbouring Si NCs and their effects on the efficiency of PL are discussed.     

Ion beam synthesis and carrier dynamics of ZnO nanoparticles embedded in a SiO2 matrix

Zinc oxide (ZnO) nanostructures have been synthesized by the implantation of ZnO molecular ions into SiO₂ followed by high temperature thermal annealing. 35 keV ZnO^? ions were implanted to a fluence of 5×10¹⁶ ions/cm² into SiO₂ at room temperature (RT). The implanted sample was annealed in an oxygen environment to allow the growth of ZnO precipitates. In the as-implanted sample, Zn nanoparticles up to 4.5 nm in diameter were observed and were distributed throughout the implanted depth in the SiO₂. The highest concentration of Zn from the implantation was at a depth of 25 nm. During annealing, Zn diffused into the substrate and combined with oxygen to form ZnO. ZnO nanostructures thus formed had diameters up to 8 nm, embedded in SiO₂. Donor-bound exciton (D, X), acceptor-bound exciton (A, X), and donor–acceptor-pair (DAP) transitions were observed in low temperature photoluminescence (PL) measurements on an annealed sample. RT-PL measurement showed band-edge emission in the ultraviolet region with a full width at half maximum of 121 meV. Time-resolved PL measurements performed at 4 K revealed an excitonic lifetime of 160 ps.     

Ion implantation damage and crystalline-amorphous transition in Ge

Experimental studies on the damage produced in (100) Ge substrates by implantation of Ge⁺ ions at different energies (from 25 to 600 keV), fluences (from 2×10¹³ to 4×10¹⁴ cm⁻²) and temperature (room temperature, RT, or liquid-nitrogen temperature, LN₂T) have been performed by using the Rutherford backscattering spectrometry technique. We demonstrated that the higher damage rate of Ge with respect to Si is due to both the high stopping power of germanium atoms and the low mobility of point defects within the collision cascades. The amorphization of Ge has been modeled by employing the critical damage energy density model in a large range of implantation energies and fluences both at RT and LN₂T. The experimental results for implantation at LN₂T were fitted using a critical damage energy density of ∼1 eV/atom. A fictitious value of ∼5 eV/atom was obtained for the samples implanted at RT, essentially because at RT the damage annihilation plays a non-negligible role against the crystalline–amorphous transition phase. The critical damage energy density model was found to stand also for other ions implanted in crystalline Ge (Ar⁺ and Ga⁺).     

The excitation mechanism of rare-earth ions in silicon nanocrystals

A detailed investigation on the excitation mechanisms of rare-earth (RE) ions introduced in Si nanocrystals (nc) is reported. Silicon nanocrystals were produced by high-dose 80-keV Si implantation in thermally grown SiO₂ followed by 1100 °C annealing for 1 h. Subsequently some of the samples were implanted by 300-keV Er, Yb, Nd, or Tm at doses in the range 2×10¹²–3×10¹⁵ /cm². The energy was chosen in such a way to locate the RE ions at the same depth where nanocrystals are. Finally an annealing at 900 °C for 5 min was performed in order to eliminate the implantation damage. These samples show intense room-temperature luminescence due to internal 4f shell transitions within the RE ions. For instance, luminescence at 1.54 μm and 0.98 μm is observed in Er-doped nc, at 0.98 μm in Yb-doped nc, at 0.92 μm in nc and two lines at 0.78 μm and 1.65 μm in Tm-doped nc. Furthermore, these signals are much more intense than those observed when RE ions are introduced in pure SiO₂ in the absence of nanocrystals, demonstrating the important role of nanocrystals in efficiently exciting the REs. It is shown that the intense nc-related luminescence at around 0.85 μm decreases with increasing RE concentration and the energy is preferentially transferred from excitons in the nc to the RE ions which, subsequently, emit radiatively. The exact mechanism of energy transfer has been studied in detail by excitation spectroscopy measurements and time-resolved photoluminescence. On the basis of the obtained results a plausible phenomenological model for the energy transfer mechanism emerges. The pumping laser generates excitons within the Si nanocrystals. Excitons confined in the nc can either give their energy to an intrinsic luminescent center emitting at around 0.85 μm nor pass this energy to the RE 4f shell, thus exciting the ion. The shape of the luminescence spectra suggests that excited rare-earth ions are not incorporated within the nanocrystals and the energy is transferred at a distance while they are embedded within SiO₂. Rare-earth excitation can quantitatively be described by an effective cross section σ_eff taking into account all the intermediate steps leading to excitation. We have directly measured σ_eff for Er in Si nc obtaining a value of ≈2×10⁻¹⁷ cm². This value is much higher than the cross section for excitation through direct photon absorption (8×10⁻²¹ cm²) demonstrating that this process is extremely efficient. Furthermore, the non-radiative decay processes typically limiting rare-earth luminescence in Si (namely back-transfer and Auger) are demonstrated to be absent in Si nc further improving the overall efficiency of the process. These data are reported and their implications. Received: 9 April 1999 / Accepted: 10 April 1999 / Published online: 2 June 1999     

DLTS and in situ C–V analysis of trap parameters in swift 50 MeV Li3+ ion-irradiated Ni/SiO2/Si MOS capacitors

Ni/SiO₂/Si MOS structures were fabricated on n-type Si wafers and were irradiated with 50 MeV Li³⁺ ions with fluences ranging from 1×10¹⁰ to 1×10¹² ions/cm². High frequency C–V characteristics are studied in situ to estimate the build-up of fixed and oxide charges. The nature of the charge build-up with ion fluence is analyzed. Defect levels in bulk Si and its properties such as activation energy, capture cross-section, trap concentration and carrier lifetimes are studied using deep-level transient spectroscopy. Electron traps with energies ranging from 0.069 to 0.523 eV are observed in Li ion-irradiated devices. The dependence of series resistance, substrate doping and accumulation capacitance on Li ion fluence are clearly explained. The study of dielectric properties (tan δ and quality factor) confirms the degradation of the oxide layer to a greater extent due to ion irradiation.     

Ion beam modification of silicide-silicon interfaces

We have modified the contact interface between Pd₂Si and n-Si by ion implantation and investigated the effect of the implantation on Schottky barrier height and rate of silicide formation by electrical current-voltage measurements and Rutherford backscattering spectroscopy. Various ions, As. P, B. O and Si at 50 keV and up to a dose of 5 × 10¹⁴ ions/cm² were implanted into Si wafers before the Pd-deposition to form Pd₂Si. In the case of As and P, the implantation showed a large erect on the subsequent Pd₂Si formation; the formation is enhanced in the as-implanted samples, but it is retarded if an annealing at 600°C precedes the Pd-deposition. Silicide formation was found generally to help reduce the implantation damage (with or without the 600°C annealing) and showed improvements on the electrical characteristics of the contact interface. Consumption of the entire implanted region by silicide formation is found necessary for obtaining a good diode performance. In the case of As implantation, a lowering of the Schottky barrier height of Pd₂Si has been observed.     

Effects of Helium and Oxygen Common Implantation in Silicon Wafer

Defect engineering for SiO2 precipitation is investigated using He-ion implantation as the first stage of separation by implanted oxygen （SIMOX）. Cavities axe created in Si by implantation with helium ions. After thermal annealing at different temperatures, the sample is implanted with 120 keV 8.0 ×1016 cm 2 0 ions. The Q ion energy is chosen such that the peak of the concentration distribution is centred at the cavity band. For comparison, another sample is implanted with O ions alone. Cross-sectionM transmission electron microscopy （XTEM）, Fourier transform infrared absorbance spectrometry （FTIR） and atomic force microscopy （AFM） measurements are used to investigate the samples. The results show that a narrow nano-cavity layer is found to be excellent nucleation sites that effectively assisted SiO2 formation and released crystal lattice strain associated with silicon oxidation.     

Phase analysis in α-Fe after high-dose Si ion implantation by depth-selective conversion-electron Mössbauer spectroscopy (DCEMS)

Si⁺ ions of 50 keV in energy were implanted into α-Fe (95% ⁵⁷Fe) with a nominal dose of 5 × 10¹⁷ cm^?2 at 350°C. The depth distribution of the Fe-Si phases formed by ion implantation after annealing at 300 and 400°C for 1 h was studied quantitatively by depth-selective conversion-electron Mössbauer spectroscopy (DCEMS). Ordered Fe₃Si and ε-FeSi was observed.     

Luminescence properties of Ge implanted SiO2:Ge and GeO2:Ge films

We have investigated cathodeluminescence (CL) of Ge implanted SiO₂:Ge and GeO₂:Ge films. The GeO₂ films were grown by oxidation of Ge substrate at 550 °C for 3 h in O₂ gas flow. The GeO₂ films on Ge substrate and SiO₂ films on Si substrate were implanted with Ge-negative ions. The implanted Ge atom concentrations in the films were ranging from 0.1 to 6.0 at%. To produce Ge nanoparticles the SiO₂:Ge films were thermally annealed at various temperatures of 600-900 °C for 1 h in N₂ gas flow. An XPS analysis has shown that the implanted Ge atoms were partly oxidized. CL was observed at wavelengths around 400 nm from the GeO₂ films before and after Ge⁻-implantation as well as from SiO₂:Ge films. After Ge⁻-implantation of about 0.5 at% the CL intensity has increased by about four times. However, the CL intensity from the GeO₂:Ge films was several orders of magnitude smaller than the intensity from the 800 °C-annealed SiO₂:Ge films with 0.5 at% of Ge atomic concentration. These results suggested that the luminescence was generated due to oxidation of Ge nanoparticles in the SiO₂:Ge films.     

Ion implantation induced by Cu ablation at high laser fluence

High energy laser plasma-produced Cu ions have been implanted in silicon substrates placed at different distances and angles with respect to the normal to the surface of the ablated target. The implanted samples have been produced using the iodine high power Prague Asterix Laser System (PALS) using 438 nm wavelength irradiating in vacuum a Cu target. The high laser pulse energy (up to 230 J) and the short pulse duration (400 ps) produced a non-equilibrium plasma expanding mainly along the normal to the Cu target surface. Time-of-flight (TOF) technique was employed, through an electrostatic ion energy analyzer (IEA) placed along the target normal, in order to measure the ion energy, the ion charge state, the energy distribution and the charge state distribution. Ions had a Boltzmann energy distributions with an energy increasing with the charge state. At a laser fluence of the order of 6 × 10⁶ J/cm², the maximum ion energy was about 600 keV and the maximum charge state was about 27+.In order to investigate the implantation processes, Cu depth profiles have been performed with Rutherford backscattering spectrometry (RBS) of 1.5 MeV helium ions, Auger electron spectroscopy (AES) with 3 keV electron beam and 1 keV Ar sputtering ions in combination with scanning electron microscopy (SEM). Surface analysis results indicate that Cu ions are implanted within the first surface layers and that the ion penetration ranges are in agreement with the ion energy measured with IEA analysis.     

Effect of hydrogen defects on nanocrystallite layers of Si solar cells by hydrogen implantation

The Si solar cells were irradiated with high energy hydrogen ions of 10, 30, 60 and 120?keV at the dose rate of 10¹⁷ H⁺ ions (proton)/cm². The structural, optical and electrical properties of the implanted samples and fabricated cells were studied. The implantation induced defects bringing structural changes before and after annealing was evidenced by the transmission electron microscopy. The Raman spectrum showed a change of crystalline to amorphous state at 480?cm^?1 when the sample was implanted by hydrogen ion of 30?keV energy. Formation of nanocrystallite layers were observed after annealing. The electroluminescence images showed that hydrogen-related defect centers were involved in the emission mechanism. The photoluminescence emission from the implanted cells was attributed to nanocrystallite layers. From current–voltage measurements, the conversion efficiencies of implanted Si solar cells were found lower than the un-implanted reference cell. The ion implantation did not passivate the defects rather acted as recombination centers.     

Structure of self-implanted silicon annealed under enhanced hydrostatic pressure

Implantation of any ions at a sufficiently high dose and energy (E) into single-crystalline Si leads to the creation of amorphous Si (aSi), with damages peaking near the projected range (R _p) of implanted species. Enhanced hydrostatic pressure (HP) at a high temperature (HT) influences the recrystallization of aSi. The structure of self-implanted Czochralski silicon (Si⁺ dose, D=2×10¹⁶ cm^?2, E=150 keV, R _p=0.22 μm) processed for 5 h at 1400 or 1520 K under HPs up to 1.45 GPa was investigated by X-ray, secondary ion mass spectrometry and photoluminescence methods. The implantation of Si produces vacancies (V) and self-interstitials (Si_i). Vacancies and Si_is form complex defects at HT–HP, also with contaminants (e.g. oxygen, always present in Czochralski silicon). The mobility and recombination of V and Si_i as well as the kinetics of recrystallization are affected by HP, thus processing at HT–HP affects the recovery of aSi.     

Nitrogen implantation in GaAs1−xPx (x=0.4; 0.65)

Nitrogen ions were implanted in GaAs_1−xP_x (x=0.4; 0.65) at room temperature at various doses from 5×10¹² cm⁻² to 5×10¹⁵ cm⁻² and annealed at temperatures from 600°C up to 950°C using a sputtered SiO₂ encapsulation to investigate the possibility of creating isoelectronic traps by ion implantation. Photoluminescence and channeling measurements were performed to characterize implanted layers. The effects of damage induced by optically inactive neon ion implantation on photoluminescence spectrum were also investigated. By channeling measurements it was found that damage induced by nitrogen implantation is removed by annealing at 800°C. A nitrogen induced emission intensity comparable to the intensity of band gap emission for unimplanted material was observed for implanted GaAs_0.6P_0.4 after annealing at 850°C, while an enhancement of the emission intensity by a factor of 180 as compared with an unimplanted material was observed for implanted GaAs_0.35P_0.65 after annealing at 950°C. An anomalous diffusion of nitrogen atoms was found for implanted GaAs_0.6P_0.4 after annealing at and above 900°C.     

Ellipsometric studies of annealing of SiO2 layers during the formation of light-emitting Si nanocrystals in them

Annealing of SiO₂ layers with excessive Si leading to the formation of silicon nanocrystals capable of fluorescing in the visible region owing to quantum-dimensional limitations is studied by the ellipsometry method. Excessive Si was introduced in SiO₂ layers by ion implantation with an energy of 25 keV and a dose of 5× 10¹⁶ cm^?2. Isochronous (10³ s) annealings were carried out in a temperature interval of 200–1150°C with a step of 100°C. An LÉF-2 ellipsometer with a 70° angle of incidence at a wavelength of 632.8 nm was used for the measurements. Fluorescence excited by a nitrogen laser was monitored concurrently. It is found that variations in optical constants of the layers at each step of annealing over the entire temperature range studied are clearly detected by ellipsometry. Variations in optical parameters of excessive Si are calculated in the Bruggeman approximation. They are found to correspond to individual stages of the formation of nanoprecipitates revealed earlier by other techniques. Nanocrystals proper producing intense visible photoluminescence are formed at annealing temperatures of 1000°C and higher.     

Quantum chemical study of the properties of an SiO<Subscript>2</Subscript>/Si(100) interface implanted with boron ions

Quantum-chemical calculations of the properties of a B⁺ ion-implanted SiO₂/Si(100) interface are presented. Dependencies of the total energy of a B⁺ ion cluster system on the location of B⁺ ions in oxygen and silicon vacancies are calculated, along with the geometric and electronic characteristics of the equilibrium cluster states with implanted boron ions.     

Preparation, structure, and properties of metal nanocomposites in lithium niobate

Crystals of lithium niobate LiNbO₃ are implanted with 60-keV Cu^? ions at different ion fluxes to a fluence of 2 × 10¹⁷ ions/cm². The structure and the linear and nonlinear optical properties of the implanted layers are investigated. The optical transmission and ion-induced photon spectra of the LiNbO₃ crystals are measured in the course of implantation. It is revealed that the implantation brings about the formation of complex nanocomposites consisting of metallic copper nanoparticles and nanodomains of the matrix. The distributions of nanoparticles and nanodomains in the implanted layers do not correlate with each other. It is shown that the variations in the linear and nonlinear optical absorption of the nanocomposites are predominantly determined by the changes in the chemical composition and the structure of the matrix.     

Investigation of weak damage in Al0.25Ga0.75As/GaAs by using RBS/C and Raman spectroscopy

The weak damage induced by 0.8 MeV Si ion implantation in the Al_0.25Ga_0.75As films epitaxially grown on GaAs substrates was studied by using Rutherford backscattering spectrometry/channeling (RBS/C) and Raman spectroscopy. RBS/C spectra measured from the implanted samples showed rather low damage level induced by the ion implantation with ion dose from 1×10¹⁴ to 5×10¹⁵ cm⁻². The Raman spectra were measured on these samples. Two kinds of phonon modes, GaAs-like and AlAs-like, are observed, which indicate the existence of multiple phonon vibrational modes in the epitaxial Al_0.25Ga_0.75As films on the GaAs substrate. Compared with the unimplanted sample, the Raman photon peaks for the implanted sample shift gradually to lower energy with the increase of the implantation dose. The strains induced in the implanted layer were also evaluated from the Raman spectra. The result from high resolution double crystal X-ray diffractometry (HRXRD) also verified the evolution of the strains in the implanted layers.