Formation of bubbles and blisters in hydrogen ion implanted polycrystalline tungsten

ABSTRACT

Tungsten (W) has been regarded as one of the most promising plasma facing materials (PFMs) in fusion reactors. The formation of bubbles and blisters during hydrogen (H) irradiation will affect the properties of W. The dependence of implantation conditions, such as fluence and energy, is therefore of great interest. In this work, polycrystalline tungsten samples were separated into two groups for study. The thick samples were implanted by 18?keV H₃⁺ ions to fluences of 1?×?10¹⁸, 1?×?10¹⁹ and 1?×?10²⁰ H⁺/cm², respectively. Another thick sample was also implanted by 80?keV H₂⁺ ions to a fluence of 2?×?10¹⁷ H⁺/cm² for comparison. Moreover, the thin samples were implanted by 18?keV H₃⁺ ions to fluences of 9.38?×?10¹⁶, 1.88?×?10¹⁷ and 5.63?×?10¹⁷ H⁺/cm², respectively. Focused ion beam (FIB) combined with scanning electron microscopy (SEM) and transmission electron microscopy (TEM) were used for micro-structure analysis, while time-of-flight ion mass spectrometry (ToF-SIMS) was used to characterize the H depth profile. It is indicated that bubbles and blisters could form successively with increasing H⁺ fluence. H bubbles are formed at a fluence of ～5.63?×?10¹⁷ H⁺/cm², and H blisters are formed at ～1?×?10¹⁹ H⁺/cm² for 18?keV H₃⁺ implantation. On the other hand, 80?keV H₂⁺ ions can create more trapping sites in a shallow projected range, and thus enhancing the blisters formation with a relatively lower fluence of 2?×?10^17?H⁺/cm². The crack-like microstructures beneath the blisters are also observed and prefer to form on the deep side of the implanted range.     

TEM study of ion implanted GaAs after pulsed electron beam annealing

Abstract

(001) GaAs single crystals were implanted with 150 keV Cr⁺ ions using a dose of 5 × 10¹⁵ ions cm^?2. The amorphized surface layers were subjected to pulsed electron beam annealing at energy densities in the range 0–1.3 J cm^?2. A detailed TEM investigation of the damaged and annealed surface layer was conducted. These observations were correlated with backscattering results.     

Ion bombardment induced phase transformations and inert gas mobility in the semiconductors Ge,Si, and GaAs

Abstract

The present study contributes some new aspects to the general understanding of the ion implantation behaviour of 3 common semiconductor materials, and of diffusion processes in these materials. Single crystals of Si, Ge, and GaAs were bombarded with Kr- or Xe-ions at energies of 40 or 500 keV and doses between 10¹¹ and 2 × 10¹⁶ ions/cm². Gas release measurements and Rutherford scattering of 1 MeV He⁺-ions combined with channeling were used to study bombardment damage (amorphization) and inert gas diffusion. At low bombardment doses (10¹¹ ions/cm²) and energy (40 keV), no damage was observed and the gas release was compatible with volume diffusion resembling Group I and VIII behaviour. Hence, the pre-exponential terms, D ₀, were low (range 10-^5±1 cm² sec^?1) and the activation enthalpies, Δ H, were much lower than those of self-diffusion or of diffusion of Group III and V elements. The Δ H's for gas diffusion followed the relation Δ H = (1.05±0.1) × 10^?3 T_m eV with the melting point, T_m , in °K. The mechanism of gas mobility might be the Turnbull dissociative mechanism. Rutherford scattering and channeling data indicated that part of the gas occupied lattice sites.

At higher doses, the bombarded layers turned amorphous. Channeling experiments showed a coincidence in temperatures for a gas release process different from the above one of volume diffusion, and recrystallization of the disordered layer to the single crystalline state. Both processes occurred in the temperature range 0.60 to 0.65 T_m . The gas release indicated a (partial) single jump character with implied Δ H's following the relation Δ H = (2.1±0.1) × 10^?3 T_m eV. Contrary to previous results on oxides, this new gas release occurred at temperatures near to those or even above those of volume diffusion of the gas.

Due to the easy formation of an amorphous layer it was difficult to observe the retarded release (trapping of gas) that has been found in many materials at high gas and damage concentrations. However, in a separate series of experiments with 500 keV Kr-ions, a release retarded with respect to volume diffusion of the gas was observed in Si and Ge.     

Crystalline to amorphous transformations in ion implanted GaP

Abstract

The amorphization process of GaP by ion implantation is studied. The samples of 〈111〉 oriented GaP were implanted at 130 K with various doses 5 × 10¹³-2 × 10¹⁶ cm^?2 of 150 keV N⁺ ions and with the doses of 6 × 10¹²-1.5 × 10¹⁵ cm^?2 of 150 keV Cd⁺ ions. Room temperature implantations were also performed to see the influence of temperature on defect production. Rutherford backscattering and channelling techniques were used to determine damage in crystals. The damage distributions calculated from the RBS spectra have been compared with the results of Monte-Carlo simulation of the defect creation.

The estimated threshold damage density appeared to be independent on ion mass and is equal 6.5 × 10²⁰ keV/cm³. It is suggested that amorphization of GaP is well explained on the basis of a homogenous model.     

The concentration profiles of the recoil implanted oxygen in Si after ion implantations into SiO2-Si substrates

Abstract

The annealing of bare thermal oxide on silicon at 400–500°C in a hydrogen bearing gas results in a reduced density of states N_ss at the substrate silicon/oxide interface. Treatments of this type have played a role in MOS processing schedules for several years. However, a similar approach applied to large areas (cm²) of poly-silicon coated oxide appears to be less effective in reducing N_ss. This may be due to the polysilicon acting as a partially impermeable barrier which tends to starve the substrate/oxide interface of hydrogen.

In the present work hydrogenation of 2-inch diameter, polysilicon coated wafers has been accomplished by hydrogen ion implantation. H2⁺ ions of 135 kV energy were implanted (to a dose of 10¹⁵ cm^?2) through a 7000 Å polysilicon coating into an underlying 1400 Å SiO₂ layer. The polysilicon was removed after 30-min anneals carried out in pure N₂ at 300, 400 or 500°C. Aluminium dots, 1 mm in diameter were then deposited on to the oxide and high frequency (1 MHz) and quasistatic C-V curves recorded for determinations of Nss. Control anneals on unimplanted material were carried out in pure N₂ and N₂-H₂ ambients. Control samples annealed in pure N₂ with their polysilicon coating intact had mid-gap N_ss values of not less than 4 × 10¹⁰ cm^?2 eV^?1. The corresponding value after N₂-H₂ anneals on polysilicon-free wafers was 3 × 10¹⁰. H₂ ⁺ implanted samples annealed in pure N₂ with their polysilicon intact had mid-gap N_ss values of 1 × 10¹⁰ cm^?2 eV^?1.

The effectiveness of ion beam hydrogenation may depend upon confinement of the associated displacement damage to the polysilicon. This allows the implanted hydrogen to be activated within the SiO₂ at temperatures similar to those employed for normal hydrogeneous gas annealing of the substrate silicon/oxide interface.     

Annealing behaviour of arsenic implants in silicon

Abstract

The annealing behaviour of 80 keV room temperature arsenic implants in silicon below the amorphization dose has been studied by comparing the physical profile and the electrical profiles following different isochronal anneals.

It is shown that the electrically active fraction, which is about 0.4 after 30 min annealing at 600°C, increases continuously until 100% electrical activation of the arsenic ions is reached at about 900°C.

The activation energy for the annealing process has been found equal to 0.4 eV. A tentative interpretation of the mechanism involved is given.

From the analysis of the physical profiles obtained after isochronal annealing, an effective diffusion coefficient at 900°C equal to 5 × 10^?16 cm² s^?1 has been calculated.     

Metallic alloy precipitates in high dose indium implanted MgO

Abstract

MgO implanted at room temperature with 150keV In⁺ ions and doses ranging from 10¹⁵ to 10¹⁷ ions cm^?2 was studied by optical absorption and transmission electron microscopy (TEM). Creation of defects in the anionic sublattice (F-, F⁺-, F₂-centers) and in the cationic sublattice (V^?-centers) are observed. Subsequent annealings of the implanted crystals have shown different behaviours depending on the implanted dose. For medium dose (2 × 10¹⁶ ions cm^?2), the formation of In³⁺ species seems to be the preponderant phenomenon. At higher dose (8 × 10¹⁶ ions cm^?2), metallic precipitates are formed between 400 and 700°C. The identification of these precipitates has been achieved using TEM: they are formed of a metallic alloy Mg₃In with a hexagonal structure and their orientation relationship with respect to the MgO matrix is: (0001)Mg₃In//(111)Mgo and [1120]_Mg3In// [l10]MgO.     

Generation of high-energy negative hydrogen ions upon the interaction of superintense femtosecond laser radiation with a solid target

The formation of a high-energy (～35 keV) beam of negative hydrogen ions was observed in the expanding femtosecond laser plasma produced at the surface of a solid target by radiation with an intensity of up to 2× 10¹⁶ W/cm². The energy spectra of the H⁺ and H^?-ions show a high degree of correlation.     

On the degradation of ZnS:Cu,Al,Au phosphor powder: The effects of temperature

Abstract

The effects of temperature are discussed when the ZnS:Cu,Al,Au (P22G) phosphor powder is bombarded by a 2 keV electron beam with a current density of 88 mA/cm² at an oxygen pressure of 2 × 10^?6 Torr at temperatures between 25 and 300°C. The rate of surface reaction decreases at higher temperatures due to the reduction in the mean stay time of the O₂ on the surface which is vital for the reactions according to an electron stimulated surface chemical reaction model. A direct correlation between the temperature and the initial cathodoluminescence (CL) brightness which depicts thermal quenching of the CL was observed.     

Hydrogen-plasma etching of hydrogenated amorphous silicon: a study by a combination of spectroscopic ellipsometry and trap-limited diffusion model

The kinetics of etching hydrogenated amorphous silicon by a hydrogen plasma has been studied by in-situ spectroscopic ellipsometry measurements. The formation of a hydrogen-rich sublayer is clearly emphasized. Its thickness increases from 7 to 27?nm when the temperature during the hydrogen-plasma treatment is raised from 100 to 250°C. This effect is interpreted by solving the differential equation for trap-limited hydrogen diffusion through a mobile surface. By assigning the thickness of this sublayer to the mean diffusion distance of hydrogen we determined values of the effective diffusion coefficient of hydrogen higher than 10^?14?cm²s^?1 with an activation energy of 0.22?eV. The density of hydrogen traps is found to decrease from 7.3 × 10¹⁸ to 4.5 × 10¹⁷?cm^?3 as the temperature of the hydrogen treatment increases from 100 to 250°C with an activation energy of 0.43?eV. This effect is interpreted by a thermal equilibrium involving hydrogen transitions between shallow states and hydrogen-trapping sites.     

Comparison of the Kinetics of the Exchange Mechanism of the Thallium Ion with 18C6 and with Pentaglyme in Acetonitrile Solutions

Abstract

In acetonitrile solutions, the exchange reaction is bimolecular in the Tl⁺ + 18C6 system, while in the Tl⁺ + pentaglyme system the associative-dissociative and the bimolecular mechanisms coexist at room temperature and the bimolecular exchange reaction dominates at 263° K. For the bimolecular mechanism in the case of Tl⁺ + 18C6 and the associative-dissociative mechanism in the case of Tl⁺ + pentaglyme, the activation energies of the exchange reactions change with temperature. At 298° K, in the Tl⁺ + 18C6 system the activation energy for the bimolecular exchange reaction is ≈ 2 kcal.mol^?1 and exchange rate constant (k₁) is (4.1 ± 0.1) × 10⁷ s^?1mol^?1; in the Tl⁺ + pentaglyme system, the activation energy for the associative-dissociative exchange reaction is ≈ 5 kcal mol^?1 and the decomplexation rate constant (k_?2) is (2.2 ± 0.4) X 10⁵ s^?1. The activation energy for the bimolecular exchange in the Tl⁺ + pentaglyme system was determined to be 3.00 ± 0.05 kcal.mol_?1 and the exchange rate constant (3.0 ± 0.1) X 10⁸ s^?1 mol^?1.     

Investigation of the reaction Dy164 (n, γ) Dy165

The level structure of Dy¹⁶⁵ has been investigated at the Karlsruhe research reactor using thermal neutron capture in Dy¹⁶⁴. The target was Dy₂O₃ enriched to 92.71% Dy¹⁶⁴. Neutrons were either monochromized by Bragg reflection from a lead crystal or transmitted through a bismuth single crystal filter. High-resolution measurements of the capture spectrum have been performed by means of a Ge(Li) 5-detector pair spectrometer and a Ge(Li) anti-Compton assembly. A large number of new lines has been observed. Cascade relationships were studied by using several techniques: a double coincidence apparatus with 4″ Ø×5″ NaI(Tl) detectors, a coincidence system containing a scintillation detector and a 34 cm³ Ge(Li)-diode as well as a two-parameter system involving the pair spectrometer (with NaI (Tl) as the primary detector) and a single 4″Ø×6″ NaI (Tl) counter. In the framework ofNilsson's model and simple microscopic pictures of vibrational states the results are consistent with the following spectroscopic interpretation: 0 keV, 7/2⁺[633]; 108.2 keV, 1/2^?[521]; 184.3 keV, 5/2″[512]; 533.5 keV, 5/2″ [523]; 538.6 keV, 7/2⁺[633] +Q₂₂; 570.3 keV, 5/2^?[512]+Q₂₂+1/2^?[510]; 573.6 keV, 3/2^? [521]+1/2^?[521]+Q₂₂; 1103.3 keV, 1/2^? [521]+Q₂₂+3/2^? [521]. For comparison preliminary results are given for the isotonic nucleus Yb¹⁶⁹.     

Effect of the dose and energy of Ar+ ions on the surface properties of vanadium and its alloys

The features of processes occurring on the surface of vanadium and its alloys irradiated using the ILU ion-beam accelerator with Ar⁺ ions at an energy of 20 and 40 keV up to doses of 5.0 × 10²¹ m^?2 and 1.0 × 10²² m^?2 at T _irr ≈ 700 K are studied. The effect of the dose and energy of implanted ions on the surface hardness is obtained. The thickness of the hardened layer is more than two orders of magnitude higher than the theoretical and experimental projected range of Ar⁺ ions at an energy of 20 and 40 keV in vanadium. Structural changes in the surface layers, which are expressed in a change in the intensity of reflections from a number of planes and an increase in the crystal-lattice parameter of the irradiated materials, are also observed.     

Charge exchange cross sections for He+ incident on Cs

The total charge-exchange cross section, σ₊₀, for He⁺ incident on Cs vapor has been measured in the energy range 0.5 to 41 keV. The cross section falls from (1664 ± 100) × 10^?17 cm² at 1.4 keV to (224 ± 20) × 10^-17 cm² at 41 keV. These measurements are compared with previous measurements and with theoretical calculations of this cross section.     

Diffusion of Butylated Hydroxy Toluol (BHT) in PVC Films

Abstract

The diffusion coefficient of butylated hydroxy toluol (BHT) in solvent casted PVC films from tetrahydrofurane (THF) was studied by UV spectroscopy. Diffusion coefficient of BHT in PVC at 140, 160 and 180°C were determined as 1.0 × 10^?12 3.0 × 10^?12 and 6.0 × 10^?12 m²/s. The activation energy of diffusion (E_a) was 66 kj/mol.

IR spectroscopic work showed that the complete removal of THF was possible by heating films 15 minutes at 140 °C, but that caused formation of C=0 groups in PVC. No dehydrochlorination of films was observed even for heating them at 180 °C for 60 minutes.

Antioxidant BHT is volatile at high temperatures, so it is not advisable to use it for high temperature applications.     

Damage and lattice location studies in Hg implanted Hg1–xCdxTe

Abstract

Rutherford backscattering (RBS) and ion induced X-ray (PIXE) channeling experiments have been used to study the damage accompanying Hg and Al implantations into Hg_0.8Cd_0.2 Te and its annealing as well as to determine the location of Hg in the crystal.

The damage induced by the implantation of 300 keV Hg and 250 keV Al ions at room temperature was found from RBS channeling studies to reach a saturation level at doses of 1 × 10¹⁴ cm^?2 and 3 × 10¹⁴ cm^?2 respectively. The damage resembles that characteristic for extended defects and it anneals at ≈ 300°C.

The location of the constituents of Hg implanted Hg_0.8 Cd_0.2 Te was studied by PIXE channeling observing the characteristic X-rays for each element. Angular scans indicate that the channels are mostly blocked by Hg atoms for both unannealed and, to a lesser extent, annealed crystals. This observation supports the suggestion that interstitial Hg atoms may be responsible for the conductivity of Hg implanted Hg_1–x Cd_g Te.     

Transformations of radicals and ions in irradiated sodium sulfate doped with nitrate ions

The structure and properties of the paramagnetic centers formed by γ-irradiation at 77 K in sodium sulfate doped with nitrate ions have been investigated by the EPR method. The NO^2? ₃, NO₂ and SO^? ₄ radicals have been identified. The orientation of NO^2? ₃ relation to crystallographic axes is determined. In the 77-400 K temperature range the transformations of observable radicals have been studied. The mechanisms of their formation and thermal annealing have been discussed. The symmetry of nitrate ions in sodium sulfate was investigated by diffuse reflectance infrared Fourier transform spectroscopy. At the concentration of NO^? ₃ up to 5.5 × 10¹⁸ g^?1 the nitrate ion was supposed to have a planar or pyramidal configuration of the D_3h or C_3V symmetries. At the concentration of the dopant higher than 5.5 × 10¹⁸ g^?1 the nitrate ions with the C_2V symmetry were observed.     

Hydrogen implantation in Ni(111) — A study of H2 desorption dynamics from the bulk

Hydrogen implanted in Ni(111) has been investigated by the use of temperature programmed desorption (TPD) as a function of implantation energy (0.08–5.0 keV) and dose (0−2.6 × 10¹⁷ H⁺₂cm⁻²). The amount of hydrogen implanted was calibrated by comparison to the amount chemisorbed on the surface since separation of the desorption features for the two types of hydrogen was possible. It is shown that trap formation plays an important role in the observed behavior of the implanted hydrogen desorption features for implantation energies above 1.0 keV. The desorption of implanted hydrogen is found to be strongly forward-peaked along the crystal surface normal. Since the surface was saturated with hydrogen when the implanted hydrogen was released, this effect is explained by recombination of an implanted and a chemisorbed hydrogen atom. Here, a translationally excited H₂ molecule desorbing from the surface is produced by a hydrogen atom originating from an elevated potential region inside the solid.     

Silicon negative ion implantation induced vacancy defects in thermally grown SiO2 thin films

ABSTRACT

Thermally grown SiO₂ thin films on a silicon substrate implanted with 100?keV silicon negative ions with fluences varying from 1?×?10¹⁵ to 2?×?10¹⁷ ions cm^?2 have been investigated using Electron spin resonance, Fourier transforms infrared and Photoluminescence techniques. ESR studies revealed the presence of non-bridging oxygen hole centers, E′-centers and P_b-centers at g-values 2.0087, 2.0052 and 2.0010, respectively. These vacancy defects were found to increase with respect to ion fluence. FTIR spectra showed rocking vibration mode, stretching mode, bending vibration mode, and asymmetrical stretching absorption bands at 460, 614, 800 and 1080?cm^?1, respectively. The concentrations of Si–O and Si–Si bonds estimated from the absorption spectra were found to vary between 11.95?×?10²¹ cm^?3 and 5.20?×?10²¹ cm^?3 and between 5.90?×?10²¹ cm^?3 and 3.90?×?10²¹ cm^?3, respectively with an increase in the ion fluence. PL studies revealed the presence of vacancies related to non-bridging oxygen hole centers, which caused the light emission at a wavelength of 720?nm.