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.     

Optimum ion implantation and annealing conditions for stimulating secondary negative ion emission

The type, energy, ion dose, and heating temperature required to ensure a stable minimum work function of a surface in one experimental cycle (at least 2–3 min) are determined. Secondary ion mass spectrograms are recorded using Cs⁺, Ba⁺, and Ar⁺ ions. Cu, Al, and Mo samples are studied. The optimum ion implantation conditions and the activation temperature that provide a stable minimum work function of the sample surfaces are found. The samples implanted by Ba⁺ ions withstand higher temperature and current loads than the samples implanted by Cs⁺ ions. However, the work function in the case of Cs⁺ ions decreases stronger (to 1.9 eV). It is shown that neutral sputtered particles do not leave the surface at eφ ≤ 1.85–1.90 eV.     

An improved radio frequency heavy ion source

Abstract

An improved r.f. heavy ion source, which can operate with gases, liquids and solids is described. The operating temperature of the ion source may reach 1000°C. It can therefore, generate ion beams of a considerable number of elements. including metallic ions. At present, ion beams of S⁺, Al⁺, As⁺. Zn⁺, Mg⁺, Cd⁺, Ag⁺, Sm⁺, Te⁺, Se⁺, Sn⁺, In⁺, Hg⁺, etc. have been extracted. The extracted total beam current ranges from several hundred microamperes to the order of milliampere. The useful fraction of ion in the total beam is 70–90%. Life span of the source ranges from 40 hours to more than 100 hours. The emittance of the source is 3 × 10^?6 cm rad. Structure and operating characteristics of this ion source are discussed.     

Complex refractive index and phosphorus concentration profiles in P+31 ion implanted silicon by ellipsometry and auger electron spectroscopy

Ellipsometrically measured complex retractive index profiles in high energy P⁺₃₁ ion implanted silicon have been compared with the phosphorus concentration profiles determined by in-depth profiling of the implanted surface using Auger electron spectroscopy in conjunction with in-situ ion sputtering. Structure was observed in the phosphorus profile which corresponds to structure in the complex refractive index profiles of unannealed specimens. This implies that the complex refractive index profile of the unannealed surface is sensitive to the concentration of the implanted species as well as the amount of structural disorder in the implanted layer. These results also indicate that the implanted phosphorus tends to build up in the more highly damaged regions, possibly through a radiation enhanced self-diffusion mechanism.     

On the nature of ion bombardment-induced phase transformations in films of transition metals

Abstract

Electron diffraction studies have been made of polycrystalline Ni films irradiated with well separated beams of ions of different nature, namely ions of inert (He⁺, Ne⁺, Ar⁺, Kr⁺, Xe⁺) and reactive (N⁺ and O⁺) gases. The Ni films were prepared under vacuum conditions (P? 3·10^?6Pa during evaporation) preventing an appreciable contamination of the films with impurities. The samples were irradiated at T? 300 K with ion beams of energies from 10 to 100 keV in the dose range between 5·10¹⁶ cm^?2 and the value leading to sample destruction.

Irradiation with noble gas ions revealed no phase transitions in the Ni films. A similar result was obtained in irradiation of Fe and Cr films with He⁺ ions. The bombardment of Ni films with reactive gas ions does cause changes in the lattice structure of the samples under study, depending on the nature of the bombarding ions. The N⁺ ion bombardment gives rise to the hcp phase with the lattice parameters typical of the Ni₃N compound, and the O⁺ ion bombardment results in the fcc phase with the NiO-type parameter.

The conclusion is drawn on the chemical origin of the phase transformations in the Ni films under ion bombardment. The necessity of revising the concept about the polymorphous nature of phase transformations induced in the films of transition metals by ion bombardment is substantiated.     

Effects of silicon negative ion implantation in semi-insulating gallium arsenide

ABSTRACT

In the present work, effects of silicon negative ion implantation into semi-insulating gallium arsenide (GaAs) samples with fluences varying between 1?×?10¹⁵ and 4?×?10¹⁷?ions?cm^?2 at 100?keV have been described. Atomic force microscopic images obtained from samples implanted with fluence up to 1?×?10¹⁷?ion?cm^?2 showed the formation of GaAs clusters on the surface of the sample. The shape, size and density of these clusters were found to depend on ion fluence. Whereas sample implanted at higher fluence of 4?×?10¹⁷?ions?cm^?2 showed bump of arbitrary shapes due to cumulative effect of multiple silicon ion impact with GaAs on the same place. GXRD study revealed formation of silicon crystallites in the gallium arsenide sample after implantation. The silicon crystallite size estimated from the full width at half maxima of silicon (111) XRD peak using Debye-Scherrer formula was found to vary between 1.72 and 1.87?nm with respect to ion fluence. Hall measurement revealed the formation of n-type layer in gallium arsenide samples. The current–voltage measurement of the sample implanted with different fluences exhibited the diode like behavior.     

Peculiarities of heavy ion channeling

Abstract

Depth distributions of implanted Mg⁺- and Ca⁺-ions and the corresponding radiation damage were studied for different channeling orientations of silicon crystals. The shape of the implantation profiles is discussed by using simple models for dechanneling and energy loss processes. A correlation between dechanneling, damage production and depth distributions of the channeled ions could be observed. This correlation is seen by the maxima shifts in damage and implanted ion distributions between channel and random incidence.     

The behaviour of mosaic blocks and electrical properties of polysilicon under ion implantation

Abstract

The change in microstrains ε, block sizes L and in the temperature dependences of conductivity of polysilicon with the grain size 30-40nm at N⁺, Ne⁺, P⁺ ion irradiation has been studied. It is shown that ε increases while L practically is not changing up to amorphization. The change in conductivity is governed by an increase in the density of states near the Fermi level and depends both on the damage rate for the given ions and their chemical activity.     

A SIMS study of ion beam induced migration of nitrogen in thermally oxidized silicon

The potential use of thin silicon nitroxide films as gate dielectrics in VLSI MOS devices has motivated much recent work. The present study shows that positive ion bombardment, as encountered in sputter depth profiling or ion implantation, can induce considerable movement of nitrogen in thin thermal oxide films on silicon. Low energy N⁺₂ implants are performed in-situ in a SIMS apparatus and are subsequently depth profiled. The effect of implant dose and oxide thickness are examined and comparisons are made to films prepared by rapid thermal nitridation and LPCVD. Profiles obtained under O⁺₂, O^-, and Cs⁺ bombardment are also compared. SIMS depth profiles of implanted 200 Å oxides using positive ion bombardment show a depletion of nitrogen near the surface, a shoulder in the nitrogen concentration near the Si-SiO₂ interface, and a peak in this concentration at the interface. Negative ion bombardment did not induce a shoulder-peak structure at the interface. The implications of these results are discussed.     

Combined field ion microscopy and transmission electron microscopy of heavy ion damage in tungsten

Abstract

A field ion microscopy (FIM) and transmission electron microscopy (TEM) investigation of radiation damage in tungsten after heavy ion bombardment has been carried out. Field ion specimens of tungsten were irradiated with 180–230 keV Xe⁺ ions. The irradiation doses were varied between 4 × 10¹¹ and 4 × 10¹² ions/cm². The irradiated specimens were examined in FIM. Experiments combining both TEM and FIM were performed in order to compare the results obtainable by these two methods. The distribution of defects visible by TEM was inhomogeneous. The influence of the imaging field in FIM on the defects visible in TEM is discussed.     

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.     

Optical reflectivity study of silicon ion implanted poly(methyl methacrylate)

The optical reflectivity (both specular and off-specular) of poly(methyl methacrylate) (PMMA) implanted with silicon ions (Si⁺) at energy of 50 keV, is studied in the spectral range 0.25-25 μm. The effect from the Si⁺ implantation on the reflectivity of two PMMA materials is examined in the dose range from 10¹⁴ to 10¹⁷ ions/cm² and is linked to the structure formed in this ion implanted plastic. As compared to the pristine PMMA, an enhancement of the reflectivity of Si⁺ implanted PMMA is observed, that is attributed to the modification of the subsurface region of PMMA upon the ion implantation. The ion-produced subsurface organic interface is also probed by laser-induced thermo-lens.     

Evaluation of secondary ion yield enhancement from polymer material by using TOF-SIMS equipped with a gold cluster ion source

We investigated the enhancement of the secondary ion intensity in the TOF-SIMS spectra obtained by Au⁺ and Au₃⁺ bombardment in comparison with Ga⁺ excitation using polymer samples with different molecular weight distributions. Since the polymer samples used in this experiment have a wide molecular weight distribution, the advantages of the gold cluster primary ion source over monoatomic ion could accurately be evaluated. It was observed that the degree of fragmentation decreased by the usage of cluster primary ion beam compared with monoatomic ion beam, which was observed as a shift of the intensity distribution in the spectra. It was also found out that the mass effect of Au⁺ and Ga⁺ as monoatomic primary ion, resulted in about 10-60 times of enhancement for both samples with different molecular distributions. On the other hand, the Au₃⁺ bombardment caused intensity enhancement about 100-2600 compared with Ga⁺ bombardment, depending on the mass range of the detected secondary ion species. The cluster primary ion effect of Au₃⁺, compared with Au⁺, therefore, was estimated to be about 10-45.     

Ion beam shaping of embedded metal nanoparticles by Si+ ion irradiation

Fine Co and Pt nanoparticles are nucleated when a silica sample is implanted with 400 keV Co⁺ and 1370 keV Pt⁺ ions. At the implanted range, Co and Pt react to form small Co _x Pt_(1?x) nanoparticles during Si⁺ ion irradiation at 300 °C. Thermal annealing of the pre-implanted silica substrate at 1000 °C results in the formation of spherical nanoparticles of various sizes. When irradiated with Si⁺ ions at 300 °C, particles in the size range of 5–17 nm undergo rod-like shape transformation with an elongation in the direction of the incident ion beam, while those particles in the size range of 17–26 nm turn into elliptical shape. Moreover, it is suspected that very big nanoparticles (size >26 nm) decrease in size, while small nanoparticles (size <5 nm) do not undergo any transformation. During Si⁺ ion irradiation, the crystalline nature of the nanoparticles is preserved. The results are discussed in the light of the thermal spike model.     

Amorphous GaP produced by ion implantation

Two types of non-crystalline states (“disordered” and “amorphous”) of GaP were produced by using ion implantation and post annealing. A structural-phase-transition-like annealing behaviour from the “disordered” state to the “amorphous” state was observed.The ion dose dependence and the annealing behaviour of the atomic structure of GaP implanted with 200 keV ? N⁺ ions were studied by using electron diffraction, backscattering and volume change measurements. The electronic structure was also investigated by measuring optical absorption and electrical conductivity.The implanted layer gradually loses the crystalline order with the increase of the nitrogen dose.The optical absorption coefficient α and electric conductivity σ of GaP crystals implanted with 200 keV?N⁺ ions of 1 × 10¹⁶ cm^?2 were expressed as αhν = C(hν ? E₀)ⁿ and log $\text{σ = A ? BT}{}^{\mathrm{<mtext>-</mtext><mtext>1</mtext><mtext>4</mtext>}}$, respectively. Moreover, the volume of the implanted layer increased about three percent and the electron diffraction pattern was diffused halo whose intensity monotonically decreases along the radial direction. These results indicate that the as-implanted layer has neither a long range order nor a short range order (“disordered state”).In the sample implanted at 1 × 10¹⁶ cm^?2, a structural phase-transition-like annealing stage was observed at around 400°C. That is, the optical absorption coefficient α abruptly fell off from 6 × 10⁴ to 7 × 10³ cm^?1 and the volume of the implanted layer decreased about 2% within an increase of less than 10 degrees in the anneal temperature. Moreover, the short range order of the lattice structure appeared in the electron diffraction pattern. According to the backscattering experiment, the heavily implanted GaP was still in the non-crystalline state even after annealing.These facts lead us to believe that heavily implanted GaP, followed by annealing at around 400°C, is in the “amorphous” state, although as-implanted Gap is not in the “amorphous” state but in the “disordered” state.     

Modification of thin oxide films on Be,Si, Al,Ti, Zr,and W under bombardment by He<Superscript>+</Superscript> and Ar<Superscript>+</Superscript> ion beams with a broad energy spectrum

Data on the distribution of Be, Al, Ti, Fe, Cu, Zr, Mo, and W atoms implanted in oxide film on metal substrates by ion mixing under the action of He⁺ and Ar⁺ ion beams with a broad energy spectrum, with average energy of 10 keV, and with radiation doses up to 1 × 10²¹ ion/cm² are presented. It is shown that layers with different concentration gradients of implanted atoms form in a thin oxide layer due to simultaneous implantation, but their concentration decreases dramatically to the background value at the oxide-metal interface. Analysis of experimental data suggests that the migration of implanted atoms takes place by means of the diffusion mechanism and is determined by the parameters of physicochemical interaction of implanted atoms with substrate atoms.     

Metal-assisted SIMS and cluster ion bombardment for ion yield enhancement

In addition to structural information, a detailed knowledge of the local chemical environment proves to be of ever greater importance, for example for the development of new types of materials as well as for specific modifications of surfaces and interfaces in multiple fields of materials science or various biomedical and chemical applications. But the ongoing miniaturization and therefore reduction of the amount of material available for analysis constitute a challenge to the detection limits of analytical methods. In the case of time-of-flight secondary ion mass spectrometry (TOF-SIMS), several methods of secondary ion yield enhancement have been proposed. This paper focuses on the investigation of the effects of two of these methods, metal-assisted SIMS and polyatomic primary ion bombardment. For this purpose, thicker layers of polystyrene (PS), both pristine and metallized with different amounts of gold, were analyzed using monoatomic (Ar⁺, Ga⁺, Xe⁺, Bi⁺) and polyatomic (SF₅⁺, Bi₃⁺, C₆₀⁺) primary ions. It was found that polyatomic ions generally induce a significant increase of the secondary ion yield. On the other hand, with gold deposition, a yield enhancement can only be detected for monoatomic ion bombardment.     

Calculation of the speed of sound in seawater from the known ion concentrations

It is shown that the method proposed earlier for calculating the speed of sound in seawater from the known ion concentrations, in a strict sense, can be applied for computing the sound speed in seas if, as a model of seawater, one uses a solution containing six ions or a solution containing four ions, namely, Na⁺, Mg²⁺, SO ₄ ^2? , and Cl^?, with the mole concentration of Na⁺ being replaced by the sum of mole concentrations of Na⁺ and K⁺ and the mole concentration of Mg²⁺ being replaced by the sum of mole concentrations of Mg²⁺ and Ca²⁺. An algorithm of calculation is proposed. It is demonstrated that, when the seawater is considered as a solution containing six ions, the computed value of the speed of sound does not depend on the choice of the specific ion whose concentration is determined from the condition of electric neutrality.     

Au5+ ion implantation induced structural phase transitions probed through structural,microstructural and phonon properties in BiFeO3 ceramics,using synergistic ion beam energy

Implanted Au⁵⁺-ion-induced modification in structural and phonon properties of phase pure BiFeO₃ (BFO) ceramics prepared by sol–gel method was investigated. These BFO samples were implanted by 15.8?MeV ions of Au⁵⁺ at various ion fluence ranging from 1?×?10¹⁴ to 5?×?10¹⁵?ions/cm². Effect of Au⁵⁺ ions’ implantation is explained in terms of structural phase transition coupled with amorphization/recrystallization due to ion implantation probed through XRD, SEM, EDX and Raman spectroscopy. XRD patterns show broad diffuse contributions due to amorphization in implanted samples. SEM images show grains collapsing and mounds’ formation over the surface due to mass transport. The peaks of the Raman spectra were broadened and also the peak intensities were decreased for the samples irradiated with 15.8?MeV Au⁵⁺ ions at a fluence of 5?×?10¹⁵?ion/cm². The percentage increase/decrease in amorphization and recrystallization has been estimated from Raman and XRD data, which support the synergistic effects being operative due to comparable nuclear and electronic energy losses at 15.8?MeV Au⁵⁺ ion implantation. Effect of thermal treatment on implanted samples is also probed and discussed.