An upgraded TOF-SIMS VG Ionex IX23LS: Study on the negative secondary ion emission of III-V compound semiconductors with prior neutral cesium deposition

A TOF-SIMS VG Ionex IX23LS with upgraded data acquisition and control system was used to study the secondary emission of negative atomic and cluster ions of non-metallic elements (P, As and Sb) upon a 19 keV Ga⁺ bombardment of non-degenerated III-V semiconductors (GaP, GaAs, GaSb, InP, InAs and InSb) with prior neutral Cs deposition from a getter dispenser. It was found that surface cesiation enhances the peak intensity of all negative ion species; in the case of atomic ions, the greatest increase (360) was observed for P⁻ emitted from InP. Such an enhancement was larger for In-based than for Ga-based compounds. We explained that in terms of an electronegativity difference between the composing atoms of III-V semiconductors. The greater electronegativity difference (bond ionicity) of In-based compounds resulted in the greater Cs-induced work function decrease leading to a higher increase in the ionization probability of secondary ions.     

Cluster emission under ion bombardment of metallic targets

Mass spectroscopic studies of the neutral particles sputtered by Ar⁺ ions at 8 keV from polycrystaline samples have been performed, using non-resonant laser ionization and subsequent time-of-flight mass spectroscopy. Besides sputtered atoms, also dimer and trimer contributions in the order of 10^–1 to 10^–2 and 10^–3 to 10^–4, respectively, are found in the sputtered flux. The data obtained here together with previously published data by other groups for different bombarding energies provide strong support for the validity of the recombination model.     

Atomic excitations in sputtering studied with the use of composite targets

Atomic excitation phenomena in sputtering have been studied with the following combinations of projectile and target. (i) Be, B, Mg, Al, and Si bombarded with 80 keV Ar⁺ at UHV as well as with the target chamber backfilled with oxygen. (ii) Mg bombarded with 80 keV O⁺, F⁺, Ne⁺, Na⁺ Cl⁺, and Ar⁺. (iii) MgO, MgF₂, MgCl₂, MgSO₄, and several alkali halides bombarded with 80 keV Ar⁺ at UHV. Results are discussed. It is concluded that the excited-state formation takes place as electron tunneling at a fairly large separation between the target surface and the particle being sputtered. It is suggested with composite targets containing a metal element that excitation takes place predominantly at locations of the target surface where the work function is low, due to a thin, metallic surface layer, and that production of ground-state, positive secondary ions mainly takes place at target surface regions with high work function. For semiconductors, the changes caused by presence of oxygen are related to the change of the bonds in the solid from being of covalent nature to being fractionally ionic.     

XPS investigation of ion beam induced conversion of GaAs(0 0 1) surface into GaN overlayer

For the advance of GaN based optoelectronic devices, one of the major barriers has been the high defect density in GaN thin films, due to lattice parameter and thermal expansion incompatibility with conventional substrates. Of late, efforts are focused in fine tuning epitaxial growth and in search for a low temperature method of forming low defect GaN with zincblende structure, by a method compatible to the molecular beam epitaxy process. In principle, to grow zincblende GaN the substrate should have four-fold symmetry and thus zincblende GaN has been prepared on several substrates including Si, 3C-SiC, GaP, MgO, and on GaAs(0 0 1). The iso-structure and a common shared element make the epitaxial growth of GaN on GaAs(0 0 1) feasible and useful. In this study ion-induced conversion of GaAs(0 0 1) surface into GaN at room temperature is optimized. At the outset a Ga-rich surface is formed by Ar⁺ ion bombardment. Nitrogen ion bombardment of the Ga-rich GaAs surface is performed by using 2-4 keV energy and fluence ranging from 3 × 10¹³ ions/cm² to 1 × 10¹⁸ ions/cm². Formation of surface GaN is manifested as chemical shift. In situ core level and true secondary electron emission spectra by X-ray photoelectron spectroscopy are monitored to observe the chemical and electronic property changes. Using XPS line shape analysis by deconvolution into chemical state, we report that 3 keV N₂⁺ ions and 7.2 × 10¹⁷ ions/cm² are the optimal energy and fluence, respectively, for the nitridation of GaAs(0 0 1) surface at room temperature. The measurement of electron emission of the interface shows the dependence of work function to the chemical composition of the interface. Depth profile study by using Ar⁺ ion sputtering, shows that a stoichiometric GaN of 1 nm thickness forms on the surface. This, room temperature and molecular beam epitaxy compatible, method of forming GaN temperature can serve as an excellent template for growing low defect GaN epitaxial overlayers.     

Secondary emission of carbon ions from graphite nanocrystallites

Emission of secondary C⁺ ions from the surface of well-oriented graphite nanocrystallites irradiated with 10 keV Ar⁺ ions has been studied. The energy distribution of emitted secondary ions has been measured. It has been found that the form of energy distribution and the energy corresponding to the maximum of distribution E_max depend on the polar angle θ of C⁺ ion emission. The linear dependence of energy in the maximum of energy spectrum of single-charged secondar y carbon ions on the polar angle of their emission E_max(θ) has been obtained. The mechanism responsible for the observed features of the energy spectra is discussed.     

Anomalous enhancement of negative sputtered ion emission by oxygen

Enhancement of negative sputtered ion yields by oxygen (either O⁺₂ bombardment or O₂ gas with Ar⁺ bombardment) is demonstrated for Si^?, As^?, P^?, Ga^?, Cu^? and Au^?, sputtered from a variety of matrices. Because oxygen also enhances positive ion yields of the same species, this effect cannot be simply explained on the basis of existing sputtered ion emission models. To rationalize these phenomena, a surface polarization model is developed which invokes localized electron emissive or electron retentive sites associated with differently oriented surface dipoles in the oxygenated surface. Such sites are considered to dominate the emission of negative and positive ions respectively. The model is shown to correctly predict that Au⁺ and Au^? ion yields are much more strongly enhanced by oxygen in dilute Au-Al alloys than in pure gold.     

Indium sputtering upon bombardment with cluster ions

A surface-ionization method is developed for measuring the integral yields of neutral particles sputtered under the effect of ion bombardment. An investigation is performed to compare the integral yield of particles sputtered upon bombarding indium with Bi _m ⁺ cluster ions (m = 1?C7) in the energy range of 2?C10 keV and the secondary ion emission under bombardment with Bi _m ⁺ cluster ions (m = 1?C5) in the energy range of 6?C18 keV. A nonadditive increase in the indium sputtering coefficient is observed with an increasing number of atoms in the bombarding clusters.     

Secondary ion emission from Si under nitrogen ion bombardment

The yield and energy distribution of positive secondary ions emitted from Si under N₂⁺ ion bombardment were measured. The obtained mass peaks correspond to three types of secondary ion species, that is, physically sputtered ions (Si⁺, Si₂⁺), chemically sputtered ions (SiN⁺ Si₂N⁺) and doubly charged ions (Si²⁺). The dependence of secondary ion emission on the primary ion energy was studied in a range of 2.0–20.0 keV. The yields of physically and chemically sputtered ions were almost independent of the primary ion energy. The yield of the doubly charged ion strongly depended on the primary ion energy. The energy distribution of secondary ions of the three types showed the same dependence on the primary ion energy. The most probable energy of the distribution increased with the primary ion energy. On the other hand, for the energy distribution curves of sputtered ions, the tail factors N in E^?N were constant and showed a m/e dependence.     

Nuclear orientation study of the decay of204BiFe

The decay of²⁰⁴Bi nuclei (I =6⁺, T_1/2=11·22 h) oriented in an iron host was investigated on the JINR low-temperature nuclear orientation facility SPIN. The orientation parameterB ₂=1·17 (6) was obtained from the analysis of six prominent E1 gamma-transitions. From the measured normalized intensities of the gamma-rays observed some 70 values of multipole mixing ratios for the gamma-transitions in²⁰⁴Pb nucleus were determined for the first time. The spins 6, 6, 5 and 4 could be uniquely assigned to the²⁰⁴Pb negative parity levels at 3891·5 keV, 3768·4 keV, 3301·5 keV and 2338·2 keV, respectively. The spin-parity assignments of the levels at 4183·8 keV, 4094·2 keV, 3782·0 keV, 2506·9 keV and 2065·1 keV were confirmed as 6^–, 6^–, 5^–, 5^– and 5⁺, respectively. For the level at 3105·1 keV spin-parity 5^– was suggested and spinparity 7^– of the level at 2696·4 keV was called in question. The possible placements of the gammatransitions 3 1351·7 keV and 1353·4 keV in the decay scheme is discussed. The reorientation parameters for the long-living levels at 2264·2 keV (T _1/2=0·45 s) and 1273·9 keV (T _1/2= =265 ns) were determined asG ₂=0·41 (14) andG ₂=0·60 (17), respectively. For the isomeric level at 2185·7 keV (T _1/2=67·2 min) the value ofG ₂=0·88 (49) was proposed.The authors would like to express their thanks to T. I. Kracíková and M. Trhlík for the valuable discussions in the course of the evaluation of the experimental data.     

Atom-probe field-ion microscopy of GaAs and GaP

The atom-probe field-ion microscope (atom-probe FIM) was applied for the first time to GaAs and GaP which belong to the III–V compound semiconductors. The general character of the pulsed field-evaporation of GaAs and GaP was quite similar. Ga field-evaporated predominantly in the form of singly charged ions. As and P also field-evaporated mainly as singly charged ions, but their abundances were small compared with Ga⁺. It appears that As (or P) atoms can field-evaporate more easily in the form of AsO⁺ (or PO⁺) in the presence of oxygen on the surface. In all experiments, GaAsⁿ⁺ and GaPⁿ⁺ were rarely detected. After chemical etching the surfaces were covered with oxide films and various oxide ions were detected. The abundance of oxide ions dramatically decreased after field evaporation in hydrogen. No distinct difference between the 〈111〉 orientations of these materials which have zinc-blende structure could be observed. Most of the experimental results obtained were explained in terms of the existing theory of field evaporation. It was concluded that field penetration effects have a considerable influence on the field evaporation processes of these materials as well as on the field ionization processes.     

Absolute measurement of sputtered ion fractions using matrix isolation spectroscopy

Sputtering yields for neutrals and ions have been measured by collecting the sputtered species in a noble gas matrix and determining their amounts from optical absorption spectroscopy. The atomic ion fractions for Ti and Zr bombarded by O₂⁺ at 2 keV are 0.8 and 0.4, respectively, whereas TiO and ZrO are sputtered largely as neutrals. Neutral sputtering yields from Ar⁺ bombardment arc consistent with previous measurements. The experimental results are compared with various theoretical models for the sputtering process.     

Optical emission spectroscopy by Ar ion sputtering of Ti surface under O2 environment

Visible light emission from atoms and ions sputtered on a polycrystalline Ti surface was observed under irradiation of 30 keV Ar³⁺ ions. A number of atomic lines of Ti I and II were observed in the wavelength of 250-850 nm. The intensity of Ti II emission increased 1.3-5.6 times by introducing oxygen molecules at a pressure of 5.8 × 10⁻⁵ Pa, whereas that of Ti I decreased 0.5-0.8 times. Factors enhancing or reducing photon intensities were plotted as a function of energy of the corresponding electrons in the excited states for Ti atoms and Ti⁺ ions.     

Analysis of C60 and Cs sputtering ions for depth profiling gold/silicon and GaAs multilayer samples by time of flight secondary ion mass spectrometry

Time of flight secondary ion mass spectrometry (ToF-SIMS) depth profiles of several inorganic layered samples using Cs⁺ and C₆₀⁺ primary sputtering ions of different energies are compared to evaluate sputter yield and depth resolution. A gold/silicon model system is employed to study interfaces between metals and semiconductors, and multilayers of AlGaAs, Al, and InAs in GaAs are analyzed to explore the ability of C₆₀⁺ to analyze semiconductor interfaces in GaAs. Roughness measurements are reported to differentiate between different factors affecting depth resolution. The best depth resolution from all samples analyzed is achieved using 1 keV Cs⁺. However, C₆₀⁺ sputtering has advantages for analyzing conductor/insulator interfaces because of its high sputter yield, and for analyzing deeper heterolayers in GaAs due to lower sputter-induced roughness.     

Laser annealing of GaAs dual implanted with Si and P ions

Laser annealing of SI(100) GaAs:Cr implanted either with Si⁺ ions (150 keV, 6×10¹³-1×10¹⁵cm^–2) or dual implanted with Si⁺ ions (150 keV, 6×10¹⁴–1×10¹⁵cm^–2) and P⁺ ions (160 keV, 1×10¹⁴–1×10¹⁵cm^–2) has been examined using backscatteringchannelling technique and via electrical measurement of Hall effect. It has been found that at laser energy densities 0·8 J cm^–2 a full recovery of the sample surface occurs. In dual implanted samples (1×10¹⁵ Si⁺ cm^–2+1×10¹⁵P⁺cm^–2) up to 46% of Si atoms become electrically active after the laser annealing. Resultant Hall mobility of carriers is, however,lower than that obtained after common thermal annealing.The authors are pleased to take the opportunity of thanking Professor M. Kubát for his encouragement and continuous support. Accelerator staff is gratefully acknowledged for its assistance in the course of experiments.     

Comparison of detection efficiencies of negatively charged gold-alkanethiolate-, gold-sulfur- and gold-clusters in ToF-SIMS

In order to improve quantification of high mass ions, the influence of cluster composition on detection efficiencies has been studied using a TOF-SIMS IV with the extended capability of postaccelerating ions up to 20 keV. In this experimental study, we focus on the comparison of detection efficiencies for three types of negatively charged secondary cluster ions: gold-alkanethiolate-clusters (Au_xM_y), gold-sulfur-clusters (Au_xS_y) and gold-clusters (Au_x). The clusters were sputtered from self-assembled monolayers of hexadecanethiols on gold substrates using 10 keV Ar⁺ primary ions. The detection efficiencies were derived on the basis of a function for the secondary electron yield and a fourth-order approximated Poisson probability distribution for electron propagation and amplification within the microchannel plate.In addition to the well-known dependence of detection efficiencies on ion mass and energy, which has already been studied for positively charged ions, we were able to show a similar behaviour for the investigated negatively charged secondary ions. We have observed major variations among the three types of clusters at similar mass and energy as predicted in a theoretical approach. The observed differences are due to the different composition of the investigated clusters which has a major influence on the kinetic ion induced electron emission within the microchannel plate. For the first time it was possible to experimentally verify these predictions for detection efficiencies.     

Composition and Structure of Ga<Subscript>1 – <Emphasis Type="Italic">x</Emphasis></Subscript>Na<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>As Nanolayers Produced near the GaAs Surface by Na<Superscript>+</Superscript> Implantation

The composition and structure of nanodimensional Ga_{1 – x}Na _x As phases produced by implantation of Na⁺ ions into the near-surface area of GaAs have been studied by Auger electron spectroscopy and fast electron diffraction. It has been found that the thickness of the ternary epitaxial layer is 10–12 nm for ion energy E₀ = 20 keV. The composition of the three-layer nanosystems is GaAs–Ga_0.5Na_0.5As–GaAs.     

Secondary ion and Auger electron emissions from Ar+-ion-sputtered FeAl alloys

Some FeAl alloys, and pure Al and Fe samples, are sputtered in ultrahigh vacuum with Ar⁺ ions between 4 and 15 keV. As previously observed with CuAl alloys, the intensity of the principal Al Auger peak at 63.5 eV is a parabolic function of the Al concentration. Symmetric collisions Al → Al are thus much more efficient for Auger emission from pure aluminium than asymmetric collisions Ar → Al, the proportion of which among effective collisions hardly reaches 20% at 15 keV. Whatever the initial ion energy, the intensities of singly charged atomic secondary ions Al⁺ and Fe⁺, normalized to pure metals, are equal to the atomic concentration of the corresponding elements, whereas the normalized intensities of the multiply charged ions Al²⁺ and Al³⁺ are roughly equal to the square of Al concentration. These results agree with the occurence of two mechanisms in intrinsic ion emission: an electronic excitation process during the separation of the outgoing particle from the target (singly charged ions) and a collisional process from the symmetric collisions Al → Al only, with multiple Auger de-excitation outside the target (multicharged ions of light elements).     

Low energy sputtering of neutral Cu2 molecules

The ratios of relative yields of neutral sputtered Cu₂ molecules to neutral sputtered Cu atoms were found to be linearly proportional to the sputtering yield of Cu, from a Cu target under bombardment by Ar⁺ ions (energy 50–90 eV), as determined by secondary neutral mass spectrometry.     

The influence of ion bombardment on emission properties of small dust grains

Dust grains that are present in many plasma and vacuum systems and in the space usually carry a non-negligible charge. Their charging significantly depends on surface properties of the grain material. In cold plasma, charging is mainly given by electron attachment, nevertheless, when plasma becomes hot, other processes (secondary electron emission, field emission, etc.) take place. Emission properties of the grain surface could be modified by grain baking or by ion bombardment. Our study is carried out at the dust charging experiment dealing with a single dust grain electro-dynamically levitated in a 3D quadrupole trap. The grain can be exposed to the ion beam in the energy range of 100 eV–5 keV and to the electron beam in the energy range of 100 eV–10 keV. We have chosen He⁺ and Ar⁺ ions for the surface treatment and the observed influence on the surface properties is discussed in terms of secondary emission. A non-negligible shift of the secondary electron emission yield, as well as a change of energy distribution of secondary electrons, were measured after Ar⁺ bombardment. A preliminary study suggests that the effects of He⁺ and Ar⁺ are comparable.     

Sputtering of metals at ion-electron irradiation

It has been found that, in contrast to the commonly accepted opinion, simultaneous irradiation by 15-keV Ar⁺ ions and 2.5-keV electrons at temperatures above 0.5T _m (T _m is the melting temperature) induces much larger sputtering of metallic copper, nickel, and steel than irradiation only by Ar⁺ ions. The effect increases with the temperature. At T = 0.7T _m, the sputtering coefficients in the case of ion-electron irradiation are more than twice as large as the sputtering coefficients in the case of irradiation by Ar⁺ ions. The experiments on the sublimation of copper show that the sublimation rate in the case of the heating of a sample by an electron beam is higher than that in the case of heating in an electric vacuum oven. The revealed effects are explained by the electron-induced excitation of adatoms (atoms stuck over the surface, which appear owing to ion bombardment). Excited adatoms have a smaller binding energy with the surface and are sputtered more easily.