Formation of Cu nanoparticles in GaAs using MeV ion implantation followed by thermal annealing

Analytical electron microscopy, high-resolution X-ray diffraction and combined Rutherford backscattering spectrometry and channeling experiments have been used to investigate the radiation damage and the effect of post-implantation annealing on the microstructure of GaAs(100) single crystals implanted with 1.00 MeV Cu⁺ ions to a dose of ≈ 3×10¹⁶ cm^-2 at room temperature. The experiments reveal the formation of a thick and continuous amorphous layer in the as-implanted state. Annealing up to 600 °C for 60 min does not result in the complete recovery of the lattice order. The residual disorder in GaAs has been found to be mostly microtwins and stacking fault bundles. The redistribution of implanted atoms during annealing results in the formation of nano-sized Cu particles in the GaAs matrix. The X-ray diffraction result shows a cube-on-cube orientation of the Cu particles with the GaAs lattice. The depth distribution and size of the Cu particles have been determined from the experimental data. A tentative explanation for these results is presented. Received: 15 February 1999 / Accepted: 18 February 1999 / Published online: 28 April 1999     

Pulsed electron-beam annealing of high-dose arsenic implanted silicon

The effects of pulsed electron-beam annealing of high-dose As implanted {111} Si single crystals has been studied. The depth distributions and lattice location of the As atoms were obtained using MeV⁴He⁺ backscattering and channeling technique. The implantation energy was 100 keV with a total dose of 3.5·10¹⁶/cm². Above the threshold energy of 0.9 J/cm² the single-crystal transition was observed with about 95% of the As atoms on substitutional lattice sites. This leads to an As concentration of 2·10²¹/cm³ which was demonstrated to be a metastable one.     

Fabrication and evolution of Cu nanoparticles in Al2O3 crystal by ion implantation and annealing at different atmospheres

Single crystal Al₂O₃ samples were implanted with 45 keV Cu ion implantation at a dose of 1 × 10¹⁷ ions/cm², and then subjected to furnace annealing in vacuum or with a flow of oxygen gas. Various techniques, such as ultraviolet-visible spectroscopy, X-ray diffraction spectroscopy and atomic force microscopy, have been used to investigate formation of Cu NPs and their evolution. Our results clearly show that the evolution of Cu NPs depends strongly on annealing atmosphere in the temperature range up to 600 °C. Annealing in vacuum only gives rise to a slight change in the size of Cu NPs. No evidence for oxidization of Cu NPs has been revealed. Remarkable modifications in Cu NPs, including the size increase and the effective transformation into CuO NPs, have been observed for the samples annealed at oxygen atmosphere. The results have been tentatively discussed in combination with the role of oxygen from atmosphere in diffusion of Cu atoms towards the surface and its interactions with Cu NPs during annealing.     

The lattice location and hyperfine field of implanted Yb in Fe as a function of annealing temperature

A combined study has been made of the lattice location and hyperfine field of Yb implanted into Fe single crystals. The location has been determined by ion channeling and back-scattering, the hyperfine field by perturbed angular correlation (PAC) measurements on¹⁶⁹Yb (decaying to excited states in¹⁶⁹Tm). The channeling experiments indicate that initially about 60% of the Yb atoms occupy substitutional sites in the Fe lattice, while the remaining atoms are not in any specific crystallographic site. On annealing, Yb migrates from substitutional to non-substitutional sites. No Yb atoms remain substitutional after a 600°C anneal. By making PAC measurements at two temperatures for two - cascades in¹⁶⁹Tm, it is found that the PAC pattern can be described using a combined static and time-dependent magnetic interaction. The PAC results show that the average hyperfine field and relaxation parameter decrease on annealing, and that the field disappears after a 600°C anneal. The correlation between the location and the hyperfine field is discussed. A comparison of the results with previous Mössbauer results for¹⁵¹Gd implanted in Fe, together with relaxation parameter measurements on a¹⁶⁹Yb₂O₃ source, suggests that the non-substitutional Yb is internally oxidized in the Fe host.Work partly carried out while at the Clarendon Laboratory, Oxford, England and Nuclear Physics Division, AERE, Harwell, England.     

CW CO2-laser annealing of arsenic implanted silicon

CW CO₂-laser annealing of arsenic implanted silicon was investigated in comparison with thermal annealing. Ion channeling, ellipsometry, and Hall effect measurements were performed to characterize the annealed layers and a correlation among the different methods was made. The laser annealing was done with power densities of 100 to 640 W cm⁻² for 1 to 20 s. It was found that the lattice disorder produced during implantation can be completely annealed out by laser annealing with a power density of 500 W cm⁻² and the arsenic atoms are brought on lattice sites up to 96±2%. The maximum sheet carrier concentration of 6×10¹⁵ cm⁻² was obtained for 1×10¹⁶ cm⁻² implantation after laser annealing, which was up to 33% higher than that after thermal annealing at 600 to 900°C for 30 min.     

硼/氮原子共掺入金刚石的晶格损伤及其退火过程的计算机模拟

借助于Tersoff势函数和分子动力学模拟技术研究了室温下500eV的能量粒子硼(4个)和氮(8个)共掺入金刚石晶体中所引起的损伤区域内晶体微细观结构的变化特征以及后续加热退火晶体结构的演变特征.结果表明：随着掺入原子数目的增加，受影响的区域范围渐渐增大，12个粒子全部注入金刚石晶体后局部影响区域的半径达0.68nm，损伤区域中心的三配位原子数增加而四配位数原子数量减少.加热退火过程中损伤中心区域的原子发生扩散，部分原子的扩散距离达到4个晶格间距.加热退火使损伤区域中心原子间的平均键长趋于金刚石结构的键长.退火后薄膜中注入的杂质原子向表面扩散引起应力分布产生变化，杂质原子经过一系列的扩散过程能够到达空位的位置，减少薄膜中空位数量，减小晶格畸变程度，原子向表面扩散引起应力产生重新分布，薄膜中应力峰值的峰位向薄膜表面发生移动，局部应力集中程度降低.通过不同退火温度的比较发现低温下退火(800℃)更有利于空位的运动和晶格损伤的恢复从而提高晶格质量. 关键词： 金刚石共掺杂 分子动力学 退火     

Effect of radiation annealing on activation of silicon implanted in gallium arsenide

We have investigated the profile of²⁸Si implanted in GaAs obtained by radiation annealing using an electron beam (P=7.6 W/cm², E=10 keV, t=10 sec, T≅750°C) and thermal annealing in a furnace (T=800°C, t=30 min). It was found that the radiation annealing provides diffusion redistribution of the impurities and a high degree of electrical activation. Tomsk Polytechnic University. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 7, pp. 89–92, July, 1998.     

Location of 125I implanted in silicon and germanium

A Mössbauer study of ¹²⁵I implanted into silicon and germanium lattices with various dose values was performed. The spectra measured after thermal annealing suggested an off-substitutional site population for I in the silicon lattice. The Mössbauer spectra showed no difference in the hyperfine splitting of ¹²⁵Te after electron capture of ¹²⁵I in comparison with that obtained after the isomeric transition of implanted ^125mTe. The site populations of Te and I atoms after implantation and thermal annealings were concluded as being the same.     

Impurity lattice location and recovery of structural defects in semiconductors studied by emission channeling

Doping of semiconductors by ion implantation usually requires implantation doses below 10¹³ cm^–2 to obtain typical impurity concentrations of <10¹⁸ cm^–3. The lattice location of impurities as well as the defect recovery after such low dose implantations can be studied using the emission channeling technique. In this technique, single crystals are doped with radioactive probe atoms and the channeling effects of electrons, positrons or -particles emitted from these atoms are measured. We present a quantitative analysis of electron emission channeling measurements after heavy-ion implantation into Si and III–V compound semiconductors by comparison with calculated channeling profiles based on the dynamical theory of electron diffraction. For In atoms implanted into Si, complete substitutionality was found after rapid thermal annealing to 1200 K. For lower annealing temperatures, the observed channeling effects indicate small mean displacements (of about 0.2 Å) of the In atoms from substitutional sites, caused by residual implantation defects. For GaAs, GaP and InP implanted at low temperatures with In or Cd isotopes, pronounced recovery stages around 300, 400 and 350 K, respectively, were observed and substitutional fractions close to 100% were derived after annealing above the stage.     

Ag-Cu离子注入玻璃后不同气氛退火的光吸收研究

采用MEVVA源（metal vapor vacuum arc ion source）引出的强束流脉冲Ag,Cu离子先后注入到SiO₂玻璃，x射线光电子能谱仪（XPS）分析显示Ag，Cu大多仍为金属态，有部分氧化态Cu存在.透射电镜观察分析和光学吸收谱都表明在衬底中形成了纳米合金颗粒.结合有效媒质理论，得到模拟的光学吸收谱，与实验结果基本符合，较好地验证了以上结论.样品退火后颗粒发生分解，分解的颗粒在氧化气氛下被氧化，且有部分向样品表面蒸发；在还原气氛下氧化态元素被还原并成核生长.故 关键词： 离子注入 纳米颗粒 退火 光学吸收率     

CEMS study of defect annealing in Fe implanted AlN

An AlN thin film grown on sapphire substrate was implanted with 45 keV ⁵⁷Fe and ⁵⁶Fe ions at several energies to achieve a homogeneous concentration profile of approximately 2.6 at.%. in the AlN film. Conversion electron Mössbauer Spectroscopy data were collected after annealing the sample up to 900 °C. The spectra were fitted with three components, a single line attributed to small Fe clusters, and two quadrupole split doublets attributed to Fe substituting Al in the wurtzite AlN lattice and to Fe located in implantation induced lattice damage. The damage component shows significant decrease on annealing up to 900 °C, accompanied by corresponding increases in the singlet component and the substitutional Fe.     

Electron irradiation assisted annealing of boron and phosphorus implanted silicon layers

Radíatíon annealing due to a 1.0 MeV election beam of intensity 25 μA/cm² was studied in silicon samples implanted with phosphorus and boron ions and annealed at 350–500°C. A significant annealing enhancement as compared to thermal annealing has been observed in phosphorus-implanted samples. In boron-implanted samples, a fast initial rise of electrical activity is followed by a continuous decrease of carrier concentration. The results are interpreted in terms of two competing processes: electron irradiation induced removal of post-implantation defects and introduction of simple electrically active defects.     

Anomalous Temperature Dependence of the EFG in AlN Measured with the PAC-Probes 181Hf and 111In

¹⁸¹Hf and ¹¹¹In ions were implanted into AlN-layers in order to investigate their immediate lattice site environment and its temperature dependence by means of the Perturbed Angular Correlation (PAC) technique. After rapid thermal annealing at 1273 K up to 50% of the probe atoms were incorporated on undisturbed lattice sites defined by an electric field gradient (EFG) of 33 MHz for In and 572 MHz for Hf for measurement at room temperature. PAC-spectra taken at temperatures between 25 and 1200 K show that the EFG measured at the site of the undisturbed probes changes with temperature. While for Hf it decreases by 3%, for In it increases by 25% within the measured temperature range. Thus, the change cannot be due only to the thermal lattice expansion. In the case of In the fraction of probe atoms on substitutional sites increases with temperature until it reaches nearly 100% at 973 K. These effects are fully reversible. For the Hf probe, an additional EFG was detected at temperatures above 300 K.     

Vacancy trapping and helium decoration in Sb ion-implanted tungsten studied by Mössbauer spectroscopy

Mössbauer effect measurements have been performed using sources of¹¹⁹Sb implanted in W without and with post-implanted helium. Each of the sources was subjected to an isochronal annealing sequence in order to study vacancy trapping, helium decoration and recovery of damage. Four sites have been identified for Sb implanted in tungsten; one of these corresponds with substitutional Sb atoms, two others are assigned to Sb atoms associated with vacancies, while the last one can be either vacancy or impurity associated. The development of site occupation as a function of annealing temperature is in accordance with the one-interstitial model. Injection of 2·10¹⁶ He/cm² leads to nucleation of helium bubbles. Helium atoms that are released from these bubbles at about 1300 K are retrapped by Sb atoms to form new bubbles.     

Mössbauer-Effect Study of Metastable c-FeSi Synthesized by Molecular Beam Epitaxy (MBE) and by Ion Implantation

Conversion electron Mössbauer spectroscopy (CEMS) has been applied to the study of the metastable c-FeSi phase (i.e. an iron silicide with CsCl lattice structure) that was synthesized by implantation of Si + ions of 50 keV in energy into f -Fe (95% 57 Fe) near room temperature with a nominal dose of 5 2 10 17 cm m 2 , and by molecular beam epitaxy (MBE). Iron silicide layers with different stoichiometry (FeSi 0.85 , FeSi, Fe 0.85 Si) were grown by codeposition of 57 Fe and Si onto an Fe buffer layer on MgO(100). For all FeSi layers the defective CsCl structure was observed after annealing at different temperatures. X-ray diffraction measurements were performed to determine the structure and epitaxial relationship of the c-FeSi films. The lattice parameter perpendicular to the film plane was found to be 2.77(5) Å. CEMS measurements revealed a lower than cubic site symmetry of the iron atoms for both the c-FeSi layers synthesized by ion implantation and by MBE. The formation of nearly undistorted c-FeSi after annealing is favored by excess Fe atoms in the deposited film.     

Damage annealing behavior of Se implanted GaAs

High resolution Rutherford backscattering-channeling (RBS-C) and transmission electron microscopy (TEM) have been used to investigate the annealing behavior of Se implanted Cr-doped GaAs layers. Two distinct annealing stages were observed; one at 250°C which is associated with amorphous zone annihilation and/or onset of solid phase epitaxial growth and the other at about 400–500°C, depending on the dose, that can be related to the dissociation of microtwins. Above 500°C, the residual defects are primarily dislocation loops and precipitates. The calculated number of atoms associated with the precipitates has been found to correspond closely to the number of implanted atoms, implying 100% precipitation for the cases studied in this work. This could explain the poor or nonexistent electrical activation of Se after low temperature annealing (6&#x0303;00°C), even though good regrowth of the amorphous layer has taken place. Experiments with high purity GaAs produced the same result, as far as the observed residual damage was concerned, thus eliminating speculation about the involvement of Cr in the nucleation of microtwins. Transmission electron microscopy investigations of the amorphous-crystalline interface in the as-implanted samples failed to reveal any extended defects. In the present paper, we discuss various mechanisms that could be responsible for the formation of twins in low temperature annealed GaAs.     

Laser annealing of radiation defects in low disordered layers

Abstract

Carrier concentration and mobility dependences on the annealing temperature have been compared for the cases of thermal (10 min) and laser (8 ms) annealing of silicon, implanted with low doses of P⁺ ions. It was found that the recovery of concentration and mobility depended on the heating time in different ways. The laser annealing requires higher temperatures for mobility recovery then the thermal treatment. The same temperature shift was observed for increase of carrier concentration but only after doses less than 3.10¹²m^?2. When the doses exceeded 3.10¹² cm^?2 laser and thermal annealing resulted in equal electron concentrations providing the equality of heating temperatures. Annealing of disordered regions was accounted for the mobility recovery. The increase of electron concentration was explained as an instantaneous decay of defect-impurity complexes. To check the validity of the assumptions laser annealing of electron and light ions irradiated materials was investigated.     

Incorporation of the transition metal Hf into GaN

The perturbed angular correlation (PAC) technique was applied to study the incorporation of the transition metal Hf into GaN after implantation. To this end the PAC probe ¹⁸¹Hf(¹⁸¹Ta) was implanted into epitaxial Wurtzite GaN layers (1.3 μm on sapphire) with an energy of 160 keV and doses of 7× 10¹² at/cm². PAC spectra were recorded during an isochronal annealing programme, using rapid thermal annealing (RTA) and furnace annealing, in the 300–1000oC temperature range. After implantation the spectra show a damped oscillation corresponding to a quadrupole interaction frequency (QIF) of ν_Q= 340 MHz for 30% of the probe nuclei. Annealing up to 600oC reduces the damping of this frequency without an increase of the probe atom fraction f_s in these sites. Above 600oC f_s grows rapidly until after the 900oC RTA step more than 80% of the Hf probes experience a well defined QIF due to the incorporation of Hf on undisturbed sites of the hexagonal GaN wurtzite lattice. An interaction frequency of ν_Q= 340 MHz is derived. RTA and furnace annealing yield similar results for annealing up to 800oC, where the undisturbed fraction reaches about 60%. Then RTA at higher temperatures increases this fraction, while furnace annealing leads to a decrease down to 22% after annealing at 1000oC. To our knowledge this is the first time that a transition metal probe like Hf is incorporated to such a large extent into a semiconductor lattice. This revised version was published online in August 2006 with corrections to the Cover Date.     

Amorphisation of GaN during processing with rare earth ion beams

GaN epilayers grown by metal organic chemical vapor deposition (MOCVD) were implanted with Tm and Eu ions with different energies and fluences and at different temperatures in order to optimize the implantation conditions. The recovery of the implantation damage was studied using both rapid thermal annealing and furnace annealing with nitrogen overpressure of 4×10⁵ Pa. Rutherford backscattering spectrometry in the channeling mode (RBS/C) was used to monitor the evolution of damage introduction and recovery in the Ga-sublattice and transmission electron microscopy (TEM) was carried out for further structural analysis. The RBS/C spectra as well as TEM images show two different damage regions, one at the surface arising from an amorphous surface layer and another one deeper in the crystal coinciding with the end of range of the implanted ions. For implantation with 150 keV at room temperature, even for fluences as low as 3×10¹⁴ at/cm², a thin amorphous surface layer, which becomes thicker with increasing implantation fluence, was observed by TEM. High temperature annealing of these highly damaged layers often results in loss of the amorphous layer and accumulation of the implanted species at the surface rather than a regrowth of the crystal. It was possible to prevent the formation of an amorphous layer by implanting at 500 C. In those samples a large part of the lattice damage was removed during annealing at 1000 C and the recovery of the lattice is similar for both applied annealing methods.     

Measurements of the electric field gradient at cadmium in the high Tc superconductor YBa2Cu3O6+x

The electric field gradient (EFG) at¹¹¹Cd probe atoms in YBa₂Cu₃O_6+x has been studied by the perturbed angular correlation (PAC) spectroscopy. After annealing at temperatures below 1000 K the probe atoms are located at the Cu(1) site; above 1100 K they preferentially occupy the Y site, whereas in the intermediate temperature range they also reside on the Ba site. A reduction of the oxygen content from x=1.0 to 0.2 resulted in a decrease of the asymmetry parameter measured at the Ba site, but in an increase of it at the Y site, indicating there a local distortion of the YBa₂Cu₃O_6+x lattice by the Cd impurity. Two different surroundings for the Cd atoms at the Cu(1) site were observed.