Growth of Ni2Si by rapid thermal annealing: Kinetics and moving species

The growth kinetics is characterized and the moving species is identified for the formation of Ni₂Si by Rapid Thermal Annealing (RTA) of sequentially deposited Si and Ni films on a 100 Si substrate. The interfacial Ni₂Si layer grows as the square root of time, indicating that the suicide growth process is diffusion-limited. The activation energy is 1.25±0.2 eV in the RTA temperature range of 350–450° C. The results extend those of conventional steady-state furnace annealing quite fittingly, and a common activation energy of 1.3±0.2 eV is deduced from 225° to 450° C. The marker experiment shows that Ni is the dominant moving species during Ni₂Si formation by RTA, as is the case for furnace annealing. It is concluded that the two annealing techniques induce the same growth mechanisms in Ni₂Si formation.     

Studies of the promising material CoSi2 on GaAs substrates

The thermal stability of CoSi₂ thin films on GaAs substrates has been studied using a variety of techniques. The CoSi₂ thin films were formed by depositing Co(500 Å) and Si(1800 Å) layers on GaAs substrates by electron-beam evaporation followed by annealing processes, where the Si inter-layer was used as a diffusion/reaction barrier at the interface. The resistivity of CoSi₂ thin films formed is about 30 cm. The Schottky barrier height of CoSi₂/n-GaAs is 0.76 eV and the ideality factor is 1.14 after annealing at 750° C for 30 min. The CoSi₂/GaAs interface is determined to be thermally stable and the thin film morphologically uniform on GaAs after 900° C/30 s anneal. The CoSi₂ thin films fulfill the requirements in GaAs self-aligned gate technology.     

Formation of palladium silicide by rapid thermal annealing

The formation of palladium silicide Pd₂Si by rapid thermal annealing of Pd layers on silicon has been studied as a function of annealing time (1–60s) in the temperature range 350–500 °C. It is shown that the results found for conventional furnace annealing (long duration, low temperature) can be extrapolated for rapid thermal annealing (shorter time, higher temperature) when taking into account the exact time dependence of the short temperature cycle. The growth rate is essentially diffusion limited and the activation energy is close to 1.1±0.1 eV. Silicide resistivity of about 30–40 cm was obtained for 200–400 nm thick Pd₂Si layers formed at 400 °C for a few seconds.     

Microstructure of aluminium-copper thin films and its relation to electromigration

The microstructure of polycrystalline aluminium — 7·6 wt % copper thin films evaporated from the starting Al-Cu alloy was studied using electron microscopy and microanalysis. The structural properties of films were confronted with electromigration lifetime measurements of Al-Cu thin film conductors. In the films Al₂Cu precipitates were observed. Thermodynamically stable -Al₂Cu precipitates were found at grain boundaries, triple points and on the film surface. Within the grains -Al₂Cu precipitates were detected. When the temperature of deposition and/or the time of annealing of the films at 480 °C in nitrogen increased, the growth of grains and of the total volume of the precipitate phase was observed. Under these conditions precipitates tended to grow preferentially at the film surface and they ceased to influence the grain size distribution. The distribution approached then the log-normal distribution function. With regard to the structural investigations it is anticipated that the best electromigration resistance among the studied samples should possess conductors deposited at 250 °C as well as conductors deposited at 150 °C and 250 °C and annealed 10 min at 480 °C. The lifetimes of conductors having this type of microstructure and tested at the current density of 3×10⁶ A/cm² had values of 210÷3500 hrs, corresponding to the testing temperature of 150 °C. Higher lifetimes were observed with wider (20 m) and shortest (120 m) conductors encapsulated in packages filled with nitrogen. The activation energy for the failure process was 0·65 eV in this case.     

The role of the emitter on the diffusion current inn + p-junctions

On three different samples of crystallinep-siliconn ⁺ p-junctions have been prepared by coating the surface with a phosphorous glass and a subsequent diffusion at 915°C for 30 min. From the measurement of the short circuit current density and the open circuit voltage under high illumination conditions the diffusion current of the solar cells has been determined as a function of the temperature between 77K and 300 K. The contribution of the emitter and the base region to the diffusion current was examined. Under the assumption of Auger recombination governing the hole lifetime in the emitter the narrowing of the mobility bandgap due to the high density of states within the bandgap of the emitter was determined. A shrinkage as high as 0.18 eV was observed in the case of a 0.2 cm sample of lower purity. For high purity 6 cm silicon the reduction of the mobility bandgap was determined as 0.10 eV. A polycrystalline sample exhibits a shrinkage of 0.15 eV. The reduction of the mobility bandgap was found to determine the lower limit of the current losses due to carrier diffusion in our solar cells at current densities around 1×10^–7 Am^–2.     

Change in the substructure of cold worked aluminum crystals on subsequent heating

In this research, a relationship has been established between the polygonization of aluminum single crystals on annealing and the hardening curve for single crystals of fec metals. It has been shown by the Guinier-Tennevin X-ray focusing method that only high-temperature (600–640 °C) polygonization develops on annealing single crystals of pure (99.99%) aluminum cold worked by extension at –196 °C within stages I and II of the hardening curve. In crystals cold worked to the end of stage II, and in the whole of stage III, the polygonization process takes place at an appreciable rate even during low-temperature (450 °C) annealing. Subsequent high-temperature annealing of these single crystals leads to an increase in the degree of perfection of the crystal lattice of the subgrains whose formation began during low-temperature annealing.     

Two groups of misfit dislocations in GaAs on Si

High-resolution cross-sectional and conventional plan-view transmission electron microscope observations have been carried out for molecular beam epitaxially grown GaAs films on vicinal Si (001) before and after annealing as a function of film thicknesses and observation directions between two orthogonal 110 directions. Two groups of misfit dislocations are characterized at the interface regions between GaAs and Si by analyzing whether their extra half planes exist in the film or the substrate side. Group I misfit dislocations due to stress caused by a lattice misfit between GaAs and Si consist of partial dislocations and 60° and 90° complete dislocations in an as-grown state. With an increase in the film thickness, partial dislocations decrease and complete dislocations increase. After annealing, partial dislocations almost completely disappear and 90° perfect dislocations are predominantly observed. Group II misfit dislocations due to thermal-expansion misfit-induced stress are all 60°-type complete dislocations regardless of film thicknesses and annealing treatment.On leave from Central Research Laboratory, Hitachi, Ltd., Tokyo 185, Japan     

Temperature dependence of positron annihilation parameters in neutron irradiated molybdenum

Positron lifetime measurements have been performed for molybdenum samples containing different densities of voids and dislocation loops. The samples consisted of single crystal molybdenum exposed to 2.7×10¹⁸ fast neutrons/cm₂ at 60°C, and subsequently annealed at 650°, 725°, 800°, and 875°C in vacuum (p<10^–7 Torr). After each annealing, where the densities of voids and loops were changed, positron lifetime measurements were performed in the temperature interval [–194°, 285°C]. In two-term fits of the measured spectra the longer lifetime, _e2-460 ps corresponds to an intensityI _e2 increasing with sample temperature. The shorter lifetime _e1 decreases with increasing temperature. A three-state trapping model with and without detrapping is discussed, and appears to be incapable of explaining the observed temperature dependences. A four-state positron trapping model including detrapping is necessary and satisfactory. It describes positron trapping to voids and trapping to dislocation loops, which is followed by a competition between detrapping and positron transition to jogs or other dislocation-bound defects. Mathematical expressions of the four-state trapping model including detrapping are worked out and calculations of the intensityI _e2 are compared with the experimental values ofI _e2. By use of special models for the temperature dependence of trapping rates, numerical values can be determined for the positron-dislocation-binding energy and for specific positron trapping rates.     

Rapid thermal annealing and titanium silicide formation

Titanium silcides have been formed on monocrystalline (111) silicon substrates by rapid thermal annealing (RTA) of Ti layers deposited on Si at 700–800 °C for 1 to 240 s. The phase composition is dependent on the annealing temperature and time: at 700° and 750 °C for short annealing, TiSi and TiSi₂ are observed. At 800 °C and by increasing the exposure time at 700 ° and 750 °C, only TiSi₂ is detected. The growth of the total silicide thickness is found to be faster for RTA than for conventional furnace annealing and governed by two different mechanisms depending on the phases formed: in the range 700–750 °C, and 750–800 °C, activation-energy values of 2.6 ± 0.2 and 1.5 ±0.2 eV are found, respectively.For a thin deposited Ti layer (< 100 nm), the whole Ti is finally transformed into TiSi₂ with 20@ cm resistivity. For thicker Ti thicknesses, titanium oxide stops the reaction.     

Optical Properties and Structure of Electroluminescent SiOx:Tb Films

Using nondestructive optical methods (measurement of transmission spectra in the visible and IR regions and multiangular ellipsometry), we have studied the structural changes in SiO _x :Tb films subjected to high–temperature annealing in air, which are responsible for the appearance of electroluminescence in light–emitting structures based on them. It has been established that the appearance of green electroluminescence in such a film (upon annealing of the film in air at temperatures of 600–800°C) is due to the structural changes in its matrix, leading to partial disproportionation of the thermally deposited SiO _x :Tb film (as a result, the film represents a mixture of several phases – Si, SiO_x, and SiO₂). Films showing blue electroluminescence (annealing temperature 1000°C) are characterized by a higher content of oxygen, a better compactness, and a better macroscopic homogeneity in comparison with films showing green electroluminescence. It is also shown that the thermal cycling accompanying the annealing leads to the appearance of birefringence and scattering in SiO _x O:Tb films. It is anticipated that the annealing–stimulated structural changes taking place at both the micro– and the macrolevel should cause changes in the local surroundings of the luminescence center and in the conditions for heating the charge carriers exciting the luminescence centers.     

Channeling measurement of residual damage in silicon

Conclusion The present resulte are in general agreement with those obtained earlier, e.g. in /2/. The complete removal of post-implantation defects in As-implanted Si may be achieved by thermal annealing at temperatures above 700°C and by laser annealing as well. More than 50% of the implanted As atoms enter the host lattice sites during the thermal annealing. By laser annealing, on the other hand, 9056 of the As atoms become substitutional.Some of the samples under study were kindly analysed by Dr. R. Grotzschel in ZfK Rossendorf (GDR). The results obtained in ZfK are in good agreement with the present ones. We thank Dr. J. ervená for her help in processing the measured spectra. The excellent collaboration with the staff of the Van de Graaff accelerator at NPI is also gratefully acknowledged.     

Opto-thermal study of the melting transition of benzophenone

We report a series of opto-thermal transient emission radiometry (OTTER) measurements on benzophenone over the temperature range 20–80°C, which includes the melting transition at 48°C. At temperatures sufficiently close, but below the melting point, the form of the opto-thermal decay curves was found to change, when the laser pulse energy was sufficient to cause transient melting near the surface. Such measurements could be useful in the study of re-crystallation dynamics in pulsed laser annealing and similar surface treatments. In addition, the experiment gives a direct measure of ₀, the initial jump in surface temperature, and a comparison of solid and liquid thermal diffusivities. The values found in the present study are ₀, andD(solid)/D(liquid)=2.2±0.2.     

Rates of change in high temperature electrical resistivity and oxygen diffusion coefficient in Ba2YCu3Ox

The change in electrical resistance with time for bulk, thick-film, and thin-film Ba₂YCu₃O_x at atmospheric pressure is described as a function of the oxygen partial pressure (100 to 0.001%) and temperature (320°–750°C). The potential usefulness of these materials as oxygen sensors is demonstrated. The rate of equilibration is faster during oxygen uptake than during its loss. Time constants to reach equilibration (1/e remaining), qualitatively scale with sample dimensions. For a 1m film at 600° C, <1 s for the range of P_O2 (O2 being a shorthand for O₂) from 100% to 0.001%. The rate increases markedly with increasing P_O2. The actual resistance decreases with P_O2 at a rate of log/log P_O2 = 0.4 at 700° C showing adequate sensitivity for sensor purposes. Times for the transient resistance change in the sample where used to estimate the oxygen diffusion coefficient in the ceramic. The diffusivities obtained are 4·10^–11–1·10^–12 cm²/s in the 435°–320° C range, with an activation energy of 27 kcal/mole.     

Threading dislocations in GaAs on Si grown with ∼1 nm thick Si interlayers

Threading dislocation morphologies and characteristics have been investigated in 3 m thick GaAs films with ultrathin (1 nm) Si interlayers grown by molecular beam epitaxy on tilted (2° toward [110]) Si (001) substrates using cross-sectional transmission electron microscopy. Four sample structures are studied in which different numbers of ultrathin Si layers are grown at different positions in the GaAs film, and the results are compared for samples observed before and after ex situ annealing. In all of the sample structures, some mixed-type dislocations are clearly blocked by the Si interlayers, although some of them pass through these layers, resulting in propagation of their threading dislocations to the sample surface. After annealing at 900 °C for 10 s or 800 °C for 30 min, the interactions of the dislocations with the interlayers are enhanced, and there is an increase in the number of dislocations which are bent along the 110 directions at the positions of the Si barrier layers. However, a considerable number of dislocations still escape from the Si barriers by gliding on {111} slip planes during annealing. Moreover, ex situ annealing generates new edge-type dislocations through interactions between moving threading dislocations. The nature of the dislocations that cross the Si barriers is especially discussed.     

Growth process and surface structure of MnSi on Si(1 1 1)

The solid-phase epitaxial growth process and surface structure of MnSi on Si(1 1 1) were investigated by coaxial impact-collision ion scattering spectroscopy (CAICISS) and atomic force microscopy (AFM). For the Si(1 1 1) sample deposited with 30 monolayers (ML) of Mn at room temperature, the intermixing of Mn and Si gradually started at 100 °C and reached equilibrium at approximately 400 °C. At this equilibrium state, the Mn atoms were transformed into crystalline MnSi film. Further annealing caused the desorption of Mn atoms. We identified the structure of MnSi as cubic B20 and the crystallographic orientation relationships as Si(1 1 1)//MnSi(1 1 1) and Si[]//MnSi[]. The MnSi(1 1 1) surface was found to have a dense Si terminating layer on its topmost surface. On the other hand, 3 ML of Mn deposited on Si(1 1 1) reacted with Si even at room temperature and formed a pseudomorphic structure. This structure was transformed into MnSi after annealing. A filmlike morphology with protrusions was observed for the sample with 30 ML of Mn, while island growth occurred for the sample with 3 ML of Mn.     

Effect of magnetic field on tempering processes in silicon iron

The effect of magnetic fied on the annealing of silicon iron (3% Si) was studied in the temperature range 480–680°C. The imposition of a magnetic field at 480°C leads to more complete tempering by comparison with similar annealing without field. The effect of the magnetic field on the primary recrystallization texture of the silicon iron is shown: this is expressed in the enhanced scattering of deformation type orientations in the annealing texture.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 1, pp. 82–87, January, 1973.     

Properties of RF sputtered ZnxCd1−xS thin films

Zn _x Cd_1–x S thin films (0x0.20) were prepared using rf sputtering in argon atmosphere and characterized using X-ray diffraction, optical transmission, electrical resistivity and photoconductive decay measurements. The films were found to possess hexagonal structure. The crystallite size and degree of preferential orientation were found to decrease with the increase ofx and to improve upon annealing in vacuum at 250 °C. The transmission edge shifted towards shorter wavelengths with the increase ofx in agreement with the expected shift in the energy band gap. The films were found to exhibit room temperature resistivity in the range 100–1000 cm. The obtained values of long wavelength transmission (70–80%) and minority carrier diffusion length (30 m) are high enough for the application of these films in the field of solar cells.     

On the mechanism of conduction and photoconduction in PbTe films

Conductivity, photoconductivity, thermoelectric, Hall and photothermoelectric measurements have been carried out on vacuum evaporated, air exposed PbTe films of different thickness in the temperature range 300 K-130 K to probe into the mechanism of conduction and photoconduction in these films. The dark electronic transport properties have been explained considering accumulation layers on the free surface and substrate-film interface and also the diffusion of oxygen inside PbTe microcrystals. It appears that both bulk and potential barrier scattering predominate in the high temperature region (300 K-250 K) and only barrier scattering can explain the low temperature carrier mobility at lower temperatures (250 K-130 K). Photoconductivity can be described with trapping of minority carriers within the PbTe microcrystals in the low temperature region and in the high temperature region with diffusion of minority carriers to the surface. The same oxygen trap situated at a depth of 0·06 eV from the conduction band is found to be responsible for both conduction and photoconduction in the low temperature region.Notation N _t Total trap concentration - N _r Total recombination centre concentration - n _t Electron concentration at the trapping centres - n _r Electron concentration at the recombination centres - _n Capture coefficient of electrons by recombination centres - _p Capture coefficient of holes by recombination centres - Capture coefficient of electrons/holes by trapping centres - E _t, E ₁ ^* Trap energies - E _c Conduction band edge - E _v Valence band edge - f Number of electron-hole pairs generated per unit volume per unit time - N _c Effective density of states at the conduction band edge - Potential barrier height - _p Life time of non-equilibrium holes - _s Surface barrier height in dark - _sl Surface barrier height under illumination - n _b Free electron concentration - P _b Free hole concentration - _s Surface mobility of holes - _b Bulk mobility of holes The authors are grateful to Prof. H. N. Bose for helpful discussions.     

Ultrathin amorphous Ni-Ti film as diffusion barrier for Cu interconnection

5-nm-thick amorphous Ni-Ti films deposited on Si by magnetron sputtering, annealed at various temperatures in high vacuum, have been studied as diffusion barriers for Cu interconnection using X-ray diffraction, atomic force microscopy and four-probe methods. Although no Cu silicide peaks are found from X-ray diffraction patterns of the samples annealed up to 750 °C, it is found that the sheet resistance of Cu/Ni-Ti/Si decreases with the increase of annealing temperature and then slightly increases when the annealing temperature is higher than 700 °C. Root mean square roughness of Cu/Ni-Ti/Si increases with the increase of annealing temperature and many island-like grains present on the surface of the 750 °C annealed sample, which is ascribed to dewetting and agglomeration.     

Magnetic diffusion anomaly in the Fe-17·6 at.%V alloy

Results of measurement between 746 and 1231 C of the diffusion coefficient Fe-59 in the Fe-17·6 at.% V alloy, together with Mirani's et al., Lai-Borg's and Hettich's et al. data analysis, are presented. All the data show a marked ferromagnetic effect, i.e. the lnD(T) values measured at the temperaturesT< are distinctly lower than those extrapolated by the linear Arrhenius plot from the paramagnetic range. The results are interpreted in terms of the Heisenberg model, Kirkwood's and Girifalco's statistical theories. The computer fit of an analytical form, derived for the excess activation enthalpyH(T), to experimental data enabled us to calculate the values of the exchange integralJ ₀ and the paramagnetic temperatureT _p. The corresponding values for the Fe-17·6% V alloy are:J ₀=(315±11)k,k is the Boltzmann constant, andT _p=(1223±±18) K. The activation enthalpy of Fe self-diffusion in a completely ordered ferromagnetic Fe-17·6% V matrix is higher by the value ofH(0)=(55·2±1·9)kJ/mol than the value 236·35 kJ/mol corresponding to a fully paramagnetic state. Applying a three paramagnetic fit to Mirani's, Lai-Borg's and Hettichs data, we have found that the ratio of the vacancy migration enthalpy and of the formation enthalpy in -Fe, in Fe-17·6% and Fe-7·64% Si, may be expressed by the valueH _M/H _F=1·62 ± 0·18. A comparison ofJ ₀(-Fe) toJ ₀(17·6 %V) and toJ ₀(7·64% Si) shows that the magnetic dilution caused by 17·6% of vanadium is negligible withJ ₀(17·6% V)/ /J ₀(-Fe)=0·999. The dilution brought about by silicium is by about 1·24 times higher, and the ratioJ ₀(7·64% Si)/J ₀(-Fe)=0·86. The paramagnetic temperatures in the materials under study are given by the relationT _P=(gQ + 137) K, being the respective Curie-temperature. The present analysis makes it possible to calculate the Fe diffusion characteristicsD _0f aH _f in a fully ordered magnetic matrix.