Optical properties of excited silicon and germanium at low temperatures

Part I of this thesis deals with 3 topics concerning the luminescence from bound multi-exciton complexes in Si. Part II presents a model for the decay of electron-hole droplets in pure and doped Ge.

Part I.

We present high resolution photoluminescence data for Si doped With Al, Ga, and In. We observe emission lines due to recombination of electron-hole pairs in bound excitons and satellite lines which have been interpreted in terms of complexes of several excitons bound to an impurity. The bound exciton luminescence in Si:Ga and Si:Al consists of three emission lines due to transitions from the ground state and two low lying excited states. In Si:Ga, we observe a second triplet of emission lines which precisely mirror the triplet due to the bound exciton. This second triplet is interpreted as due to decay of a two exciton complex into the bound exciton. The observation of the second complete triplet in Si:Ga conclusively demonstrates that more than one exciton will bind to an impurity. Similar results are found for Si:Al. The energy of the lines show that the second exciton is less tightly bound than the first in Si:Ga. Other lines are observed at lower energies. The assumption of ground state to ground-state transitions for the lower energy lines is shown to produce a complicated dependence of binding energy of the last exciton on the number of excitons in a complex. No line attributable to the decay of a two exciton complex is observed in Si:In.

We present measurements of the bound exciton lifetimes for the four common acceptors in Si and for the first two bound multi-exciton complexes in Si:Ga and Si:Al. These results are shown to be in agreement with a calculation by Osbourn and Smith of Auger transition rates for acceptor bound excitons in Si. Kinetics determine the relative populations of complexes of various sizes and work functions, at temperatures which do not allow them to thermalize with respect to one another. It is shown that kinetic limitations may make it impossible to form two-exciton complexes in Si:In from a gas of free excitons.

We present direct thermodynamic measurements of the work functions of bound multi-exciton complexes in Al, B, P and Li doped Si. We find that in general the work functions are smaller than previously believed. These data remove one obstacle to the bound multi-exciton complex picture which has been the need to explain the very large apparent work functions for the larger complexes obtained by assuming that some of the observed lines are ground-state to ground-state transitions. None of the measured work functions exceed that of the electron-hole liquid.

Part II.

A new model for the decay of electron-hole-droplets in Ge is presented. The model is based on the existence of a cloud of droplets within the crystal and incorporates exciton flow among the drops in the cloud and the diffusion of excitons away from the cloud. It is able to fit the experimental luminescence decays for pure Ge at different temperatures and pump powers while retaining physically reasonable parameters for the drops. It predicts the shrinkage of the cloud at higher temperatures which has been verified by spatially and temporally resolved infrared absorption experiments. The model also accounts for the nearly exponential decay of electron-hole-droplets in lightly doped Ge at higher temperatures.

Superconductivity, spin-glass properties, and ferromagnetism in amorphous La-Gd-Au alloys

The superconducting and magnetic properties of splat cooled amorphous alloys of composition (La_100-xGd_x)₈₀Au₂₀ (0 ≤ x ≤ 100) have been studied. The La₈₀Au₂₀ alloys are ideal type II super-conductors (critical temperature T_c = 3.5° K ). The concentration range (x less than 1) where superconductivity and spin-glass freezing n1ight coexist has been studied in detail. The spin-glass alloys (0 less than x less than 70) exhibit susceptibility maxima and thermomagnetic history effects. In the absence of complications due to crystal field and enhanced matrix effects, a phenomenological model is proposed in which the magnetic clusters are treated as single spin entities interacting via random forces using the molecular field approach. The fundamental parameters (such as the strength of the forces and the size of clusters) can be deduced from magnetization measurements. The remanent magnetization is shown to arise from an interplay of the RKKY and dipolar forces. Magnetoresistivity results are found to be consistent with the aforementioned picture. The nature of magnetic interactions in an amorphous matrix is also discussed. The moment per Gd atom (7µ_B) is found to be constant and close to that of the crystalline value throughout the concentration range investigated. Finally, a detail study is made of the critical phenomena and magnetic properties of the amorphous ferromagnet: Gd₈₀Au₂₀. The results are compared with recent theories on amorphous magnetism.

The electrical and magnetic properties of amorphous Pd-Cu-P alloys

The amorphous phases of the Pd-Cu-P system has been obtained using the technique of rapidly quenching from the liquid state. Broad maxima in the diffraction pattern were obtained in the X-ray diffraction studies which are indicative of a glass-like structure. The composition range over which the amorphous solid phase is retained for the Pd-Cu-P system is (Pd_100-xCu_x)₈₀P₂₀ with 10 ≤ x ≤ 50 and (Pd₆₅Cu₃₅)_100-yP_y with 15 ≤ y ≤ 24 and (Pd₆₀Cu₄₀)_100-yP_y with 15 ≤ y ≤ 24.

The electrical resistivity for the Pd-Cu-P alloys decreases with temperature as T² at low temperatures and as T at high temperatures up to the crystallization temperature. The structural scattering model of the resistivity proposed by Sinha and the spin-fluctuation resistivity model proposed by Hasegawa are re-examined in the light of the similarity of this result to the Pt-Ni-P and Pd-Ni-P systems. Objections are raised to these interpretations of the resistivity results and an alternate model is proposed consistent with the new results on Pd-Cu-P and the observation of similar effects in crystalline transition metal alloys. The observed negative temperature coefficients of resistivity in these amorphous alloys are thus interpreted as being due to the modification of the density of states with temperature through the electron-phonon interaction. The weak Pauli paramagnetism of the Pd-Cu-P, Pt-Ni-P and Pd-Ni-P alloys is interpreted as being modifications of the transition d-states as a result of the formation of strong transition metal-metalloid bonds rather than a large transfer of electrons from the glass former atoms (P in this case) to the d-band of the transition metal in a rigid band picture.

Silicide formation and the interaction of metals with polycrystalline Si

The main factors affecting solid-phase Si-metal interactions are reported in this work. The influence of the orientation of the Si substrates and the presence of impurities in metal films and at the Si-metal interface on the formation of nickel and chromium silicides have been demonstrated. We have observed that the formation and kinetic rate of growth of nickel silicides is strongly dependent on the orientation and crystallinity of the Si substrates; a fact which, up to date, has never been seriously investigated in silicide formation. Impurity contaminations in the Cr film and at the Si-Cr interface are the most dominant influencing factors in the formation and kinetic rate of growth of CrSi₂. The potentiality and use of silicides as a diffusion barrier in metallization on silicon devices were also investigated.

Two phases, Ni₂Si and NiSi, form simultaneously in two distinct sublayers in the reaction of Ni with amorphous Si, while only the former phase was observed on other substrates. On (111) oriented Si substrates the growth rate is about 2 to 3 times less than that on <100> or polycrystalline Si. Transmission electron micrographs establish-·that silicide layers grown on different substrates have different microcrystalline structures. The concept of grain-boundary diffusion is speculated to be an important factor in silicide formation.

The composition and kinetic rate of CrSi₂ formation are not influenced by the underlying Si substrate. While the orientation of the Si substrate does not affect the formation of CrSi₂ , the purity of the Cr film and the state of Si-Cr interface become the predominant factors in the reaction process. With an interposed layer of Pd₂Si between the Cr film and the Si substrate, CrSi₂ starts to form at a much lower temperature (400°C) relative to the Si-Cr system. However, the growth rate of CrSi₂ is observed to be independent of the thickness of the Pd2Si layer. For both Si-Cr and Si-Pd₂Si-Cr samples, the growth rate is linear with time with an activation energy of 1.7 ± 0.1 ev.

A tracer technique using radioactive ³¹Si (T_1/2 = 2.26 h) was used to study the formation of CrSi₂ on Pd₂Si. It is established from this experiment that the growth of CrSi₂ takes place partly by transport of Si directly from the Si substrate and partly by breaking Pd₂Si bonds, making free Si atoms available for the growth process.

The role of CrSi₂ in Pd-Al metallization on Si was studied. It is established that a thin CrSi₂ layer can be used as a diffusion barrier to prevent Al from interacting with Pd₂Si in the Pd-Al metallization on Si.

As a generalization of what has been observed for polycrystalline-Si-Al interaction, the reactions between polycrystalline Si (poly Si) and other metals were studied. The metals investigated include Ni, Cr, Pd, Ag and Au. For Ni, Cr and Pd, annealing results in silicide formation, at temperatures similar to those observed on single crystal Si substrates. For Al, Ag and Au, which form simple eutectics with Si annealing results in erosion of the poly Si layer and growth of Si crystallites in the metal films.

Backscattering spectrometry with 2.0 and 2.3 MeV ⁴He ions was the main analytical tool used in all our investigations. Other experimental techniques include the Read camera glancing angle x-ray diffraction, scanning electron, optical and transmission electron microscopy. Details of these analytical techniques are given in Chapter II.

Influence of composition on the structure, electric and magnetic properties of Pd-Mn-P and Pd-Co-P amorphous alloys

The influence of composition on the structure and on the electric and magnetic properties of amorphous Pd-Mn-P and Pd-Co-P prepared by rapid quenching techniques were investigated in terms of (1) the 3d band filling of the first transition metal group, (2) the phosphorus concentration effect which acts as an electron donor and (3) the transition metal concentration.

The structure is essentially characterized by a set of polyhedra subunits essentially inverse to the packing of hard spheres in real space. Examination of computer generated distribution functions using Monte Carlo random statistical distribution of these polyhedra entities demonstrated tile reproducibility of the experimentally calculated atomic distribution function. As a result, several possible "structural parameters" are proposed such as: the number of nearest neighbors, the metal-to-metal distance, the degree of short-range order and the affinity between metal-metal and metal-metalloid. It is shown that the degree of disorder increases from Ni to Mn. Similar behavior is observed with increase in the phosphorus concentration.

The magnetic properties of Pd-Co-P alloys show that they are ferromagnetic with a Curie temperature between 272 and 399°K as the cobalt concentration increases from 15 to 50 at.%. Below 20 at.% Co the short-range exchange interactions which produce the ferromagnetism are unable to establish a long-range magnetic order and a peak in the magnetization shows up at the lowest temperature range . The electric resistivity measurements were performed from liquid helium temperatures up to the vicinity of the melting point (900°K). The thermomagnetic analysis was carried out under an applied field of 6.0 kOe. The electrical resistivity of Pd-Co-P shows the coexistence of a Kondo-like minimum with ferromagnetism. The minimum becomes less important as the transition metal concentration increases and the coefficients of ℓn T and T^2 become smaller and strongly temperature dependent. The negative magnetoresistivity is a strong indication of the existence of localized moment.

The temperature coefficient of resistivity which is positive for Pd- Fe-P, Pd-Ni-P, and Pd-Co-P becomes negative for Pd-Mn-P. It is possible to account for the negative temperature dependence by the localized spin fluctuation model and the high density of states at the Fermi energy which becomes maximum between Mn and Cr. The magnetization curves for Pd-Mn-P are typical of those resulting from the interplay of different exchange forces. The established relationship between susceptibility and resistivity confirms the localized spin fluctuation model. The magnetoresistivity of Pd-Mn-P could be interpreted in tenns of a short-range magnetic ordering that could arise from the Rudennan-Kittel type interactions.

Structure and properties of an amorphous ferromagnetic alloy

The structure and the electrical and magnetic properties of an amorphous alloy containing approximately 80 at .% iron, 13 at.% phos phorus and 7 at.% carbon (Fe_(80)Fe_(13)C_7) obtained by rapid quenching from the liquid state have been studied. Transmission electron diffraction data confirm the amorphous nature of this alloy. An analysis of the radial distribution function obtained from X-ray diffraction data indicates that the number of nearest neighbors is approximately seven, at a distance of 2.6A. The structure of the alloy can be related to that of silicate glasses and is based on a random arrangement of trigonal prisms of Fe_2P and Fe_3C types in which the iron atoms have an average ligancy of seven. Electrical resistance measurements show that the alloys are metallic. A minimum in the electrical resistivity vs. temperature curve is observed between 10° K to 50° K depending on the specimen, and the temperature at which the minimum occurs is related to the degree of local ordering. The Fe-P-C amorphous alloys are ferromagnetic. The Curie temperature measured by the induction method and by Mossbauer spectroscopy is 315° C. The field dependence of the magneto-resistance at temperatures from liquid helium to room temperature is similar to that found in crystalline iron. The ordinary Hall coefficient is approximately 10^(-11) volt-cm/amp-G. The spontaneous Hall coefficient is about 0.6 x 10^(-9) volt-cm/amp-G and is practically independent of temperature from liquid helium temperature up to 300° c.

Space-charge-limited current in fast neutron irradiated silicon

DC and transient measurements of space-charge-limited currents through alloyed and symmetrical n^+ν n^+ structures made of nominally 75 kΩcm ν-type silicon are studied before and after the introduction of defects by 14 MeV neutron radiation. In the transient measurements, the current response to a large turn-on voltage step is analyzed. Right after the voltage step is applied, the current transient reaches a value which we shall call "initial current" value. At longer times, the transient current decays from the initial current value if traps are present.

Before the irradiation, the initial current density-voltage characteristics J(V) agree quantitatively with the theory of trap-free space-charge-limited current in solids. We obtain for the electron mobility a temperature dependence which indicates that scattering due to impurities is weak. This is expected for the high purity silicon used. The drift velocity-field relationships for electrons at room temperature and 77°K, derived from the initial current density-voltage characteristics, are shown to fit the relationships obtained with other methods by other workers. The transient current response for t > 0 remains practically constant at the initial value, thus indicating negligible trapping.

Measurement of the initial (trap-free) current density-voltage characteristics after the irradiation indicates that the drift velocity-field relationship of electrons in silicon is affected by the radiation only at low temperature in the low field range. The effect is not sufficiently pronounced to be readily analyzed and no formal description of it is offered. In the transient response after irradiation for t > 0, the current decays from its initial value, thus revealing the presence of traps. To study these traps, in addition to transient measurements, the DC current characteristics were measured and shown to follow the theory of trap-dominated space-charge-limited current in solids. This theory was applied to a model consisting of two discrete levels in the forbidden band gap. Calculations and experiments agreed and the capture cross-sections of the trapping levels were obtained. This is the first experimental case known to us through which the flow of space-charge-limited current is so simply representable.

These results demonstrate the sensitivity of space-charge-limited current flow as a tool to detect traps and changes in the drift velocity-field relationship of carriers caused by radiation. They also establish that devices based on the mode of space-charge-limited current flow will be affected considerably by any type of radiation capable of introducing traps. This point has generally been overlooked so far, but is obviously quite significant.

I. Reactively sputtered Ti-Si-N thin films for diffusion barrier applications. II. Oxidation, diffusion and crystallization of an amorphous Zr_(60)Al_(15)Ni_(25) alloy.

Films of Ti-Si-N obtained by reactively sputtering a TiSi_2, a Ti_5Si_3, or a Ti_3Si target are either amorphous or nanocrystalline in structure. The atomic density of some films exceeds 10^23 at./cm^3. The room-temperature resistivity of the films increases with the Si and the N content. A thermal treatment in vacuum at 700 °C for 1 hour decreases the resistivity of the Ti-rich films deposited from the Ti_5Si_3 or the Ti_3Si target, but increases that of the Si-rich films deposited from the TiSi_2 target when the nitrogen content exceeds about 30 at. %.

Ti_(34)Si_(23)N_(43) deposited from the Ti_5Si_3 target is an excellent diffusion barrier between Si and Cu. This film is a mixture of nanocrystalline TiN and amorphous SiN_x. Resistivity measurement from 80 K to 1073 K reveals that this film is electrically semiconductor-like as-deposited, and that it becomes metal-like after an hour annealing at 1000 °C in vacuum. A film of about 100 nm thick, with a resistivity of 660 µΩcm, maintains the stability of Si n+p shallow junction diodes with a 400 nm Cu overlayer up to 850 °C upon 30 min vacuum annealing. When used between Si and Al, the maximum temperature of stability is 550 °C for 30 min. This film can be etched in a CF_4/O_2 plasma.

The amorphous ternary metallic alloy Zr_(60)Al_(15)Ni_(25) was oxidized in dry oxygen in the temperature range 310 °C to 410 °C. Rutherford backscattering and cross-sectional transmission electron microscopy studies suggest that during this treatment an amorphous layer of zirconium-aluminum-oxide is formed at the surface. Nickel is depleted from the oxide and enriched in the amorphous alloy below the oxide/alloy interface. The oxide layer thickness grows parabolically with the annealing duration, with a transport constant of 2.8x10^(-5) m^2/s x exp(-1.7 eV/kT). The oxidation rate is most likely controlled by the Ni diffusion in the amorphous alloy.

At later stages of the oxidation process, precipitates of nanocrystalline ZrO_2 appear in the oxide near the interface. Finally, two intermetallic phases nucleate and grow simultaneously in the alloy, one at the interface and one within the alloy.

Energy loss of light ions channeling in silicon

Experimental measurements of rate of energy loss were made for protons of energy .5 to 1.6 MeV channeling through 1 μm thick silicon targets along the <110>, <111>, and <211> axial directions, and the {100}, {110}, {111}, and {211} planar directions. A .05% resolution automatically controlled magnetic spectrometer was used. The data are presented graphically along with an extensive summary of data in the literature. The data taken cover a wider range of channels than has previously been examined, and are in agreement with the data of F. Eisen, et al., Radd. Eff. 13, 93 (1972).

The theory in the literature for channeling energy loss due to interaction with local electrons, core electrons, and distant valence electrons of the crystal atoms is summarized. Straggling is analyzed, and a computer program which calculates energy loss and straggling using this theory and the Moliere approximation to the Thomas Fermi potential, V_TF, and the detailed silicon crystal structure is described. Values for the local electron density Z_loc in each of the channels listed above are extracted from the data by graphical matching of the experimental and computer results.

Zeroth and second order contributions to Z_loc as a function of distance from the center of the channel were computed from ∇²V_TF = 4πρ for various channels in silicon. For data taken in this work and data of F. Eisen, et al., Rad. Eff. 13, 93 (1972), the calculated zeroth order contribution to Z_loc lies between the experimentally extracted Z_loc values obtained by using the peak and the leading edge of the transmission spectra, suggesting that the observed straggling is due both to statistical fluctuations and to path variation.