Short-wavelength photoluminescence of SiO2 layers implanted with high doses of Si+, Ge+, and Ar+ ions

The short-wavelength (400–700 nm) photoluminescence (PL) spectra of SiO₂ layers implanted with Si⁺, Ge⁺, and Ar⁺ ions in the dose range 3.2×10¹⁶–1.2×10¹⁷ cm⁻² are compared. After Ar⁺ implantation an extremely weak luminescence, which vanishes completely after annealing for 30 min at 400 °C or 20 ms at 1050 °C, was observed. After implantation of group-IV elements the luminescence intensities were 1 to 2 orders of magnitude higher, and the luminescence remained not only with annealings but it could also increase. The dose and heating dependences of the luminescence show that it is due to the formation of impurity clusters and this process is more likely to be of a percolation than a diffusion character. For both group-IV impurities an intense blue band and a weaker band in the orange part of the spectrum were observed immediately after implantation. The ratio of the excitation and emission energies of the blue luminescence is characteristic of oxygen vacancies in SiO₂; its properties are determined by the direct interaction of group-IV atoms. On this basis it is believed that the centers of blue PL are chains of Si (or Ge) atoms embedded in SiO₂. The orange luminescence remained after annealings only in the case of Si⁺ implantation. This is attributed directly to the nonphase precipitates of Si in the form of strongly developed nanometer-size clusters. Fiz. Tekh. Poluprovodn. 32, 439–444 (April 1998)     

Effect of low-temperature annealing on photoluminescence of silicon nanocluster structures

Experimental data on the photoluminescence spectra of Si nanocluster structures obtained after high-temperature annealing (1150°C) of SiO _x films deposited onto Si and subsequent low-temperature annealing of the films at the temperature 450°C in different ambient are reported. It is shown that the photoluminescence intensity substantially increases after low-temperature annealing and the most-pronounced effect is observed after annealing in the oxygen-nitrogen mixture. In this case, the photoluminescence spectrum is shifted to longer wavelengths and shaped as a broad band with a peak around 800 nm. The processes responsible for the increase in the PL intensity on low-temperature annealing in the oxygen-nitrogen mixture are defined by reconstruction of the Si/SiO₂ interfaces and by energy levels formed at the interfaces and involved in recombination of nonequilibrium charge carriers. The quasichemical reactions that bring about the formation of such levels involve oxygen and nitrogen atoms, and the centers, at which the reactions are initiated, are unsaturated valence bonds at the interfaces between Si nanoclusters and the SiO₂ matrix.     

Radiative recombination in Ge<Superscript>+</Superscript>-implanted SiO<Subscript>2</Subscript> films annealed under hydrostatic pressure

Photoluminescence (PL) spectra and PL excitation spectra were recorded at room temperature from SiO₂ films implanted with Ge⁺ ions and annealed at temperature T _a =450–1100°C under hydrostatic pressure P=12 kbar. The emergence of features in the violet and green bands of the PL and PL excitation spectra correlates with the formation of hydrostatically strained Ge nanocrystals. The shift of the PL bands to higher energies, which occurs as the annealing temperature is raised to T _a ≥800°C, can be attributed to a shift of the energy levels related to the radiative recombination centers, which is caused by the increasing deformation potential. The observed PL is accounted for by the enhanced probability of direct radiative transitions in Ge nanocrystals with an X-like conduction band.     

Effect of ion dose and annealing mode on photoluminescence from SiO2 implanted with Si ions

This paper discusses the photoluminescence spectra of 500-nm-thick layers of SiO₂ implanted with Si ions at doses of 1.6×10¹⁶, 4×10¹⁶, and 1.6×10¹⁷ cm⁻² and then annealed in the steady-state region (30 min) and pulsed regime (1 s and 20 ms). Structural changes were monitored by high-resolution electron microscopy and Raman scattering. It was found that when the ion dose was decreased from 4×10¹⁶ cm⁻² to 1.6×10¹⁶ cm⁻², generation of centers that luminesce weakly in the visible ceased. Moreover, subsequent anneals no longer led to the formation of silicon nanocrystallites or centers that luminesce strongly in the infrared. Annealing after heavy ion doses affected the photoluminescence spectrum in the following ways, depending on the anneal temperature: growth (up to ∼700 °C), quenching (at 800–900 °C), and the appearance of a very intense photoluminescence band near 820 nm (at >900 °C). The last stage corresponds to the appearance of Si nanocrystallites. The dose dependence is explained by a loss of stability brought on by segregation of Si from SiO₂ and interactions between the excess Si atoms, which form percolation clusters. At low heating levels, the distinctive features of the anneals originate predominantly with the percolation Si clusters; above ∼700 °C these clusters are converted into amorphous Si-phase nanoprecipitates, which emit no photoluminescence. At temperatures above 900 °C the Si nanocrystallites that form emit in a strong luminescence band because of the quantum-well effect. The difference between the rates of percolation and conversion of the clusters into nanoprecipitates allows the precipitation of Si to be controlled by combinations of these annealings. Fiz. Tekh. Poluprovodn. 32, 1371–1377 (November 1998)     

Behavior of germanium ion-implanted into SiO<Subscript>2</Subscript> near the bonding interface of a silicon-on-insulator structure

The properties of germanium implanted into the SiO₂ layers in the vicinity of the bonding interface of silicon-on-insulator structures are studied. It is shown that, under conditions of high-temperature (1100°C) annealing, germanium nanocrystals are not formed, while the implanted Ge atoms segregate at the Si/SiO₂ bonding interface. It is established that, in this case, Ge atoms are found at sites that are coherent with the lattice of the top silicon layer. In this situation, the main type of traps is the positive-charge traps; their effect is interpreted in the context of an increase in the surface-state density due to the formation of weaker Ge-O bonds. It is found that the slope of the drain-gate characteristics of the back MIS transistors increases; this increase is attributed to an increased mobility of holes due to the contribution of an intermediate germanium layer formed at the Si/SiO₂ interface.     

Influence of irradiation with swift heavy ions on multilayer Si/SiO2 heterostructures

The influence of Xe ions with an energy of 167 MeV and a dose in the range 10¹²-3 × 10¹³ cm^?2 on heterostructures consisting of six pairs of Si/SiO₂ layers with the thicknesses ～8 and ～10 nm, correspondingly, is studied. As follows from electron microscopy data, the irradiation breaks down the integrity of the layers. At the same time, Raman studies give evidence for the enhancement of scattering in amorphous silicon. In addition, a yellow-orange band inherent to small-size Si clusters released from SiO₂ appears in the photoluminescence spectra. Annealing at 800°C recovers the SiO₂ network, whereas annealing at 1100°C brings about the appearance of a more intense photoluminescence peak at ～780 nm typical of Si nanocrystals. The 780-nm-peak intensity increases, as the irradiation dose is increased. It is thought that irradiation produces nuclei, which promote Si-nanocrystal formation upon subsequent annealing. The processes occur within the tracks due to strong heating because of ionization losses of the ions.     

Modeling Si nanoprecipitate formation in SiO2 layers with excess Si atoms

Computer simulations based on the Monte Carlo method are used to analyze processes leading to the formation of luminescence centers in SiO₂ implanted with Si ions. The simulations, which take place in a two-dimensional space, mimic the growth of silicon nanoprecipitates in layers containing several at.% of excess silicon. It is assumed that percolation clusters made up of neighboring Si atoms form first. As the annealing temperature increases, these clusters grow and compactify into nano-sized inclusions of a well-defined phase. It is shown that a dose dependence arises from an abrupt enhancement of the probability of forming direct Si-Si bonds when the concentration of silicon exceeds ∼1 at. %. Under these conditions, percolation chains and clusters form even before annealing begins. The effect of the temperature of subsequent anneals up to 900 °C is modeled via the well-known temperature dependence of Si diffusion in SiO₂. It is assumed that annealing at moderate temperatures increases the mobility of Si atoms, thereby facilitating percolation and development of clusters due to an increase in the interaction radius. Intrinsic diffusion processes that occur at high temperatures transform branching clusters into nanoprecipitates with well-defined phase boundaries. The dose and temperature intervals for the formation of precipitates obtained from these simulations are in agreement with the experimental intervals of dose and temperatures corresponding to the appearance of and changes in luminescence. Fiz. Tekh. Poluprovodn. 33, 389–394 (April 1999)     

Si and Ge nanocluster formation in silica matrix

High resolution transmission electron microscopy, scanning transmission electron microscopy, and cathodoluminescence have been used to investigate Si and Ge cluster formation in amorphous silicon-dioxide layers. Commonly, cathodoluminescence emission spectra of pure SiO₂ are identified with particular defect centers within the atomic network of silica including the nonbridging oxygen hole center associated with the red luminescence at 650 nm (1.9 eV) and the oxygen deficient centers with the blue (460 nm; 2.7 eV) and ultraviolet band (295 nm; 4.2 eV). In Ge⁺ ion-implanted SiO₂, an additional violet emission band appears at 410 nm (3.1 eV). The strong increase of this violet luminescence after thermal annealing is associated with formation of low-dimension Ge aggregates such as dimers, trimers, and higher formations, further growing to Ge nanoclusters. On the other hand, pure silica layers were modified by heavy electron beam irradiation (5 keV; 2.7 A/cm²), leading to electronic as well as thermal dissociation of oxygen and the appearance of under-stoichiometric SiO_x. This SiO_x will undergo a phase separation and we observe Si cluster formation with a most probable cluster diameter of 4 nm. Such largely extended Si clusters will diminish the SiO₂-related luminescence and Si-crystal-related luminescence in the near IR. The text was submitted by the authors in English.     

Ultra-low-energy ion-beam-synthesis of Ge nanocrystals in thin ALD Al2O3 layers for memory applications

Structural and electrical properties of ALD-grown 5 and 7 nm-thick Al₂O₃ layers before and after implantation of Ge ions (1 keV, 0.5–1 × 10¹⁶ cm^?2) and thermal annealing at temperatures in the 700–1050 °C range are reported. Transmission Electron Microscopy reveals the development of a 1 nm-thick SiO₂-rich layer at the Al₂O₃/Si substrate interface as well as the formation of Ge nanocrystals with a mean diameter of ～5 nm inside the implanted Al₂O₃ layers after annealing at 800 °C for 20 min. Electrical measurements performed on metal–insulator–semiconductor capacitors using Ge-implanted and annealed Al₂O₃ layers reveal charge storage at low-electric fields mainly due to location of the Ge nanocrystals at a tunnelling distance from the substrate and their spatial dispersion inside the Al₂O₃ layers.     

Structural transformations and silicon nanocrystallite formation in SiOx films

The results of a comprehensive study by the methods of IR absorption, Raman scattering, photoluminescence (PL), and electron spin resonance (ESR) of SiO_x films prepared by thermal evaporation of SiO in a vacuum are presented. The nature of structural transformations occurring on annealing the films is determined. Annealing in the temperature range 300–600°C gives rise to a PL band at 650 nm, presumably related to structural defects in SiO_x film. Raising the annealing temperature further leads to healing of such defects and quenching of the PL band. Silicon precipitates pass from the amorphous to the crystalline state on being annealed at T _ann=1100°C, which gives rise to a new PL band at 730 nm. ESR spectra of P _b centers were recorded at the interface between randomly oriented silicon nanocrystallites and SiO₂.     

Annealing-induced evolution of the structural and morphological properties of a multilayer nanoperiodic SiO x /ZrO2 system containing Si nanoclusters

The structural and morphological properties of nanoperiodic structures produced by the alternate vacuum evaporation of SiO and ZrO₂ followed by annealing at temperatures of 500–1100°C are studied by the transmission electron microscopy of a transverse cross section. Upon annealing at temperatures below 700°C, the layers are amorphous. Upon annealing at 900°C and 1000°C, nanocrystals separated by twinned boundaries or amorphous regions are formed in the ZrO₂ layers. The formation of Si nanocrystals in the SiO _x layers occurs upon annealing at 1000°C and 1100°C. At 1100°C, because of the reaction between SiO _x and ZrO₂, spherical Si _x Zr _y O _z -type nanocrystals are formed in place of the ZrO₂ layers; the nanocrystal diameters exceed the initial layer thickness. The annealing-induced structural evolution is consistent with the previously considered behavior of the optical and luminescence properties of the system.     

Silicide formation and interdiffusion effects in Si-Ta,SiO2-Ta AND Si-PtSi-Ta thin film structures

The formation of TaSi₂ in the Si-PtSi-Ta and Si-Ta systems has been studied using Auger spectroscopy, x-ray diffraction and electron diffraction techniques. The reaction of tantalum with PtSi was observed by Sinha, et al.^l to take place with high temperature (800°-900°c) annealing of thin film systems consisting of Si-PtSi-Ta-W¹. In the present investigation, it is shown that tantalum reacts with PtSi at approximately 600°C to form a mixture of Ta₅Si₃ and TaSi₂ and predominantly TaSi₂ at 785°C. Platinum is displaced at the refractory metal (Ta)-PtSi interface, whereupon the more stable refractory metal-silicide is formed. The displaced platinum reacts further with the excess silicon which diffuses from the Si-PtSi interface. The Si-PtSi-Ta reaction is similar to the Si-PtSi-W reaction. However, unlike tungsten which migrates very little in the Si-PtSi-W system, tantalum appears to interdiffuse with the PtSi at temperatures as low as 600°C. In the case of the Si-Ta couple, TaSi₂ forms at approximately 750°C as determined by transmission electron microscopy (TEM) measurements. The kinetics of TaSi₂ formation at the Si-Ta interface are compared to that which takes place at the PtSi-Ta interface to determine the influence of the PtSi layer. Silicide formation was not observed in SiO₂-Ta specimens. after anneals up to 800°c. At 750°C Ta₂O₅ formed as observed by electron diffraction.     

Thermally stable Ge/Cu/Ti ohmic contacts to n-type GaN

The performance of a novel Ge/Cu/Ti metallization scheme on n-type GaN has been investigated for obtaining thermally and electrically stable low-resistance ohmic contacts. Isochronal (2 min.) anneals in the 600–740°C temperature range and isothermal (690°C) anneals for 2–10 min. duration were performed in inert atmosphere. For the 690°C isothermal schedule, ohmic behavior was observed after annealing for 3 min. or longer with a lowest contact resistivity of 9.1 × 10⁻⁵ Ωcm² after the 10 min. anneal for a net donor doping concentration of 9.2 × 10¹⁷ cm^−Ω3. Mean roughness (R_a) for anneals at 690°C was almost constant at around 5 nm, up to an annealing duration of 10 min., which indicates a good thermal stability of the contact scheme.     

High thermal annealing effect on structural and optical properties of ZnO–SiO2 nanocomposite

The effect of annealing temperature on photoluminescence (PL) of ZnO–SiO₂ nanocomposite was investigated. The ZnO–SiO₂ nanocomposite was annealed at different temperatures from 600 °C to 1000 °C with a step of 100 °C. High Resolution Transmission Electron Microscope (HR-TEM) pictures showed ZnO nanoparticles of 5 nm are capped with amorphous SiO₂ matrix. Field Emission Scanning Electron Microscope (FE-SEM) pictures showed that samples exhibit spherical morphology up to 800 °C and dumbbell morphology above 800 °C. The absorption spectrum of ZnO–SiO₂ nanocomposite suffers a blue-shift from 369 nm to 365 nm with increase of temperature from 800 °C to 1000 °C. The PL spectrum of ZnO–SiO₂ nanocomposite exhibited an UV emission positioned at 396 nm. The UV emission intensity increased as the temperature increased from 600 °C to 700 °C and then decreased for samples annealed at and above 800^°C. The XRD results showed that formation of willemite phase starts at 800 °C and pure willemite phase formed at 1000 °C. The decrease of the intensity of 396 nm emission peak at 900 °C and 1000 °C is due to the collapse of the ZnO hexagonal structure. This is due to the dominant diffusion of Zn into SiO₂ at these temperatures. At 1000 °C, an emission peak at 388 nm is observed in addition to UV emission of ZnO at 396 nm and is believed to be originated from the willemite.     

Photoluminescence of Si3N4 films implanted with Ge+ and Ar+ ions

The room-temperature photoluminescence emission and excitation spectra of Si₃N₄ films implanted with Ge⁺ and Ar⁺ ions were investigated as a function of the ion dose and temperature of subsequent annealing. It was established that the implantation of bond-forming Ge atoms during annealing right up to temperature T _a=1000 °C stimulates the formation of centers emitting in the green and violet regions of the spectrum. Implantation of inert Ar⁺ ions introduces predominantly nonradiative defect centers. Comparative analysis of the photoluminescence spectra, Rutherford backscattering data, and Raman scattering spectra shows that the radiative recombination is due not to quantum-well effects in Ge nanocrystals but rather recombination at the defects ≡Si-Si≡, ≡Si-Ge≡, and ≡Ge-Ge≡. Fiz. Tekh. Poluprovodn. 33, 559–566 (May 1999)     

Influence of an increase in the implantation dose of erbium ions and annealing temperature on photoluminescence in AlGaN/GaN superlattices and GaN epitaxial layers

Room-temperature photoluminescence (PL) has been studied in AlGaN/GaN superlattices and GaN epitaxial layers implanted with 1-MeV erbium at a dose of 3 × 10¹⁵ cm^?2 and annealed in argon. The intensity of PL from Er³⁺ ions in the superlattices exceeds that for the epitaxial layers at annealing temperatures of 700–1000°C. The strongest difference (by a factor of ～2.8) in PL intensity between the epitaxial layers and the superlattices and the highest PL intensity for the superlattices are observed upon annealing at 900°C. On raising the annealing temperature to 1050°C, the intensity of the erbium emission from the superlattices decreases substantially. This circumstance may be due to their thermal destruction.     

Crystallization of Amorphous Si<Subscript>0.6</Subscript>Ge<Subscript>0.4</Subscript> Nanoparticles Embedded in SiO<Subscript>2</Subscript>: Crystallinity Versus Compositional Stability

Si_0.6Ge_0.4 nanocrystals, of diameter <5 nm, embedded in SiO₂ in the form of single layers (2.1 × 10¹² nanoparticles cm^–2) and five-period multilayers (above 10¹³ nanoparticles cm^–2) have been fabricated using a low-thermal-budget process consisting of deposition by low-pressure chemical vapor deposition and crystallization by rapid thermal annealing at several temperatures and for different times. The crystallization process was monitored by Raman spectroscopy and transmission electron microscopy. The loss of integrity and compositional changes of the nanoparticles during the annealing process were characterized by Rutherford backscattering spectrometry. During the annealing process, crystallization and Ge out-diffusion have been observed to compete with each other. Annealing of samples with nanoparticles of 4.6 nm diameter at low temperature (750°C) yields poor crystallization of the nanoparticles and causes the Ge to leave them by a pure diffusive mechanism, thus destroying their integrity. At higher temperatures (≥800°C), crystallization takes place in a short period of time (<30 s) and diffusion from the crystallized material is initially hindered. For samples with nanoparticles of 3.3 nm diameter, partial crystallization is detected at 800°C and 900°C and the crystalline quality is improved in both cases as the annealing time increases. Also, the detection capabilities of the Raman spectroscopy system for the detection of a certain density of SiGe nanocrystals of given diameter and composition have been explored and the lower limit estimated.     

Ion-beam synthesis of InSb nanocrystals in the buried SiO2 layer of a silicon-on-insulator structure

The ion-beam synthesis of InSb nanocrystals in the buried SiO₂ layer of a silicon-on-insulator structure is investigated. The distributions of In and Sb atoms after annealing at a temperature of T _a = 500–1100°C are studied. It is established that the redistribution of implanted atoms is unsteadily dependent on the annealing temperature. The formation of InSb nanocrystals occurs at Ta ≥ 800°C near the Si/SiO₂ interface and at a depth corresponding to the mean paths R _p . Analysis of the profiles of implanted atoms and of the structure and depth distribution of nanocrystals formed allows an inference regarding the two-stage character of formation of the InSb phase. In the initial stage, antimony precipitates are formed; further the precipitates serve as nuclei for indium and antimony to flow to them.     

Dynamics of SiO2 Buried Layer Removal from Si-SiO2-Si and Si-SiO2-SiC Bonded Substrates by Annealing in Ar

Silicon-on-silicon-carbide substrates could be ideal for high-power and radiofrequency silicon devices. Such hybrid wafers, when made by wafer bonding, contain an intermediate silicon dioxide layer with poor thermal characteristics, which can be removed by high-temperature annealing in an inert atmosphere. To understand the dynamics of this process, removal of 2.4-nm-thick SiO₂ layers from Si-SiO₂-Si and Si-SiO₂-SiC substrates has been studied at temperatures ranging from 1100°C to 1200°C. The substrates were analyzed by transmission electron microscopy, electron energy-loss spectroscopy, secondary-ion mass spectroscopy, and ellipsometry, before and after annealing. For oxide thickness less than 2.4 nm, the activation energy for oxide removal was estimated to be 6.4 eV, being larger than the activation energy reported for removal of thicker oxides (4.1 eV). Under the same conditions, the SiO₂ layer became discontinuous. In the time domain, three steps could be distinguished: bulk diffusion, bulk diffusion with void formation, and bulk diffusion with disintegration. The void formation, predominant here, has an energetic cost that could explain the larger activation energy. The oxide remaining after prolonged annealing corresponds to one layer of oxygen atoms.     

Ge-nanocluster formation in Ge-doped polysilicon films under oxidation and heat treatment

An experimental investigation is conducted into the formation Ge nanoclusters by heat treatment of germanosilicate-glass (Si _x Ge _y O _z ) films that are produced by oxidation of Ge-doped nanostructured polysilicon. It employs Auger and IR spectroscopy, high-resolution electron microscopy, and x-ray diffraction. The process by which Ge atoms in the films are transported toward the substrate is found to include the following stages: (1) the formation of a GeO₂ and a SiO₂ phase, (2) the reduction of GeO₂ to Ge by Si, (3) Ge-crystallite nucleation, and (4) Ge-crystallite growth. Heat treatment in humid oxygen at ≥ 800°C is found to increase Ge-nanocluster size, the point of crystallization being 500°C. It is established that heat treatment at a temperature close to the Ge melting point results in complete aggregation of the germanium into clusters, with a twofold increase in both the mean size and the number of clusters. Germanium is found to accumulate at the interface between oxidized and unoxidized polysilicon.