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.

Intense greeen upconversion luminescence in Er3+: Yb3+ codoped fluorophosphate glass ceramic containing SrTe5O11 nanocrystals

Er3+:Yb3+ codoped tellurite-fluorophosphate (TFP) glass ceramic exhibits much stronger upconversion luminescence. The intensity of the 540 nm green light and 651 nm red light of the TFP glass ceramic is 120 times and 44 times stronger than that of the fluorophospahte (FP) glass, respectively. XRD analysis shows that the nanocrystal in TFP glass ceramic is SrTe5O11. TFP glass ceramic also displays much higher upconversion fluorescence lifetime and crystallization stability. The narrow and strong peak at 540 nm is very ideal for practical upconversion luminescence realization. This work is a new trial for exploring non-PbF2 involved nanocrystal upconversion glass ceramics.

Ultrabroadband infrared luminescence and optical amplification in bismuth-doped germanosilicate glass

This letter reports the ultrabroadband infrared luminescence from 1000- to 1700-nm wavelength range and demonstrate optical amplification at the second optical communication window in a novel bismuth-doped germanosilicate glass. The full-width at half-maximum of the luminescence is about 300 mn and the optical gain is larger than 1.37 within the wavelength region from 1272 to 1348 nm with pump power 0.97 W. This material could be useful to fabricate ultrabroadband optical fiber amplifiers.

Effects of melting temperature on the broadband infrared luminescence of bi-doped and Bi/Dy co-doped chalcohalide glasses

Bismuth (Bi)-doped and Bi/Dy co-doped chalcohalide glasses are investigated as promising materials for amplifiers in optical communication. The samples synthesized at lower melting temperatures (MTs) are characterized by more intensified infrared emissions. With respect to the redox process of a liquid mixture at different MTs, we attribute an emission at 1230 nm to low-valent Bi ions. The lower MT favors the formation of LVB ions, i.e. Bi+ or Bi2+, while the higher MT promotes the production of higher-valent Bi ions Bi3+. An enhanced broadband infrared luminescence with the full-width at half-maximum over 200 nm is achieved from the present Bi/Dy co-doped chalcohalide glasses.

Intense infrared luminescence in transparent glass-ceramics containing beta-Ga2O3 : Ni2+ nanocrystals

Transparent glass-ceramics containing beta-Ga2O3:Ni2+ nanocrystals were synthesized and characterized by X-ray diffraction, transmission electron microscopy, and electron energy loss spectroscopy. Intense broad-band luminescence centering at 1200 nm was observed when the sample was excited by a diode laser at 980 nm. The room-temperature fluorescent lifetime was 665 mu s, which is longer than the Ni2+-doped ZnAl2O4 and LiGa5O8 glass-ceramics and is also comparable to the Ni2+-doped LiGa5O8 single crystal. The intense infrared luminescence with long fluorescent lifetime may be ascribed to the high crystal field hold by Ni2+ and the moderate lattice phonon energy of beta-Ga2O3. The excellent optical properties of this novel material indicate that it might be a promising candidate for broad-band amplifiers and room-temperature tunable lasers.

Mechanisms of Yb3+ sensitization to Tm3+ for blue upconversion luminescence in fluorophosphate glass

The sensitization mechanisms of Yb3+ to Tm3+ for the blue upconversion luminescence in fluorophosphate glass were studied. Two different mechanisms exist in the sensitization. One is the sequential sensitization that Tm3+ is excited from H-3(6) to (1)G(4) through absorbing three photons transferred from Yb3+ one by one. Another is the cooperative sensitization that two Yb3+ ions form a couple cluster firstly, and then the couple cluster Yb3+ ions transfer their energy to Tm3+ and excite it to (1)G(4). With the increment of the concentration of Yb3+ ions, the sequential sensitization becomes weak and the cooperative sensitization becomes intense, and the transformation trend of sensitization mechanism with the increment of Yb3+ concentration can be clarified by the introduction of Th3+ ions in the glass. (c) 2006 Elsevier B.V. All rights reserved.

Tuning the Eu luminescence in glass materials synthesized in air by adjusting glass compositions

The doped Eu3+ ions can be partly reduced to Eu2+ in a series of MO-B2O3: Eu (M=Ba, Sr, Ca) glasses synthesized in air atmosphere, but not in the 12CaO-7Al(2)O(3): Eu glass. The different redox-behavior of Eu ions in these two glass systems is attributed to the different host optical basicity. It is found that a lower valence state of Eu2+ is more favorable in acidic glasses, which have lower optical basicities. A notion of the critical value of optical basicity is introduced empirically, which can be used as a guide for the selection of glass composition suitable to incorporate Eu2+ for luminescence. (C) 2006 Elsevier B.V. All rights reserved.

Bismuth-doped zinc aluminosilicate glasses and glass-ceramics with ultra-broadband infrared luminescence

Broadband infrared luminescence covering the optical telecommunication wavelength region of 0, E and S bands was observed from bismuth-doped zinc aluminosilicate glasses and glass-ceramics. The spectroscopic properties of the glasses and glass-ceramics depend on the thermal-treatment history. With the appearance of gahnite (ZnAl2O4) crystalline phase, the fluorescent peak moves to longer wavelength, but the fluorescent intensity decreases. The similar to 1300 nm fluorescence with a FWHM larger than 250 nm and a lifetime longer than 600 mu s possesses these optical materials with potential applications in laser devices and broadband amplifiers. The broad infrared luminescence from the bismuth-doped zinc aluminosilicate glasses and glass-ceramics might be from BiO or bismuth clusters rather than from Bi5+ and Bi3+. (c) 2005 Elsevier B.V. All rights reserved.

Ultrabroad infrared luminescence from Bi-doped aluminogermanate glasses

We report ultrabroad infrared luminescence from Bi-doped aluminogermanate glasses. The infrared luminescence almost covers the whole low loss wavelength region (1200-1650 nm) of silica glass fiber when excited by a diode laser at 980 nm. The full width at half maximum (FWHM) of the luminescence is 510 nm. The luminescence peak can be divided into three Gaussian peaks, and the fluorescence lifetime of the three emissions are 297 mu s, 470 mu s and 1725 mu s, respectively. These fluorescence properties indicate that the glasses are promising material for broadband optical amplifiers. (C) 2007 Elsevier Ltd. All rights reserved.

Intense frequency upconversion luminescence in Yb3+/Tm3+-codoped oxychloride germanate glasses

Yb3+/Tm3+-codoped oxychloride germanate glasses for developing potential upconversion lasers have been fabricated and characterized. Structural properties were obtained based on the Raman spectra analysis, indicating that PbCl2 plays an important role in the formation of glass network and has an important influence on the maximum phonon energies of host glasses. Intense blue and weak red emissions centered at 477 and 650 nm, corresponding to the transitions (1)G(4) -> H-3(6) and (1)G(4) -> H-3(4), respectively, were observed at room temperature. With increasing PbCl2 content, the intensity of blue (477 nm) emission increases significantly, while the red (650 nm) emission increases slowly. The results indicate that PbCl2 has more influence on the blue emissions than the red emission in oxychloride germanate glasses. The possible upconversion mechanisms are discussed and estimated. Intense blue upconversion luminescence indicates that these oxychloride germanate glasses can be used as potential host material for upconversion lasers. C (c) 2005 Springer Science + Business Media, Inc.