Transformation of the short-range order upon melting of Cu<Emphasis Type="Italic">Hal</Emphasis> nanocrystals in glasses

The reduced density of states at the edge of interband transitions in CuCl and CuBr nanocrystals is described by a step at T → 0. As the temperature increases, the step is smeared toward the band gap and the long-wavelength absorption tail agrees with the Urbach rule. A change in the phase state of CuCl or CuBr nanoparticles (the crystal-melt transition) is accompanied by an insignificant change in the band gap, and the long-wavelength absorption tail for the interband transitions considerably extends deeper into the band gap as compared to that for crystals at the same temperature. The change observed in the band gap upon melting is explained by the transformation of short-range order in CuCl and CuBr melts. An increase in thermal smearing of the long-wavelength absorption tail for nanomelts is associated with the severalfold increase in the amplitude of thermal fluctuations of the band gap, possibly, due to the disappearance of the long-range order in the melts. A lower melting temperature of large (>30 nm) CuCl and CuBr particles as compared to the melting temperature of bulk samples indicates the presence of the second component NaCl or NaBr. Consequently, the CuCl-NaCl and CuBr-NaBr eutectic nanosystems undergo melting and crystallization. A small shift in the band gap observed in this case upon melting confirms the conclusion drawn by Zalkin that eutectic melts have a microheterogeneous structure.     

Optical properties of Cu+ centers in NaCl

Different aggregation-precipitation states of Cu⁺ have been characterized by absorption bands peaked at 305, 350 and 372–383 nm.The absorption bands at 372–383 nm, observed exclusively in the most doped crystal, have been associated with the Z₁₂, Z₃ excitons of CuCl microcrystals incorporated into the NaCl matrix Their positions shift to low energies with increasing concentration, as expected for a decrease in the stress over the precipitate.The Z1₁₂, Z₃ exciton bands of CuCl microcrystals precipitated in NaCl can be observed by the optical absorption spectrum without reaching saturation Therefore, this technique could be an alternative method to studies of CuCl thin-film depositions or reflectivity of CuCl single crystals.The red emission band observed at 600 nm is a long-lived emission (τ? 29 ms) at variance with the behavior reported for the Cu⁺ emission It is related to energy transfer processes from Cu⁺ to Mn²⁺.     

Comparison of the interaction of Cl2 and Br2 with Cu(100)

The adsorption, reaction and etching of Cu(100) by Cl₂ was studied using temperature programmed desorption (TPD) and low energy electron diffraction (LEED), and the results were compared with recent results for Br₂. Although the general etching mechanism was the same for both gases (adsorption rate limited Cu halide formation followed by halide sublimation), significant differences between the behavior of Cl₂ and Br₂ were observed. The desorption of CuCl was characterized by a single zero order sublimation peak, independent of CuCl coverage, while limiting the CuBr coverage resulted in a desorption peak at temperatures lower than a prediction based on vapor pressure data of all known phases of CuBr. In addition, Cl₂ was found to be at least an order of magnitude less reactive than Br₂ towards halide formation. For both Cl₂ and Br₂, the halide formation rate reversibly decreased with increasing reaction temperature. However, for Br₂, but not Cl₂, annealing a chemisorbed halogen layer prior to further reaction irreversibly increased the halide formation rate. Structural differences between CuCl and CuBr on Cu(100) were also observed. For CuCl, LEED data suggested that highly faceted crystallites form at 325 K and remain stable until desorption, while LEED data for CuBr reveal a compressed epitaxial (111) layer that disorders below 400 K and then desorbs. The implications of these differences on etching and oxidation processes are discussed.     

Energy fluctuations in optical transitions in CuHal crystals

This paper reports on a comprehensive study of fundamental-absorption spectra of CuCl and CuBr nanocrystals measured in the temperature range extending from 80 K up to the melting point. The temperature dependences of the energy E, oscillator strength f, and temperature-broadening coefficient σ of optical-transition spectral to excitonic states were determined. A new approach to the calculation of the shape and temperature-broadening of absorption spectra, based on quantum statistics, was employed. The crystal is treated as a quantum statistical ensemble. The set of atoms involved in the electronic transition initiated by a photon absorption is taken as an element of the ensemble. Energy fluctuations of electronic states occurring in the elements of the ensemble give rise to temperature broadening of the optical-transition spectra. The temperature dependence of the χ coefficient of thermodynamic fluctuations of the Z _{1, 2} and Z ₃ exciton states was found. A theoretical substantiation of the Urbach rule was obtained in terms of the model proposed.     

CuCl nanocrystals in alkali-halide matrices under hydrostatic pressure

CuCl nanocrystals in crystalline alkali-halide matrices have been investigated under hydrostatic pressures up to 18 GPa. The pressures of structural phase transitions in CuCl have been determined both for different nanocrystal sizes and for different matrices (NaCl, LiCl, KCl). For CuCl nanocrystals in NaCl an increase of the transition pressure with decreasing nanocrystal size is observed, which is explained by the increasing importance of surface pressure for small nanocrystals. We found higher transition pressures for the LiCl matrix than for the NaCl matrix. The reason for this is that the pressure which acts on the nanocrystal differs from the external pressure. A simple elastic model describes the effective pressure transmitted from the matrix to the nanocrystal. With CuCl nanocrystals embedded in KCl we have studied the behavior of nanocrystals during a phase transition of the matrix. Additionally we have determined the pressure coefficients of the exciton energies of the CuCl nanocrystals, which depend on the elastic properties of the matrix. Received 4 March 1999     

玻璃中CuClxBr1-x(x=0—1)胶体的激子光谱

一个物质未必具有大晶体一样的周期结构,但只要形成了似晶体的集团,也可以显示出晶体一样的基本光吸收。本工作研究了含CuCl_xBr_1-x(x=0—1)胶体的玻璃制备和光吸收性质。实验结果表明玻璃中达到一定大小的CuCl,CuCl_xBr_1-x和CuBr胶体粒子也可显示出与相应大块晶体相同的激子吸收光谱,玻璃具有和相应晶体相同的紫外吸收限。 关键词：     

Stress-Induced Changes in the Optical Parameters in Copper Chloride

We have calculated the stress-induced variations in refractive indices (of the index of refraction Δn and of the extinction coefficient Δk) of CuCl by the means of the Kramers–Kronig relationship from the piezoreflectance spectra of the 1s Z₃ and 1s Z₁₂ excitons. In the two studied configurations corresponding with the applied stress p //[001] and p //[111] the spectrum of the differential parameters Δk consist of two principals absorption lines in the region of the Z₃ band. The corresponding energetic separation is comparable with the transverse-longitudinal splitting. The longitudinal Z₃ exciton Γ_5L is mixed with the transverse exciten Γ_5T by virtue of the stress-induced k-linear term and became optically active.     

A new application of the diamond anvil cell: Measurements under uniaxial stress

We present optical absorption measurements on thin films of CuCl and CuBr at 100K under uniaxial stress up to ～3.0 GPa. The thin films were prepared by evaporating onto the inner face of one diamond of a diamond anvil cell. From the splitting of the excitons we were able to determine the shear deformation potential d = -0.69 ± 0.03 eV for CuBr and d = +0.45 ± 0.08 eV for CuCl. Our measurements indicate also that the spin-orbit splitting increases in both materials with increasing pressure. A new shear-induced phase is found for CuCl above 4.8 GPa.     

Multiplet structure of P-excitons in CuBr due to valence band degeneracy

The two-photon absorption spectrum of CuBr shows a fourfold energy splitting of the 2P- and 3P-excitons of the Z_1,2 series. The splitting results from d-like contributions to the kinetic energy of the hole (Γ_δ) which lead to a coupling between angular momentum and hole spin. The energy splitting allows to determine the spherical and cubic parameters μ and δ of the reduced exciton mass. The results are compared with corresponding values of an existing band structure calculation.     

Effect of 3d transition metal substitution on microstructure and microwave absorption properties of FeSiB nanocrystalline flakes

Effect of 3d transition metal substitution (Co and Ni) is studied on microstructure and absorption properties of FeSiB flakes in GHz. Fe_78−xM_xSi₉B₁₃ (M=Co or Ni, x=0, 5, 10 and 15) nanocrystalline flakes with nanocrystal/amorphous two-phase structure were prepared by ball milling. Substitution decreases the nanocrystal size and affects microwave behavior both compositionally and structurally according to the substitution mechanism. Compositional influence is contributing to the change of intrinsic magnetization parameters; structural influence works on exchange coupling. Absorption band of Fe₇₈Si₉B₁₃ flakes shifts towards lower frequency by the substitution, and Fe₆₃Co₁₅Si₉B₁₃ absorber shows promising absorption at C-band.     

Quantum confinement in CdSxSe1−x spherical nanocrystals in a fluorophosphate glass matrix

Differential (wavelength-modulated) absorption of sulfoselenide solid-solution nanocrystals has been studied in a glassy fluorophosphate matrix near the fundamental absorption edge at 360–620 nm. The observed oscillations in the absorption are attributed to size quantization of electrons and holes under strong quantum-confinement conditions. The sulfur content in the mixed semiconductor has been refined from Raman scattering spectra in CdS_xSe_1?x samples with x=0.30, and the nanocrystal size (R?30 Å) has been derived from low-frequency Raman scattering spectra. These data were used to calculate the energies of electron-hole transitions in nanocrystals of mixed composition, and their subsequent comparison with experiment. The calculations were found to be in a good agreement with the observed experimental absorption spectrum for nanocrystals about 45 Å in size. The applicability of band-structure simulation for a nonspherical nanocrystal grown in a fluorophosphate glass matrix is discussed.     

Size-quantization effects in the optical spectra of PbI2 and HgI2 nanocrystals

Size-quantization effects (short-wavelength shift of the structure and broadening) in low-temperature absorption spectra of PbI₂ and HgI₂ nanocrystals embedded in porous sodium borosilicate glass matrix with pores ranging in size from 2 to 50 nm have been observed and studied. The nanocrystal size was evaluated in the strong quantization approximation. It is shown that the size does not depend on the pore diameter of the matrices used, but is determined by the concentration of the solution introduced into the pores. The absorption and luminescence spectra of the systems thus obtained are shown to evolve as the substance emerges from the pores out onto the surface. The dynamics of formation and the phase composition of the PbI₂ and HgI₂ crystals on the surface are studied. Fiz. Tverd. Tela (St. Petersburg) 39, 468–473 (March 1997)     

Third order optical nonlinearities in ZnFe2O4 nanocrystals

Using Z-scan method with picosecond laser at 532 nm, the third order optical nonlinearities of ZnFe₂O₄ were investigated. The nonlinear refractive index is positive for all ZnFe₂O₄ samples and decrease with the nanocrystal size. The nonlinear absorption dominated by saturable absorption for 19 nm and 11 nm ZnFe₂O₄ but by two photon absorption for 5 nm ZnFe₂O₄ organosol. Origin of the optical nonlinearities and the size effect has been discussed.     

High intensity effect on two-photon resonant,coherent Raman scattering via excitonic molecules in CuCl and CuBr

Two-phonon resonant, coherent Raman scattering (four-photon degenerate coherent scattering) via excitonic molecules has been studied as a function of intensity of incident light in CuCl and CuBr. Observed line-shaped of coherent scattering spectra broadens as excitation intensity is raised. This broadening is found to be closely correlated with that of the two-photon absorption. These results are qualitatively explained by taking account of the excitation intensity-dependence of χ⁽³⁾, but cannot be explained by the autoinization model.     

Efimov physics beyond universality

We report the characteristics of cavity polaritons in a CuBr microcavity consisting of a λ/2-thick CuBr active layer and HfO₂/SiO₂ distributed Bragg reflectors: λ corresponds to an effective resonant wavelength of the lowest-lying exciton. The excitonic system of a CuBr crystal has three kinds of excitons labeled Z_f, Z_1,2, and Z₃ in which the Z_f exciton originates from a triplet state. We have investigated the dispersion relations of the cavity polaritons in the CuBr microcavity with the use of angle-resolved reflectance spectroscopy. The experimental results demonstrate the formation of four cavity-polariton branches due to the strong coupling between the Z_f, Z_1,2, and Z₃ excitons and cavity photon. The cavity-polariton dispersions were well analyzed with a phenomenological Hamiltonian for the strong coupling. The evaluated Rabi-splitting energies are 28, 95, and 74 meV for the Z_f, Z_1,2, and Z₃ excitons, respectively. These Rabi-splitting energies reflect the magnitudes of the oscillator strengths of the relevant excitons. Furthermore, it was confirmed that the cavity polaritons are fully stable at room temperature. We discuss the temperature dependence of the cavity-polariton energies and detuning, comparing with that of the bare exciton.     

Energies,oscillator strengths,and phonon side bands for an exciton in polar semiconductors

Within the Wannier exciton model for polar semiconductors, energies, oscillator strengths, and phonon side bands are calculated for the exciton ground- as well as the excited-states. Numerical results for CuCl and CuBr have been found to agree quite well with experiments. In particular, the one phonon side band for the 2s-state in CuCl is shown to be as strong as the zero phonon line.     

Nanocrystal and interface defects related photoluminescence in silicon-rich Al2O3 films

In this study, silicon nanocrystal-rich Al₂O₃ film has been prepared by co-sputtering a silicon and alumina composite target and subsequent annealing in N₂ atmosphere. The microstructure of the film has been characterized by infrared (IR) absorption, Raman spectra and UV-absorption spectra. Typical nanocrystal and interface defects related photoluminescence with the photon energy of 1.54 (IR band) and 1.69 eV (R band) has been observed by PL spectrum analysis. A post-annealing process in oxygen atmosphere has been carried out to clarify the emission mechanism. Despite the red shift of the spectra, enhanced emission of the 1.69 eV band together with the weak emission phenomenon of the 1.54 eV band has been found after the post-annealing. The R band is discussed to originate from silicon nanocrystal interface defects. The IR band is concluded to be a coupling effect between electronic and vibrational emissions.     

X-ray photoemission of valence electrons in cuprous halides,and lead and cadmium iodides.

The XPS spectra of valence bands in CuCl, CuBr, and CuI show the existence of two separate bands after appropriate deconvolution. The evaluation of the average p-d mixing rates on the basis of the tight-binding approximation with a few simplifying assumptions indicates, in accordance with optical data, that the upper valence band arises mainly from the 3d state of copper. The XPS spectra coincide qualitatively but not quantitatively with the spectra obtained by excitation with monochromatized synchrotron radiation at 40, 61, and 76 eV. A major difference is that the ratio of integrated intensity of the upper band to that of the lower band is larger in the case of excitation at 40, 61, or 76 eV. The XPS spectra of PbI₂ and CdI₂ have also been measured. In both materials, the valence band spectra have composite structures and give two well-defined peaks after deconvolution. The profile of the spectrum of PbI₂ appears to have some deviation from the reported energy band structure.     

Absorption cross-sections and lifetimes as a function of size in Si nanocrystals embedded in SiO2

The photoluminescence (PL) emission yield of Si nanocrystals embedded in SiO₂ depends on their size and on Si–SiO₂ interface passivation. In this work we aim at clarifying the relative importance of both contributions by studying lifetimes and absorption cross-sections as a function of size, for samples with and without passivation in forming gas. We find that while the PL lifetime increases steadily (quasi-linear dependence), the radiative lifetime increases exponentially with the nanocrystal size. Thus, as expected, radiative oscillator strengths are much smaller for large nanocrystals, but this reduction is partially compensated by a less effective quenching at interfacial non-radiative states. The absorption cross-section per nanocrystal rises as the nanocrystal size decreases, for all excitation wavelengths, implying that the variation of oscillator strength dominates over the reduction of the density of states. Passivation processes do not affect the emission mechanism and increase the emission yield while reducing the density of non-radiative recombination centers at the Si–SiO₂ interface (P_b centers).     

Structure of copper halide nanocrystals in photochromic glasses

The crystal structure of CuCl nanocrystals with effective radii ranging from 2.4 to 18.5 nm in photochromic glasses heat treated under different conditions is investigated using exciton spectroscopy, x-ray powder diffraction, and small-angle x-ray scattering. It is revealed that the size dependence of the energy of the Z ₃ exciton exhibits an anomalous behavior. The results obtained suggest that small-sized CuCl nanocrystals can crystallize in a modification different from the stable cubic modification.