Photoacoustic spectroscopy of diamond powders and polycrystalline films

Photoacoustic spectroscopy is used to study optical absorption in diamond powders and polycrystalline films. The photoacoustic spectra of diamond powders with crystallite sizes in the range from ∼100 μm to 4 nm and diamond films grown by chemical vapor deposition (CVD) had a number of general characteristic features corresponding to the fundamental absorption edge for light with photon energies exceeding the width of the diamond band gap (∼5.4 eV) and to absorption in the visible and infrared by crystal-structure defects and the presence of non-diamond carbon. For samples of thin (∼10 μm) diamond films on silicon, the photoacoustic spectra revealed peculiarities associated with absorption in the silicon substrate of light transmitted by the diamond film. The shape of the spectral dependence of the amplitude of the photoacoustic signal in the ultraviolet indicates considerable scattering of light specularly reflected from the randomly distributed faces of the diamond crystallites both in the polycrystalline films and in the powders. The dependence of the shape of the photoacoustic spectra on the light modulation frequency allows one to estimate the thermal conductivity of the diamond films, which turns out to be significantly lower than the thermal conductivity of single-crystal diamond. Fiz. Tverd. Tela (St. Petersburg) 39, 1787–1791 (October 1997)     

Luminescence of CsBr:Eu films grown by liquid-phase epitaxy

By liquid-phase epitaxy from an aqueous alcoholic solution, we have obtained films of the well-known storage phospor CsBr:Eu, and we have studied their cathodoluminescence and photoluminescence (PL) spectra compared with the undoped CsBr films. We have established that the structure of the photoluminescence centers of the CsBr:Eu films when excited by laser radiation in the absorption band of the Eu²⁺ ions (λ = 337 nm) includes Eu²⁺-V_Cs isolated dipole centers and CsEuBr₃ aggregate centers, and also luminescence centers based on inclusions of hydroxyl group OH⁻ with the corresponding emission bands in the 440 nm, 520 nm, and 600 nm regions. We have studied the dependence of the spectra and the intensity of the photoluminescence for CsBr:Eu films on annealing temperature in air at 423–483 K, compared with analogous dependences for CsBr:Eu single crystals obtained from the melt. We have shown that annealing the films at T = 423–463 K leads to rapid formation of CsEuBr3 aggregate luminescence centers, while for T > 473 K thermal degradation of these centers occurs. We conclude that the observed differences between the photoluminescence spectra of CsBr:Eu films and CsBr:Eu single crystals may be due to additional doping of the films with OH⁻ ions. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 2, pp. 191–194, March–April, 2006.     

Nonlinear photoacoustic response of opaque media in gas microphone signal detection

We have theoretically studied the effect of thermal nonlinearity, due to the temperature dependence of the thermophysical and optical parameters for thermally thick opaque media, on the characteristics of the fundamental photoacoustic signal when the signal is detected by a gas microphone. We have shown that the dependence of the amplitude of the nonlinear component of the signal on the intensity of the incident radiation I₀ is expressed by means of the dependence of the temperature rise for the irradiated sample surface Θ₀ on I₀, and the thermal nonlinearity does not affect the phase of the photoacoustic signal. We propose a theory for generation of the second harmonic of the photoacoustic signal. We have established that the phase shift of the photoacoustic signal is equal to 3π/4, while its amplitude depends on the frequency (∼ω^−3/2) and the intensity (∼ I ₀ ² ). __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 2, pp. 170–176, March–April, 2006.     

Transmission spectra of films of Mn<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Fe<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Se solid solutions

Films of Mn_1−x Fe _x Se (x = 0–0.45) solid solutions were flash-sputtered. We measured the transmission spectra of the films in the wavelength range 200–1000 nm at room temperature. From these spectra, we calculated the absorption coefficients and determined the fundamental absorption edge, the position of which is shifted from 2.65 eV in MnSe to 2.30 eV in solid solutions of compositions x = 0.20–0.45. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 1, pp. 136–138, January–February, 2007.     

Effect of thermal annealing on r.f. sputtering-deposited nanocrystalline GaN<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>As<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript> thin films

GaNAs thin films were deposited on Corning glass substrates by radio frequency (r.f.) sputtering in molecular nitrogen ambient. The stoichiometry in the GaNAs alloy was controlled by changing the nitrogen incorporation in the film during the growth process, through the variation of the r.f. power in the range 30–80 watts which produced films with N concentrations in the range: x = 0.85–0.90. The structural and optical properties of the GaNAs thin films were studied by X-ray diffraction (XRD), photoacoustic (PA) and photoluminescence (PL) spectroscopies. XRD measurements show a broad diffraction band with a peak close to the (002) diffraction line of the GaN hexagonal phase, and a slight shoulder at the position corresponding to the (111) GaAs cubic phase. The PA absorption spectra showed a remarkable shift to higher energies of the absorption edge as the r.f. power decreases corresponding to the films with higher N concentrations. Thermal annealing of the GaNAs films at temperatures of 450 °C produced a GaAs nanocrystalline phase with grain sizes in the range 10–13 nm, as confirmed by the XRD measurements that showed a well-defined peak in the (111) GaAs direction, and also by the PA spectra which showed an absorption band at energies around 1.45 eV due to the quantum confinement effects. PL spectra of thermal-annealed GaNAs films showed a very intense emission at 1.5 eV which we have associated to transitions between the first electron excited level and acceptor states in the GaAs nanocrystallites.     

Optical properties of films of the ternary compound CuIn<Subscript>3</Subscript>Se<Subscript>5</Subscript>

We have used the laser vaporization method to obtain films of the ternary compound CuIn₃Se₅ and have studied the composition and structure of the films obtained. We have determined the energy and nature of the optical transitions for the indicated compound from the transmission spectra in the region of the intrinsic absorption edge. We have calculated the valence-band crystal-field (Δ_CF) and spin-orbit (Δ_SO) splitting energies according to Hopfield’s quasicubic model for the ternary compound CuIn₃Se₅. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 1, pp. 82–85, January–February, 2007.     

Investigation of the optical properties of AgGaTe2 films obtained by laser deposition

We obtain thin films of AgGaTe₂ by laser vaporization of starting crystals. The compositions of the starting crystals and of the films obtained are determined by x-ray spectral analysis, with their structure and the parameters of the crystal lattice being determined by the x-ray method. The energies of interband transitions and crystalline (Δ _cr ) and spin-orbit (Δ _so ) splitting are calculated from transmission spectra in the region of the main absorption band. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 6, pp. 793–796, November–December, 1997.     

High-resolution photoacoustic and direct absorption spectroscopy of main greenhouse gases by use of a pulsed entangled cavity doubly resonant OPO

An entangled cavity doubly resonant optical parametric oscillator (ECOPO) has been developed to provide tunable narrow line width (<100 MHz) pulsed (8 ns) radiation over the 3.8–4.3 μm spectral range at a multi-kilohertz repetition rate with up to 100-W peak power. We demonstrate that coarse single mode tuning is obtained over the full spectral range of oscillation (300 cm⁻¹), while automated mode-hop-free fine tuning is carried out over more than 100 GHz. High-resolution spectra of main greenhouse gases (CO₂, N₂O, SO₂ and CH₄) have been obtained in good agreement with calculated spectra from the HITRAN database. These experiments outline the unique capabilities of the ECOPO for multi-gas sensing based on direct absorption as well as photoacoustic spectroscopy.     

Molar extinction coefficients of IR absorption bands of Cu(II) dipivaloylmethanate

IR absorption spectra of an intracomplex chelate compound of Cu(II) bis-dipivaloylmethanate in the spectral range 4000–300 cm⁻¹ are investigated. A comparison is made between the spectra of the complex in different aggregative states: as a solution in heptane and as condensed films. The molar extinction coefficients of absorption bands are calculated. The extinction coefficients found are used to evaluate the thickness of Cu(dpm)₂ films. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 1, pp. 34–37, January–February, 2000.     

Enhanced photosensitivity in sol–gel derived 20GeO2:80SiO2 thin films

We investigate the photosensitivity of binary 20GeO₂:80SiO₂ (germanosilicate) inorganic films. The samples have been fabricated by the sol–gel spin-coating method and the densification has been performed by rapid thermal annealing at various temperatures ranging from 500 °C to 1000 °C. The –OH absorption bands in the Fourier-transform infrared (FTIR) spectra and the refractive-index data show that the films annealed below 900 °C are porous and the films annealed at 900 °C and above are dense. An ultraviolet (UV) KrF laser at 248 nm has been used to induce the change in the refractive index of the samples. We have achieved a large refractive-index change (Δn) of 0.0098 after UV illumination in excess of 1 min for our dense germanosilicate films. This UV-induced refractive-index change is attributed to the formation of GeE’/SiE’ centers from Ge–Ge/Si–Si (neutral oxygen monovacancy) and Ge²⁺ centers and to the creation of oxygen deficiency related defects. From our experiments, the oxygen deficiency related defects correspond to the absorption band at 620–740 cm^-1 in the FTIR spectra and these are the defects which make a large contribution to Δn. The attenuation coefficient of the as-deposited and UV-illuminated dense samples is about 0.42 dB/cm at 1550 nm. For porous samples, UV exposure has densified the samples to some extent. PACS 82.50.Hp; 71.23.Cq; 81.20.Fw     

Thermal properties of 15-mol% gadolinia doped ceria thin films prepared by pulsed laser ablation

Thermal properties of 15-mol% gadolinia doped ceria thin films (Ce_0.85Gd_0.15 O_1.925) prepared by pulsed laser ablation on silicon substrates in the temperature range 473–973 K are presented. Thermal diffusivities and thermal conductivities were evaluated using photoacoustic spectroscopy. The influence of grain size on thermal properties of the films as a function of deposition temperature is studied. It is observed that the thermal diffusivity and the conductivity of these films decreases up to 873 K and then increases with substrate temperatures. The thermal properties obtained in these films are discussed on the basis of influence of grain size on phonon scattering.     

Structure and optical properties of films of the ternary compound CuGa5Se8

We have used a laser deposition method to obtain films of the ternary compound CuGa₅Se₈. We have studied their composition and structure. We have established that both the crystals and the films of the indicated compound crystallize in a defect-containing chalcopyrite structure. We have determined the energy and nature of the optical transitions from the transmission spectra in the region of the intrinsic absorption edge. We have calculated the valence-band crystal-field (Δ_CF) and spin–orbit (Δ_SO) splitting energies according to Hopfield’s quasicubic model for the ternary compound CuGa5Se8.     

Optical and IR studies on r.f. magnetron sputtered ultra-thin MoO3 films

Ultra-thin MoO₃ films were deposited onto glass and Si substrates by r.f. magnetron sputtering. The optical and IR properties of the films were studied in the range of 250 to 1000 nm and 400 to 1500 cm⁻¹, respectively. The optical transmission spectra show a significant shift in absorption edge. The energy gap of the films deposited at 373 K and 0.1 mbar was found to be 3.93 eV, and it decreases with increasing substrate temperature and decreasing sputtering pressure. The IR transmittance spectra shows strong modes of vibrations of Mo=O and Mo–O–Mo units of MoO₃ molecule. A significant change in energy gap and a shift in frequency of IR modes were observed in ultra-thin MoO₃ films.     

Photoelectrochemical characteristics of pulse electrodeposited CuInS<Subscript>2</Subscript> films

CuInS₂ films were deposited by the single-step pulse electrodeposition technique at different duty cycles in the range of 6–50% at 80 °C using conducting glass and titanium substrates. The films exhibited a single-phase tetragonal structure. Optical transmission spectra exhibited interference fringes. A direct band gap value of 1.42 eV was obtained. The refractive index value calculated by the envelope method was 1.2. Electrical resistivity of the films was in the range of 15–33 Ω cm. Photoelectrochemical cells made with the as deposited films yielded low photo output. After post-heat treatment in argon atmosphere at different temperatures, the films yielded higher photo output compared to earlier reports.     

Optical properties of silver selenium indate films obtained by the method of pulse laser vaporization

The spectra of transmission and reflection are measured in the region of 0.4–2.5 μm on thin silver selenium indate films obtained by means of pulse laser vaporization. The magnitudes of the refractive index and absorption coefficient are calculated. The energies of interband transitions and the values of crystalline and spin-orbit splitting are determined. The experimental results for the AgInSe₂ films agree with the data for bulk crystals. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 4, pp. 512–514, July–August, 2000.     

Preparation and investigation of composite SiO<Subscript>2</Subscript>-TiO<Subscript>2</Subscript> films

SiO₂-TiO₂ films [Si:Ti = 1:(0.06–2.3)] are obtained by the sol-gel method. The structural and photoluminescent properties of the films and powders heat-treated at different temperatures are studied. It is shown that after 700°C the composite consists of TiO₂ crystallites that are structurally similar to anatase and distributed in an amorphous SiO₂ matrix. The photoluminescence spectra have maxima at 450–500 nm. The photoluminescence intensity depends on the treatment temperature and TiO₂ content. __________ Translated from Zhurnal Prikladnoi Spektroskopii Vol. 74, No. 3, pp. 357–361, May–June, 2007.     

Application of reflection-absorption spectroscopy to quaternary solid solutions

In the present work the author describes a method for investigating phonon spectra of thin films of semiconductor solid solutions that is based on reflection-absorption spectroscopy in the far IR region. Analysis of spectra is carried out for two radiation polarizations (of the s- and p-type) and for the following experimental conditions: the spectral region 30–250 cm⁻¹ and an angle of incidence of 45°. By comparing theoretical and experimental spectra for quaternary solid solutions of Zn_xCd_yHg_1−x−yTe (ZCMT), the frequencies of LO- and TO-phonons are found and the three-mode behavior of the phonon spectra of ZCMT is established. Reported at the Second International Scientific and Technical Conference on Quantum Electronics, Minsk, November 23–25, 1998. Institute of Physics, Pedagogical University, 16A, Reitan Str., Rzeszów, 35–310, Poland. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 5, pp. 669–671, September–October, 1999.     

Vibrational spectra of thin films of lead and bismuth tungstates

The IR reflection spectra are investigated for the systems “thin film of PbWO₄ or Bi₂WO₆-molten quartz v-SiO₂ substrate” within the region of 400–1600 cm⁻¹ at T=295 K. Interference in the thin films is considered. Interpretation of the bands belonging to the PbWO₄ and Bi₂WO₆ films is carried out. I. Franko L’vov State University, 50, Dragomanova St., 290005, L’vov, Ukraine. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 65, No. 3, pp. 459–461, May–June, 1998.     

Photoelectric properties ofp-CuInSe2 thin films obtained by pulsed laser vaporization

Using the method of phase-sensitive detection, we investigated the photoconductivity spectra of polycrystalline p-CuInSe₂ films obtained in vacuum by the method of pulsed laser vaporization of initial single crystals. We show that, in contrast to single crystals, films are characterized by monopolar photoconductivity in the extrinsic and intrinsic regions of optical absorption and by a linear mechanism of recombination of nonequilibrium charge carriers at the intensities of illumination 0–100 mW/cm² in the temperature range 80–300 K. Institute of the Solid-State and Semiconductor Physics, National Academy of Sciences of Belarus, 17, P. Brovka St., Minsk 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii. Vol. 66, No. 1, pp. 138–141, January–February, 1999.     

Resonance photoacoustic spectroscopy and gas analysis of gaseous flow at reduced pressure

The results of theoretical and experimental studies of sensitivity of a resonant photoacoustic Helmholtz resonator detector for gas flowing through a photoacoustic cell under reduced pressure are presented. The measurements of the sensitivity and ultimate sensitivity of the differential photoacoustic cell were performed with a near-IR room-temperature diode laser using the well-known H₂O absorption line (12496.1056 cm^-1) as a reference. The measured value of the sensitivity (6–17 Pa W m^-1) is in satisfactory agreement with the calculated one, which equals 6–35 Pa W m^-1. The obtained value of the ultimate sensitivity ((3–5)×10^-7 W m^-1 Hz^-1/2) provides measurements of the concentration of molecules at the ppb–ppm level. Received: 19 April 2001 / Revised version: 18 September 2001 / Published online: 7 November 2001