Thermal annealing effect of on optical constants of vacuum evaporated Se75S25−xCdx chalcogenide thin films

Chalcogenide glasses are interesting materials due to their infrared transmitting properties and photo induced effects exhibited by them. Thin films with thickness of 3000 Å of the glasses Se₇₅S_25−xCd_x with x=6, 8 and 10 at% prepared by melt quench technique were evaporated by thermal evaporation onto glass substrates under a vacuum of 10⁻⁶ Torr. The optical constants (absorption coefficient, refractive index and extinction coefficient) of as-prepared and annealed films have been studied as a function of photon energy in the wave length region 400-1000 nm. Analysis of the optical absorption data shows that the rule of non-direct transitions predominates. It has been found that the absorption coefficient and optical band gap increase with increasing annealing temperatures. The refractive index (n) and the extinction coefficient (k) were observed to decrease with increasing annealing temperature.     

Structural and optical properties of nitrogen-incorporated HfO2 gate dielectrics deposited by reactive sputtering

High-k HfO_xN_y thin films with different nitrogen-incorporation content have been fabricated on Si (1 0 0) substrate by means of radio-frequency reactive sputtering method. Analyses from X-ray diffraction (XRD) and atomic force microscopic have indicated that the increase of the crystallization temperature of HfO₂ thin films and the decrease of the roughness root-mean-square value of HfO₂ thin films due to the incorporation of nitrogen. Based on a parameterized Tauc-Lorentz (TL) dispersion model, the optical properties of the HfO_xN_y thin films related to different nitrogen-incorporation content are systematically investigated by spectroscopic ellipsometer. Increase in the refractive index and the extinction coefficient and reduction in band gap with increase of nitrogen-incorporation content are discussed in detail.     

Effects of post-thermal annealing temperature on the optical and structural properties of gold particles on silicon suboxide films

In this work, silicon suboxide (SiO_x) thin films were deposited using a RF magnetron sputtering system. A thin layer of gold (Au) with a thickness of about 10 nm was sputtered onto the surface of the deposited SiO_x films prior to the thermal annealing process at 400 °C, 600 °C, 800 °C and 1000 °C. The optical and structural properties of the samples were studied using scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), X-ray diffractometry (XRD), Fourier transform infrared spectroscopy (FTIR) and optical transmission and reflection spectroscopy. SEM analyses demonstrated that the samples annealed at different temperatures produced different Au particle sizes and shapes. SiO_x nanowires were found in the sample annealed at 1000 °C. Au particles induce the crystallinity of SiO_x thin films in the post-thermal annealing process at different temperatures. These annealed samples produced silicon nanocrystallites with sizes of less than 4 nm, and the Au nanocrystallite sizes were in the range of 7-23 nm. With increased annealing temperature, the bond angle of the Si-O bond increased and the optical energy gap of the thin films decreased. The appearance of broad surface plasmon resonance absorption peaks in the region of 590-740 nm was observed due to the inclusion of Au particles in the samples. The results show that the position and intensity of the surface plasmon resonance peaks can be greatly influenced by the size, shape and distribution of Au particles.     

Influence of composition on electrical and optical properties of new chalcogenide thin films from Ge-Se-Tl system

Bulk Ge₂₀Se_80−xTl_x (x ranging from 0 to 15 at%) chalcogenide glasses were prepared by conventional melt quenching technique. Thin films of these compositions were prepared by thermal evaporation, on glass and Si wafer substrates at a base pressure of 10⁻⁶ Torr. X-ray diffraction studies were performed to investigate the structure of the thin films. The absence of any sharp peaks in the X-ray diffractogram confirms that the films are amorphous in nature. The optical constants (absorption coefficient, optical band gap, extinction coefficient and refractive index) of Ge₂₀Se_80−xTl_x thin films are determined by absorption and reflectance measurements in a wavelength range of 400-900 nm. In order to determine the optical gap, the absorption spectra of films with different Tl contents were analyzed. The absorption data revealed the existence of allowed indirect transitions. The optical band gap showed a sharp decrease from 2.06 to 1.79 eV as the Tl content increased from 0% to 15%. It has been found that the values of absorption coefficient and refractive index increase while the extinction coefficient decreases with increase in Tl content in the Ge-Se system. These results are interpreted in terms of the change in concentration of localized states due to the shift in Fermi level. DC electrical conductivity of Ge₂₀Se_80−xTl_x thin films was carried out in a temperature range 293-393 K. The electrical activation energy of these films was determined by investigating the temperature dependence of dc conductivity. A decrease in the electrical activation energy from 0.91 to 0.55 eV was observed as the Tl content was increased up to 15 at% in Ge₂₀Se_80−xTl_x system. On the basis of pre-exponential factor, it is suggested that the conduction is due to thermally assisted tunneling of the carriers in the localized states near the band edges.     

FTIR sensitivity enhancement on Pt/SiO2/Au layered structures: A novel method for CO adsorption studies on Pt surfaces

Specular reflectance FTIR study of carbon monoxide adsorbed on platinum is performed on Pt/SiO₂/Au layered structures prepared by deposition of thin films on silicon (1 0 0) wafers. The layered structures consist of 5 nm thick platinum films over SiO₂ films of varying thicknesses with 50 nm thick reflecting gold films underneath. Due to optical interference effects, the reflectance of each of these structures varies with the incident infrared wavelength and goes through a minimum at a wavelength that depends on the thickness of the SiO₂ layer. The decrease in the reflectance R causes an effective increase in the ΔR/R value resulting in a large increase in the infrared absorption band intensity of linearly-adsorbed CO. The peak height changes with changing the SiO₂ thickness in the structures and is greatest for the sample which has lowest reflectance near the absorption wavelength of CO (∼2100 cm⁻¹). This improvement in the ratio of FTIR signal to background reflectance can be very useful for probing low surface area model catalytic surfaces at atmospheric pressures and under reaction conditions. A spectrum of CO adsorbed on nanofabricated Pt nanowire catalysts on TiO₂ support is also shown as an example of the sensitivity enhancement on layered structures.     

Absorption and emission of light in spark-processed silicon

Spark-processed Si (sp-Si) exhibits blue, green and red photoluminescence at around 385, 525 and 650 nm, depending on the wavelength of excitation. Its optical absorption spectrum reveals bands peaked approximately at 245, 277, 325 and 389 nm. The centers where absorption takes place were modeled as Si and silica clusters in an amorphous SiO_xN_y matrix using various embedding schemes. Geometry optimizations were applied prior to calculations of the absorption spectra of the clusters. The measured absorption spectrum of sp-Si and calculated absorption spectra were compared. Best agreement is achieved for Si particles embedded in amorphous SiO_xN_y matrix. The importance of the various embedding schemes is discussed and conclusions for the centers of emission are established.     

Optical characterization of PLD grown nitrogen-doped TiO2 thin films

Nitrogen-doped TiO₂ thin films were prepared by pulsed laser deposition (PLD) by ablating metallic Ti target with pulses of 248 nm wavelength in reactive atmospheres of O₂/N₂ gas mixtures. The layers were characterized by UV-VIS spectrophotometry and variable angle spectroscopic ellipsometry with complementary profilometry for measuring the thickness of the films. Band gap and extinction coefficient values are presented for films deposited at different substrate temperatures and for varied N₂ content of the gas mixture. The shown tendencies are correlated to nitrogen incorporation into the TiO_2-xN_x layers. It is shown that layers of significantly increased visible extinction coefficient with band gap energy as low as 2.89 eV can be obtained. A method is also presented how the spectroscopic ellipsometric data should be evaluated in order to result reliable band gap values.     

Optical characterization of xTiO2-(60 − x)SiO2-40Na2O glasses: II. Absorption edge, Fermi level, electronic polarizability and optical basicity

In the present work different optical properties of xTiO₂-(60 − x)SiO₂-40Na₂O (wt%) optical glasses are determined. The characterization is done over a wide energy range, 0.41-6.2 eV. The refractive index and the extinction coefficient data are used to measure the absorption coefficient of the different glass compositions. Studying the UV-absorption edge, both direct and indirect allowed transitions with their optical energy gaps are carried out. In the same time, the Urbach energy is evaluated. From the extinction coefficient data, the Fermi energy of the glasses is calculated. The molar refraction, electronic polarizability and the optical basicity are obtained using the measured glass refractive indices.     

Hf1−xSixOy dielectric films deposited by UV-photo-induced chemical vapour deposition (UV-CVD)

Hf_1−xSi_xO_y is an attractive candidate material for high-k dielectrics. We report in this work the deposition of ultra-thin Hf_1−xSi_xO_y films (0.1 ≤ x ≥ 0.6) on silicon substrate at 450 °C by UV-photo-induced chemical vapour deposition (UV-CVD) using 222 nm excimer lamps. Silicon(IV) and hafnium(IV) organic compounds were used as the precursors. Films from around 5 to 40 nm in thickness with refractive indices from 1.782 to 1.870 were grown. The deposition rate was found to be of 6 nm/min at a temperature of 450 °C. The physical, interfacial and electrical properties of hafnium silicate (Hf_1−xSi_xO_y) thin films were investigated by using X-ray photoelectron spectroscopy, ellipsometry, FT-IR, C-V and I-V measurements. XRD showed that they were basically amorphous, while Fourier transform infrared spectroscopy (FT-IR), clearly revealed Hf-O-Si absorption in the photo-CVD deposited Hf_1−xSi_xO_y films. Surface and interfacial properties were analysed by TEM and XPS. It is found that carbon content in the films deposited by UV-CVD is very low and it also decreases with increasing Si/(Si + Hf) ratio, as low as about 1 at.% at the Si/(Si + Hf) ratio of 60 at.%.     

Fabrication of multilayered Ge nanocrystals embedded in SiOxGeNy films

Multilayered Ge nanocrystals embedded in SiO_xGeN_y films have been fabricated on Si substrate by a (Ge + SiO₂)/SiO_xGeN_y superlattice approach, using a rf magnetron sputtering technique with a Ge + SiO₂ composite target and subsequent thermal annealing in N₂ ambient at 750 °C for 30 min. X-ray diffraction (XRD) measurement indicated the formation of Ge nanocrystals with an average size estimated to be 5.4 nm. Raman scattering spectra showed a peak of the Ge-Ge vibrational mode downward shifted to 299.4 cm⁻¹, which was caused by quantum confinement of phonons in the Ge nanocrystals. Transmission electron microscopy (TEM) revealed that Ge nanocrystals were confined in (Ge + SiO₂) layers. This superlattice approach significantly improved both the size uniformity of Ge nanocrystals and their uniformity of spacing on the ‘Z’ growth direction.     

X-ray photoemission and X-ray absorption studies of Hf-silicate dielectric layers

Photoelectron spectroscopy and X-ray absorption spectroscopy (XAS) measurements have been performed on HfSi_xO_y and HfSi_xO_yN_z dielectric layers, which are potential candidates as high-k transistor gate dielectrics. The hafnium silicate layers, 3-4 nm thick, were formed by codepositing HfO₂ and SiO₂ (50%:50%) by MOCVD at 485 °C on a silicon substrate following an IMEC clean. Annealing the HfSi_xO_y layer in a nitrogen atmosphere at 1000 °C resulted in an increase in the Si⁴⁺ chemical shift from 3.5 to 3.9 eV with respect to the Si⁰ peak. Annealing the hafnium silicate layer in a NH₃ atmosphere at 800 °C resulted in the incorporation of 10% nitrogen and the decrease in the chemical shift between the Si⁴⁺ and the Si⁰ to 3.3 eV. The results suggest that the inclusion of nitrogen in the silicate layer restricts the tendency of the HfO₂ and the SiO₂ to segregate into separate phases during the annealing step. Synchrotron radiation valence band photoemission studies determined that the valence band offsets were of the order of 3 eV. X-ray absorption measurements show that the band gap of these layers is 4.6 eV and that the magnitude of the conduction band offset is as little as 0.5 eV.     

IR and XPS investigation of visible-light photocatalysis—Nitrogen-carbon-doped TiO2 film

To use solar irradiation or interior lighting efficiently, we sought a photocatalyst with high reactivity under visible light. Nitrogen and carbon doping TiO_2−x−yN_xC_y films were obtained by heating the TiO₂ gel in an ionized N₂ gas and then were calcined at 500 °C. The TiO_2−x−yN_xC_y films have revealed an improvement over the TiO₂ films under visible light (wavelength, 500 nm) in optical absorption and photocatalytic activity such as photodegradation of methyl orange. X-ray photoemission spectroscopy, infrared spectrum and UV-visible (UV-vis) spectroscopy were used to find the difference of two kinds of films. Nitrogen and carbon doped into substitutional sites of TiO₂ has been proven to be indispensable for band-gap narrowing and photocatalytic activity.     

Characterization of HfOxNy gate dielectrics using a hafnium oxide as target

Hafnium oxynitride (HfO_xN_y) gate dielectric has been deposited on Si (1 0 0) by means of radio frequency (rf) reactive sputtering using directly a HfO₂ target in N₂/Ar ambient. The thermal stability and microstructural characteristics for the HfO_xN_y films have been investigated. XPS results confirmed that nitrogen was successfully incorporated into the HfO₂ films. XRD analyses showed that the HfO_xN_y films remain amorphous after 800 °C annealing in N₂ ambient. Meanwhile the HfO_xN_y films can also effectively suppress oxygen diffusion during high temperature annealing and prevent interface layer from forming between HfO_xN_y films and Si substrates. AFM measurements demonstrated that surface roughness of the HfO_xN_y films increase slightly as compared to those pure HfO₂ films after post deposition annealing. By virtue of building reasonable model structure, the optical properties of the HfO_xN_y films have been discussed in detail.     

Infrared optical properties of Ba(Zr0.20Ti0.80)O3 and Ba(Zr0.30Ti0.70)O3 thin films prepared by sol-gel method

Ba(Zr_xTi_1−x)O₃ (BZT) (x = 0.20 and 0.30) thin films are deposited on Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrate by sol-gel method. X-ray diffraction patterns show that the thin films have a good crystallinity. Optical properties of the films in the wavelength range of 2.5-12 μm are studied by infrared spectroscopic ellipsometry (IRSE). The optical constants of the BZT thin films are determined by fitting the IRSE data using a classical dispersion formula. As the wavelength increases, the refractive index decreases, while the extinction coefficients increase. The effective static ionic charges are derived, which are smaller than that in a purely ionic material for the BZT thin films.     

Nanocomposite L10 FePt–SiNx and FePt–SiNx–C films with large coercivity and small grain size on a TiN intermediate layer

FePt–SiN_x–C films with high coercivity, (001) texture and small grain size were obtained by co-sputtering FePt, Si₃N₄ and C on TiN/CrRu/glass substrate at 380 °C. Without C doping, FePt–SiN_x films with good perpendicular anisotropy and a single layer structure were obtained. However, the grain size was still too large and the grain isolation was poor. When C was doped into the FePt–SiN_x films, the out-of-plane coercivity increased due to the decrease of the exchange coupling. In addition, the grain size of the FePt films decreased, and well-separated FePt grains with uniform size were formed. The microstructure of [FePt–SiN_x 40 vol%]−20 vol% C films changed from a single layer structure to a multiple layer structure when the FePt thickness was increased from 4 to 10 nm. By optimizing the sputtering process, the [FePt (4 nm)–SiN_x 40 vol%]−20 vol% C (001) film with coercivity higher than 21.5 kOe, a single layer structure, and small average FePt grain size of 5.6 nm was obtained, which makes it suitable for ultrahigh density perpendicular recording.     

Optical properties of Ge-As-Te thin films

Different compositions of Ge_xAs₁₀Te_90−x (x=5, 10, 15, 20, and 25 at%) chalcogenide glasses were prepared by the usual melt quench technique. Amorphous Ge_xAs₁₀Te_90−x thin films were deposited onto cleaned glass substrates using the thermal evaporation method. Transmission spectra, T(λ), of the films at normal incidence were measured in the wavelength range 400-2500 nm. A straightforward analysis proposed by Swanepoel based on the use of the maxima and minima of the interference fringes has been used to drive the film thickness, d, the complex index of refraction, n, and the extinction coefficient, k. It was found that, the addition of Ge content at the expense of Te atoms shifts the optical band gap to the short wavelength side (blue shift of the optical band gap) while the refractive index are found to decreases. The obtained results of the refractive index were discussed in terms of the electronic polarizability and the single-oscillator Wemple and DiDomenico model (WDD). The optical absorption is due to the allowed non-direct optical transitions. The observed increase in the optical band gap with the increase in Ge content was discussed in terms of the width of the tail states in the gap and the covalent bond approach.     

Compositional dependence of the optical properties of amorphous semiconducting glass Ge10AsxSe(90−x) thin films

Optical properties of ternary chalcognide amorphous Ge₁₀As_xSe_(90−x) (with 10?x?25 at%) thin films prepared by thermal evaporation have been measured in visible and near-infrared spectral region. The straightforward analysis proposed by Swanepoel has been successfully employed, and it has allowed us to determine the average thickness , and the refractive index, n, of the films, with high accuracy. The refractive index, n and the average thickness has been determined from the upper and lower envelopes of the transmission spectra measured at normal incidence, in the spectral range 400-2500 nm. The absorption coefficient α, and therefore extinction coefficient k, have been determined from the transmission spectra in the strong-absorption region. The dispersion of the refractive index is discussed in terms of the single oscillator Wemple-DiDomenico model, and the optical absorption edge is described using the ‘nondirect transition’ model proposed by Tauc. Likewise, the optical energy gap is derived from Tauc's extrapolation. The relationship between the optical gap and chemical composition in Ge₁₀As_xSe_(90−x) amorphous system is discussed in terms of the average heat of atomization H_s and average coordination number N_c. Finally, the chemical bond approach has been also applied successfully to interpret the decrease of the glass optical gap with increasing As content.     

Thickness measurement of a thin hetero-oxide film with an interfacial oxide layer by X-ray photoelectron spectroscopy

The general equation T_ove = L cos  θ ln(R_exp/R₀ + 1) for the thickness measurement of thin oxide films by X-ray photoelectron spectroscopy (XPS) was applied to a HfO₂/SiO₂/Si(1 0 0) as a thin hetero-oxide film system with an interfacial oxide layer. The contribution of the thick interfacial SiO₂ layer to the thickness of the HfO₂ overlayer was counterbalanced by multiplying the ratio between the intensity of Si⁴⁺ from a thick SiO₂ film and that of Si⁰ from a Si(1 0 0) substrate to the intensity of Si⁴⁺ from the HfO₂/SiO₂/Si(1 0 0) film. With this approximation, the thickness levels of the HfO₂ overlayers showed a small standard deviation of 0.03 nm in a series of HfO₂ (2 nm)/SiO₂ (2-6 nm)/Si(1 0 0) films. Mutual calibration with XPS and transmission electron microscopy (TEM) was used to verify the thickness of HfO₂ overlayers in a series of HfO₂ (1-4 nm)/SiO₂ (3 nm)/Si(1 0 0) films. From the linear relation between the thickness values derived from XPS and TEM, the effective attenuation length of the photoelectrons and the thickness of the HfO₂ overlayer could be determined.     

XRR and GISAXS study of silicon oxynitride films

Thin films of silicon oxynitride have largely replaced pure silicon oxide films as gate and tunnel oxide films in modern technology due to their superior properties in terms of efficiency as boron barrier, resistance to electrical stress and high dielectric strength. A single chamber system for plasma enhanced chemical vapor deposition was employed to deposit different films of SiO_xN_yH_z with 0.85 < x < 1.91. All films were previously characterized by Rutherford back-scattering and infrared spectroscopy to determine the stoichiometry and the presence of various bonding configurations of constituent atoms. We used X-ray reflectivity to determine the electron density profile across the depth, and we showed that the top layer is densified. Moreover, grazing incidence small-angle X-ray scattering was used to study inhomogeneities (clustering) in the films, and it is shown that plate-like inhomogeneities exist in the top and sphere-like particles at the bottom part of the film. Their shape and size depend on the stoichiometry of the films.     

Investigation of nonlinear optical parameters of zinc based amorphous chalcogenide films

Third order nonlinear optical properties of amorphous Zn_x–S_y–Se_100−x−y chalcogenide films have been investigated using single beam transmission z-scan technique at 1064 nm of Nd:YAG laser. Measurement of optical properties of amorphous Zn_x–S_y–Se_100−x−y chalcogenide films prepared by thermal evaporation technique has been made. X-ray diffraction patterns of chalcogenide films confirm the amorphous nature. Optical band gap (E_g) has been estimated using Tauc's plot method from transmission spectra that is found to decrease with increase in content due to valence band broadening and band tailing the system. Nonlinear refractive index (n₂), nonlinear absorption coefficient (β) and third order nonlinear susceptibility (χ³) of chalcogenide films have been estimated. Self-focusing effect has been observed in closed aperture and reverse saturable absorption in open aperture scheme. Limiting threshold and dynamic range have been calculated from optical limiting studies. The increase in nonlinearity with increase in Zn content has been observed that is understood to be due to decrease in band gap on Zn doping. High nonlinearity makes these films a potential candidate for waveguides, fibers and two photon absorption in optical limiters.