Light emission from a-Si:C:O:H films fabricated by C2F6 and O2/C2F6 plasma treating silicone oil liquid

Amorphous Si:C:O:H films were fabricated at low temperature by C₂F₆ and O₂/C₂F₆ plasma treating silicone oil liquid. The a-Si:C:O:H films fabricated by C₂F₆ plasma treatment exhibited white photoluminescence at room temperature, while that by O₂/C₂F₆ plasma treatment exhibited blue photoluminescence. Fourier transformed infrared spectroscopy and Raman spectroscopy studies showed that the sp³ and sp² hybridized carbons, SiC bond, SiO bond and carbon-related defects in a-Si:C:O:H films correlated with photoluminescence. It is suggested that the blue emission at 469 nm was related to the sp³ and sp² hybridized carbons, SiC bond, carbon dangling bonds as well as SiO short chains and small clusters, while the light emitting at 554 nm was related to the carbon-related defects.     

Structural and electrical properties of high-k HfO2 films modified by CHF3 and C4F8/O2 plasmas

As-deposited HfO₂ films were modified by CHF₃, C₄F₈, and mixed C₄F₈/O₂ plasmas in a dual-frequency capacitively coupled plasma chamber driven by radio frequency generators of 60 MHz as the high frequency (HF) source and 2 MHz as the low frequency source (60/2 MHz). The influences of various surface plasma treatments under CHF₃, C₄F₈, and C₄F₈/O₂ were investigated in order to understand the chemical and structural changes in thin-film systems, as well as their influence on the electrical properties. Fluorine atoms were incorporated into the HfO₂ films by either CHF₃ or C₄F₈ plasma treatment; meanwhile, the C/F films were formed on the surface of the HfO₂ films. The formation of C/F layers decreased the k value of the gate stacks because of its low dielectric constant. However, the addition of O₂ gas in the discharge gases suppressed the formation of C/F layers. After thermal annealing, tetragonal HfO₂ phase was investigated in both samples treated with CHF₃ and C₄F₈ plasmas. However, the samples treated with O-rich plasmas showed monoclinic phase, which indicated that the addition of O plasmas could influence the Hf/O ratio of the HfO₂ films. The mechanism of the t-HfO₂ formation was attributed to oxygen insufficiency generated by the incorporation of F atoms. The capacitors treated with C₄F₈/O₂ plasmas displayed the highest k value, which ascribed that the C/F layers were suppressed and the tetragonal phase of HfO₂ was formed. Good electrical properties, especially on the hysteresis voltage and frequency dispersion, were obtained because the bulk traps were passivated by the incorporation of F atoms. However, the H-related traps were generated during the CHF₃ plasma treatments, which caused the performance degradation. All the treated samples showed lower leakage current density than the as-deposited HfO₂ films at negative bias due to the reduced trap-assisted tunneling by the incorporation of F to block the electrons transferring from metal electrode to the trap level.     

Luminescence and structure of nanosized inclusions formed in SiO2 layers under double implantation of silicon and carbon ions

Luminescent and structural characteristics of SiO₂ layers exposed to double implantation by Si⁺ and C⁺ ions in order to synthesize nanosized silicon carbide inclusions have been investigated by the photoluminescence, electron spin resonance, transmission electron microscopy, and electron spectroscopy methods. It is shown that the irradiation of SiO₂ layers containing preliminary synthesized silicon nanocrystals by carbon ions is accompanied by quenching the nanocrystal-related photoluminescence at 700–750 nm and by the enhancement of light emission from oxygen-deficient centers in oxide in the range of 350–700 nm. Subsequent annealing at 1000 or 1100°C results in the healing of defects and, correspondingly, in the weakening of the related photoluminescence peaks and also recovers in part the photoluminescence of silicon nanocrystals if the carbon dose is less than the silicon dose and results in the intensive white luminescence if the carbon and silicon doses are equal. This luminescence is characterized by three bands at ～400, ～500, and ～625 nm, which are related to the SiC, C, and Si phase inclusions, respectively. The presence of these phases has been confirmed by electron spectroscopy, the carbon precipitates have the sp ³ bond hybridization. The nanosized amorphous inclusions in the Si⁺ + C⁺ implanted and annealed SiO₂ layer have been revealed by high-resolution transmission electron microscopy.     

Defect evolution and photoluminescence in anion-defective alumina single crystals exposed to high doses of gamma-rays

A method of luminescent UV and VUV spectroscopy was used to study the evolution of color centers in anion-defective alumina single crystals exposed to high doses of gamma-radiation. A sharp drop in the intensity of the emission bands and, therefore, the concentration of F⁺ and F-centers associated with the formation of aggregate F₂-type centers was found. The aggregate centers create an additional emission band in the range of (1.8–2.8) eV. When the crystals are exposed to middle and high doses, the photoluminescence (PL) intensity is the highest in the emission band of F₂²⁺-centers, which indicates a high concentration of the aggregates from singly charged oxygen vacancies (of F⁺-centers). When PL of the crystals exposed to high doses is excited with synchrotron radiation of the VUV range, a wide emission band in the red and near infrared (NIR) regions is registered. The centers related presumably to impurity defects, their aggregates and clusters consisting of several oxygen vacancies are responsible for this emission band.     

Adsorption of oxygen molecular on pristine and defected SiC nanotubes

The structural and electronic properties of oxygen molecular adsorbed on the exterior surface of pristine and N_C or B_C defected (10,0) or (6,6) SiCNT have been investigated systematically using the first-principles projector-augmented wave potential within the density-functional theory under the generalized-gradient approximation. We find that for both pristine tubes the preferred adsorption sites of the O₂ molecule are above and nearly parallel to armchair Si-C bond whether physisorption or chemisorption. The strong chemical interaction between O₂ molecule and tube leads to not only a vanishing in magnetism of the O₂ molecule but also an outward relaxation of the underlying Si-C bond. The C atom substituted by N or B atom assists O₂ molecule adsorption above and nearly parallel to zigzag Si-N or Si-B bond as well as imparts a metallic character on the SiCNTs with higher concentration of the defects or a magnetism on the SiCNTs with lower concentration of the defects. Therefore, a combination of N or B doping followed by exposure to air may be an effective way to tune the electronic properties of the semiconducting SiCNTs. Furthermore, the lower binding energies for the pair of oxygen interstitials chemisorbed on N_C or B_C defected (10,0) or (6,6) SiCNT show that the oxygen molecule will dissociate to the pair of oxygen interstitials at the sidewall of N_C or B_C defected SiCNTs.     

Carbon-13 enrichment by IR laser chemistry of CHF3-Cl2

IR laser chemistry of CHF₃ is investigated in both neat form and in the presence of Cl₂ for carbon-13 enrichment. Infrared multiple-photon dissociation of CHF₃ is an order of magnitude more efficient in the scavenged system compared to the neat case. The photolysis of CHF₃/Cl₂ mixture results in two products, viz., CF₂Cl₂ and C₂F₄Cl₂ but with different enrichment factors. The parametric studies show that C₂F₄Cl₂ arises due to MPD of CF₂Cl₂ in secondary photolysis.     

Deep UV resonance Raman spectroscopic study of CnF2n+2 molecules: the excitation of C–C σ bond

The σ–σ* transition of C–C bond in C_nF_2n+2 molecules was studied by deep UV resonance Raman spectroscopy. With the C–C σ bond selectively excited by the deep UV laser at 177.3 nm, the resonance Raman spectra of C_nF_2n+2 molecules were obtained on our home‐assembled deep UV Raman spectrograph. The Raman bands at 1299, 1380 and 2586 cm⁻¹ due to the C–C skeletal stretching modes are evidently enhanced owing to the resonance Raman effect. Based on the resonance Raman spectra and theoretical calculation results, it is proposed that the electronic geometry of C_nF_2n+2 molecules at the σσ* excited state is displaced along the directions perpendicular and parallel to the C–C skeleton, and the excited C–C bond is not dissociative due to the delocalization of the excited electron in σ* orbital. Copyright © 2012 John Wiley & Sons, Ltd.     

Study of the visible-excitation luminescence of NTA-TiO2(AB) with single-electron-trapped oxygen vacancies

A new kind of TiO₂ (NTA-TiO₂(AB)) with single-electron-trapped oxygen vacancies was prepared by the dehydration of nanotubed titanic acid under vacuum. Under visible-light excitation (λ_ex=420 nm to 650 nm) NTA-TiO₂(AB) showed a relatively intense emission, which red shifts with the increase of excitation wavelength. Analyzing the photoluminescence spectra, a sub-band induced by single-electron-trapped oxygen vacancies within E_g(NTA-TiO₂(AB)) was obtained. PACS 71.20.-b     

机械-化学方法在硅(100)表面制备芳香烃重氮盐单层膜

利用机械-化学方法同时实现硅表面的图形化和功能化. 在芳香烃重氮盐(C₆H₅N₂BF₄)中用金刚石刀具刻划单晶硅(100),使单晶硅表面的Si-O键断裂,形成硅的自由基,进而它们与溶液中含有的有机分子共价结合以形成自组装单层膜. 用原子力显微镜对自组装前后的表面形貌进行表征,用飞行时间二次离子质谱和红外光谱对自组装单层膜进行检测和分析,通过确认C₆H₅离子的存在证明自组装单层     

Ti<Superscript>3+</Superscript>-doped TiO<Subscript>2</Subscript> hollow sphere with mixed phases of anatase and rutile prepared by dual-frequency atmospheric pressure plasma jet

A novel method of synthesizing Ti³⁺-doped TiO₂ was proposed. Ti³⁺-doped TiO₂ hollow spheres were prepared with different thickness of carbon shell by using atmospheric pressure plasma jet generated by dual-frequency power sources. The as-synthesized Ti³⁺-doped TiO₂ hollow microspheres were characterized by X-ray diffraction (XRD) pattern, scanning electron microscope (SEM) images, high-resolution transmission electron microscopy (HRTEM) images, Raman spectra, X-ray photoelectron spectroscopy (XPS), and UV–vis spectra. These results indicated that these samples had mixed phases of anatase and rutile and the structure of hollow sphere varied with different thickness of carbon shell. The Ti-O-C chemical bond was the connection between the TiO₂ hollow sphere and carbon layer. Amount of Ti³⁺ ions were found, which were accompanied with the formation of oxygen vacancies. Meantime, the as-synthesized catalysts also display strong absorption in the visible light region and have a narrow band energy gap. Optical emission spectroscopy (OES) was used to observe different excited species in the discharge area. These results showed that the oxygen content had a significant impact on the number of oxygen vacancies. Finally, the photocatalytic activities of as-prepared samples were evaluated by decomposition of rhodamine B aqueous solution, which showed better photocatalytic activity under UV–vis light irradiation.     

Preparation of visible light responsive N doped TiO2 via a reduction-nitridation procedure by nonthermal plasma treatment

A visible light responsive N-doped TiO₂ was prepared via a reduction-nitridation procedure by nonthermal plasma treatment. X-ray diffraction, N₂ adsorption, UV-vis spectroscopy, photoluminescence, and X-ray photoelectron spectroscopy were used to characterize the prepared TiO₂ samples. The plasma treatment did not change the phase composition and particle sizes of TiO₂ samples, but extended its absorption edges to the visible light region. The photocatalytic activities were tested in the degradation of an aqueous solution of a reactive dyestuff, methylene blue, under visible light. The photocatalytic activities of TiO₂ prepared by reduction-nitridation procedure were much higher than that of samples prepared by simple nitridation treatment. The enhanced activity was ascribed to the substitutional N-doping and appropriate concentration of oxygen vacancies. TOHN10 prepared by reduction-nitridation procedure exhibited excellent photocatalytic stability. A possible mechanism for the photocatalysis was proposed.     

Color centers in irradiated MgF2

Abstract

Color centers in rutile-structured MgF₂ single crystals irradiated at 20K/360K by reactor neutrons are investigated spectroscopically at LNT. Four different types of the F-F vacancy bond in MgF₂ are possibly identified to the observed absorption bands as due to the F₂ centers; instead of previous assignments, the 300nm band to the F₂(D_2h), the 325nm band to the F₂(C₁), the 355nm band to the F₂(C_2v), and the 400nm band to the F₂(C_2h) centers.     

Effect of calcination atmosphere on photoluminescence properties of nanocrystalline ZrO2 thin films prepared by sol–gel dip coating method

Highly transparent and homogeneous nanocrystalline ZrO₂ thin films were prepared by the sol–gel dip coating method. The X-ray diffraction (XRD) pattern of ZrO₂ thin films calcined in air, O₂ or N₂ shows the formation of tetragonal phase with varying crystallite size. X-ray photoelectron spectroscopy (XPS) gives Zr 3d and O 1s spectra of thin film annealed in air, which reveal zirconium suboxide component (ZrO_x, 0<x<2), Zr–O bond and surface defects. An average transmittance greater than 85% (in UV–vis region) is observed in all calcined samples. Photoluminescence (PL) reveals an intense emission peak at 379 nm and weak peaks at 294, 586 and 754 nm for ZrO₂ film calcined in air. An enhancement of PL intensity and red-shift is observed in films calcined in O₂ and N₂ atmosphere. This is due to the reconstruction of zirconium nanocrystal interfaces and vacancies, which help passivate the non-radiative defects. The oxygen deficient defect, which is due to the distorted Zr–O bond, is suggested to be responsible for photoluminescence. The defect states in the nanocrystalline zirconia thin films play an important role in the energy transfer process. The luminescence defects in the film make it suitable for gas sensors development and tunable lasers.     

Lattice distortion and corresponding changes in optical properties of CeO2 nanoparticles on Nd doping

Doping of Nd distorts the lattice structure of CeO₂, increases the lattice strain and expands the lattice. Oxygen vacancies and other ceria related defects contribute to the lattice strain. Shifting and broadening of the F_2g Raman peak of doped sample, compared to pure CeO₂, is indicative of local structure distortion on doping. Dopant induced enhancement of oxygen vacancies, in the CeO₂ lattice, is further confirmed by the generation of a new Raman peak at 543 cm^?1 that is otherwise absent in the pure one. UV–vis spectroscopy gives an understanding of the different types of f–f electronic transition of Nd in the crystalline environment of CeO₂. Effective band gap of CeO₂ reduces upto Nd concentration of 2.5%. The band gap, however, increases at 4% of Nd due to Burstein–Moss shift. Photoluminescence intensity of pure CeO₂ decreases with Nd concentration owing to the increase in the number of non radiative oxygen vacancies. These vacancies act as luminescence quencher and reduce the emission intensity. Photoluminescence excitation spectra confirm the presence of these oxygen vacancies in the CeO₂ nanocrystallites.     

Optical properties of TiO2 anatase - Carbon nanotubes composites studied by cathodoluminescence spectroscopy

Luminescence spectra obtained by electron bombardment (cathodoluminescence, CL) on TiO₂ (anatase)/carbon nanotubes (CNT) composite, show only one visible band at 498 nm, while the spectra taken from pure anatase samples show two bands at 498 and 545 nm. We demonstrate that the visible luminescence bands are originated by TiO₂ surface defects due to oxygen vacancies, and that this luminescence signal is independent of TiO₂ mineral form (anatase or rutile). Moreover we obtain that the 545 nm band quenching in TiO₂/CNT composites is caused by empty oxygen vacancies (OV) related to oxygen given from oxygen-rich pristine powder of carbon nanotubes. Our conclusions are also supported by X-ray photoelectron spectroscopy (XPS), SEM analysis and energy dispersed X-ray measurements (EDX). Furthermore we can confirm that the NIR TiO₂ luminescence emission is linked only to the presence of Ti rutile form as described in several works in literature.     

电子回旋共振等离子体增强沉积氟化非晶碳薄膜的光学性质

用紫外可见光透射光谱(UV-VIS)并结合键结构的X射线光电子能谱(XPS)和红外谱(FTIR)分析,研究了电子回旋共振等离子体增强化学气相沉积法制备的氟化非晶碳薄膜的光吸收和光学带隙性质.在微波功率为140—700W、源气体CHF₃∶C₆H₆比例为1∶1—10∶1条件下沉积的薄膜,光学带隙在1.76—2.85eV之间.薄膜中氟的引入对吸收边和光学带隙产生较大的影响,吸收边随氟含量的提高而增大,光学带隙则主要取决于CF键的含量,是由于强电负 关键词： 氟化非晶碳薄膜 光吸收与光学带隙 电子回旋共振等离子体     

ANALYSIS OF THE X-RAY PHOTOELECTRON SPECTRA OF a-SiOCF FILMS PREPARED BY PLASMA-ENHANCED CHEMICAL VAPOUR DEPOSITION

The preparation of a-SiOCF films from Si(OC₂H₅)₄, C₄F₈ and/or Ar using the plasma-enhanced chemical vapour deposition method is reported. The chemical bonding structures of the films are analysed by x-ray photoelectron spectroscopy (XPS). In the case of the films deposited from the mixture with and without Ar, the configurations of F-Si-O-Si, Si-OH, Si-O-Si, C-CF and C-F are contained. However, there is also the C-C configuration in the film prepared from the mixture with Ar. Moreover, it is found that the photoelectron peaks of Si 2p, O 1s and F 1s for the film deposited from the feeding gas with Ar show the same shift of about 1eV toward high binding energy in comparison with those for the film prepared from the feeding gas without Ar. No evidence reveals the presence of an Si-C bond in the films.     

Determination of C60/C70 ratios in fullerene mixtures and film characterization by scanning tunneling microscopy

Fullerene powder mixtures with different C₆₀/C₇₀ ratios have been analyzed by a variety of techniques, and results have been compared. The fullerence mixtures have been characterized as solutions in n-hexane by high-pressure liquid chromatography (HPLC) and UV-VIS spectroscopy. Thin films of fullerenes on Au(111) have been prepared from the mixtures by sublimation. The sublimation process has been studied by simultaneous thermogravimetric and differential thermal analyses. Thin fullerene films on Au(111) have been investigated by scanning tunneling microscopy (STM). The STM images show primarily two types of ballshaped molecules arranged in a lattice with hexagonal symmetry (fcc(111) face, nearest neighbour distance: 1 nm). The two species differ in diameter. STM images of films made of mixtures of different C₆₀/C₇₀ ratios show that C₇₀ molecules display a larger apparent diameter (0.8 nm) and corrugation than C₆₀ molecules (0.7 nm). The C₆₀/C₇₀ ratios obtained by counting the corresponding molecular species in the STM images of the thin films are compared to the C₆₀/C₇₀ ratios determined by HPLC on hexane solutions of the mixtures. The observed differences might be explained by different rates of sublimation for the two species. The STM images reveal film defects (vacancies and boundaries) and dynamic processes (displacement of C₇₀ molecules and vacancies). In films prepared to have a C₆₀ coverage of less than one monolayer, stable structural units of the C₆₀(111) surface consisting of three or seven C₆₀ molecules are revealed by STM. Occasionally, substructure within individual fullerene molecules is observed.     

Oxygen defect dependent variation of band gap,Urbach energy and luminescence property of anatase,anatase–rutile mixed phase and of rutile phases of TiO2 nanoparticles

TiO₂ nanoparticles are prepared by a sol–gel method and annealed both in air and vacuum at different temperatures to obtain anatase, anatase–rutile mixed phase and rutile TiO₂ nanoparticles. The phase conversion from anatase to anatase–rutile mixed phase and to rutile phase takes place via interface nucleation between adjoint anatase nanocrystallites and annealing temperature and defects take the initiate in this phase transformation. The samples are characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), UV–vis and photoluminescence spectroscopy (PL). Anatase TiO₂ exhibits a defect related absorption hump in the visible region, which is otherwise absent in the air annealed samples. The Urbach energy is very high in the vacuum annealed and in the anatase–rutile mixed phase TiO₂. Vacuum annealed anatase TiO₂ has the lowest emission intensity, whereas an intense emission is seen in its air annealed counterpart. The oxygen vacancies in the vacuum annealed samples act as non-radiative recombination centers and quench the emission intensity. Oxygen deficient anatase TiO₂ has the longest carrier lifetime. Time resolved spectroscopy measurement shows that the oxygen vacancies act as efficient trap centers of electrons and reduce the recombination time of the charge carriers.     

Power determination and hydrino product characterization of ultra-low field ignition of hydrated silver shots

Hydrated silver shots comprising a source of H and HOH catalyst were ignited by passing a low voltage, high current through the shot to produce explosive plasma that emitted brilliant light predominantly in the short-wavelength 10 to 300 nm region. Based on Stark broadening, the initially optically thick essentially 100% ionized plasma expanded at sound speed or greater and thinned to emit EUV and UV light. The peak power of 20 MW was measured using absolute spectroscopy over the 22.8–647 nm region wherein the optical emission energy was 250 times the applied energy. Synchronized high-speed video and spectroscopic recording of the plasma emission and the measurement of the applied ignition power over time showed that plasma persisted even after the ignition power decayed to zero. Continuous megawatt-level power was recorded on a hydrino reactor wherein continuous brilliant plasma was maintained by HOH and H produced from water-entrained injected molten silver matrix. The molten fuel produced the same EUV spectrum as the shots, but converted to 5700 K blackbody radiation of about 1 m² surface area with a positive feedback cycle of silver vaporization and absorption of the hydrino reaction emission with the plasma becoming increasingly optically thick. The calorimetrically measured power of a typical 80 mg, 10 microliter shot ignition released by the nascent HOH catalyzed transition of H to hydrino state H₂ (1/4) was 400,000 W. Based on the shockwave propagation velocity and the corresponding pressure, the high-current ignition of water in a silver matrix was measured to produce a shock wave that was equivalent to about 10 times more moles of gunpowder. The catalysis reaction product H₂(1/4) was identified by Raman spectroscopy, photoluminescence emission spectroscopy, X-ray photoelectron spectroscopy, and MAS ¹H NMR.