Optical properties of ZnO and Al2O3 implanted with silver ions

ZnO and Al₂O₃ samples implanted with 30-keV silver ions with fluences in the interval (0.25–1.00) × 10¹⁷ ions/cm² are studied by the method of optical photometry in the visible part of the spectrum. The optical transmission spectra of the implanted samples exhibit a selective band associated with surface plasmon resonance absorption of silver nanoparticles. The intensity of this band nonmonotonically depends on the implantation fluence. The silver ion depth distribution in the samples is calculated. It is shown that the non-monotonicity observed in experiments is due to an increase in the substrate sputtering ratio with increasing implantation fluence. It is found that vacuum thermal annealing of the implanted Al₂O₃ layers up to 700°C causes a considerable narrowing of the plasmon absorption bandwidth without a tangible change in its intensity. At higher annealing temperatures, the plasmon absorption band broadens and its intensity drops. Annealing of the ZnO films under such conditions causes their complete vaporization.     

Spectrally broadened excitonic absorption and enhanced optical nonlinearities in Dy<Superscript>3+</Superscript>-doped ZnO nanoparticles

We have synthesized Dy³⁺-doped ZnO nanoparticles at room temperature through the sol–gel method. X-ray diffraction and Scanning electron microscopic studies confirm the crystalline nature of the particles. Excitonic absorption of ZnO shows three different bands, and we observe that incorporation of Dy³⁺ results in the shifting and broadening of the n=1 absorption band of ZnO. Photoluminescence studies done at the excitation wavelength of 335 nm show broad emission containing five different bands. Open-aperture z-scan studies done at 532 nm using 5 ns laser pulses show an optical limiting behavior, which numerically fits to a three-photon type absorption process. The nonlinearity is essentially resonant, as it is found to increase consistently with Dy³⁺ concentration. This feature makes Dy³⁺-doped ZnO a flexible optical limiter for potential device applications.     

Transition of synthetic chromium oxide gel to crystalline chromium oxide: a hot‐stage Raman spectroscopic study

Chromium oxide gel material was synthesised and appeared to be amorphous in X‐ray diffraction study. The changes in the structure of the synthetic chromium oxide gel were investigated using hot‐stage Raman spectroscopy based upon the results of thermogravimetric analysis. The thermally decomposed product of the synthetic chromium oxide gel in nitrogen atmosphere was confirmed to be crystalline Cr₂O₃ as determined by the hot‐stage Raman spectra. Two bands were observed at 849 and 735 cm⁻¹ in the Raman spectrum at 25 °C, which were attributed to the symmetric stretching modes of O Cr^III OH and O Cr^III O. With temperature increase, the intensity of the band at 849 cm⁻¹ decreased, while that of the band at 735 cm⁻¹ increased. These changes in intensity are attributed to the loss of OH groups and formation of O Cr^III O units in the structure. A strongly hydrogen‐bonded water H O H bending band was found at 1704 cm⁻¹ in the Raman spectrum of the chromium oxide gel; however, this band shifted to around 1590 cm⁻¹ due to destruction of the hydrogen bonds upon thermal treatment. Six new Raman bands were observed at 578, 540, 513, 390, 342 and 303 cm⁻¹ attributed to the thermal decomposed product Cr₂O₃. The use of the hot‐stage Raman spectroscopy enabled low‐temperature phase changes brought about through dehydration and dehydroxylation to be studied. Copyright © 2010 John Wiley & Sons, Ltd.     

Cr4+在八面体格位中的光谱特性研究

采用提拉法生长了Cr单掺和Cr，Mg共掺Al₂O₃晶体，后者具有900—1600nm的宽带吸收.研究了该吸收带在不同气氛、不同温度退火下的变化规律.通过建立合理的晶格缺陷模型，成功地解释了所有的实验结果，并确定Cr，Mg共掺Al₂O₃晶体红外波段宽吸收带属于八面体格位中的Cr⁴⁺离子. 关键词： 4+离子')" href="#">Cr⁴⁺离子 八面体格位 晶格缺陷     

Cr4+在Al2O3多晶体中的光谱性能研究

采用传统无压烧结工艺制备Cr:Al₂O₃透明多晶陶瓷.测定了其退火前后的吸收光谱和荧光光谱，发现在Al₂O₃六配位的八面体结构中，Cr⁴⁺的荧光发射也处在1100—1600nm波段的红外区间，荧光发射峰位于1223nm附近，类似Cr⁴⁺在四面体中的发光行为.同时由于氧化铝晶格常数较小，晶体场强较强，使Cr⁴⁺:Al₂O_{3< 关键词： 4+')" href="#">Cr⁴⁺ 2}O₃透明陶瓷')" href="#">Cr:Al₂O₃透明陶瓷 光谱性质 八面体     

Birth of room‐temperature magnons and Raman line enhancement in ZnO nanostructures containing cobalt oxide

Cobalt (Co) addition and thermal annealing induced structural and vibrational properties of ZnO nanostructures were analysed. X‐ray diffraction pattern reveals that the nanostructures are in hexagonal wurtzite type and the formation of Co₃O₄. The Co ion induced morphology changes have been studied by high‐resolution scanning electron microscope images and energy dispersive spectroscopy measurements confirm the presence of Co ions. CoO‐related magnon excitation bands are emerged at room temperature for the Co‐added samples. There are no changes in the band positions of the Raman spectra of pure and Co‐added materials. Annealed sample exhibits the suppression of magnon bands and formation of Co₃O₄: ZnO composites. Raman line width and the electron phonon coupling constant are decreased with respect to the annealing temperature. The formation of Co₃O₄ : ZnO composite phases have further confirmed by infrared spectra. Copyright © 2013 John Wiley & Sons, Ltd.     

Cr3+ doped Al2O3 nanoparticles: Effect of Cr3+ content in intensifying red emission

Cr³⁺-doped α-Al₂O₃ nanoparticles (Al_2−xCr_xO₃, 0.005 ≤ x ≤ 0.05) were synthesized by co-precipitation method. X-ray diffraction (XRD) patterns of Cr³⁺:Al₂O₃ nanoparticles revealed the crystallite size of ∼53 nm and electron microscopy (SEM & TEM) confirmed the spherical nanoparticle formation. Diffuse reflectance spectra (DRS) displayed peaks at 406 and 558 nm corresponding to the Cr³⁺ transitions which became prominent with the increase in Cr³⁺ concentration which was also evidenced by the gradually increasing pink coloration of the samples. Photoluminescence (PL) studies showed the sharp red emission at 694 nm (ruby line) which was observed for all samples. The Dq/B value for all samples was found to be greater than 2.3 confirming the presence of Cr³⁺ ions in the octahedral sites. Chromaticity diagrams displayed the maximum red appearance for the sample with x = 0.01 and a lifetime of 4 ms. The synthesized Cr³⁺:Al₂O₃ nanoparticles with smaller crystallite sizes and narrow near monochromatic emission can be used in various applications including sensing, lasing, and bioimaging applications.     

AgI(Cr2O3)复合离子导体的光谱研究

本文研究了AgI(Cr₂O₃)复合离子导体的红外吸收光谱,近紫外、可见反射光谱。发现复合离子导体的两种谱图均与纯AgI,Cr₂O₃的不同。红外吸收光谱在882—889cm^-1处有一新吸收峰。电子谱中,AgI从430nm开始向长波方向表现的光离解特性消失。本来Cr₂O₃由配位场效应而引起的d—d吸收跃迁以410nm,530nm为中心的反射谱带,现在410nm处的谱带消失。530nm处的谱带稍有红移,且随加入Cr₂O₃量的增多而强度减弱。代之以整个紫外、可见区的较强吸收。对此,结合透射电子显微镜的分析,用双声子耦合和介质的变形极化以及配位场理论对AgI(Cr₂O₃)复合离子导体的声子谱和电子谱进行了解析。 关键词：     

Studies on the complex behavior of optical phonon modes in wurtzite (ZnO)1−x (Cr2O3) x

This paper reports on the use of phonon spectra obtained with laser Raman spectroscopy for the uncertainty concerned to the optical phonon modes in pure and composite ZnO_1?x (Cr₂O₃) _x . Particularly, in previous literature, the two modes at 514 and 640 cm^?1 have been assigned to ZnO are not found for pure ZnO in our present study. The systems investigated for the typical behavior of phonon modes with 442 nm as excitation wavelength are the representative semiconductor (ZnO)_1?x (Cr₂O₃) _x (x = 0, 5, 10 and 15 %). Room temperature Raman spectroscopy has been demonstrated polycrystalline wurtzite structure of ZnO with no structural transition from wurtzite to cubic with Cr₂O₃. The incorporation of Cr³⁺ at most likely on the Zn sub-lattice sites is confirmed. The uncertainty of complex phonon bands is explained by disorder-activated Raman scattering due to the relaxation of Raman selection rules produced by the breakdown of translational symmetry of the crystal lattice and dopant material. The energy of the E ₂ (high) peak located at energy 53.90 meV (435 cm^?1) due to phonon–phonon anharmonic interaction increases to 54.55 meV (441 cm^?1). A clear picture of the dopant-induced phonon modes along with the B ₁ silent mode of ZnO is presented and has been explained explicitly. Moreover, anharmonic line width and effect of dislocation density on these phonon modes have also been illustrated for the system. The study will have a significant impact on the application where thermal conductivity and electrical properties of the materials are more pronounced.     

V centers in single crystal Al2O3

From optical and thermal bleaching experiments it is concluded that the 400 nm absorption band which appears in Al₂O₃ after γ-irradiation is a composite V band. One of its components is attributed to the V^-_OH center which also is responsible for a localized vibrational band at 3316 cm^-11 analogous to the one observed for the V_OH center in MgO. The irradiation also results in electron trapping at Cr³⁺ impurity ions to produce a band at 227 nm. Annealing at 170°C destroys the V^-_OH center by releasing holes which convert the Cr²⁺ to Cr³⁺ with an attendant thermoluminescence.     

Silicon MIS diodes with Cr2O3 nanofilm: Optical, morphological/structural and electronic transport properties

In this work we report the optical, morphological and structural characterization and diode application of Cr₂O₃ nanofilms grown on p-Si substrates by spin coating and annealing process. X-ray diffraction (XRD), non-contact mode atomic force microscopy (NC-AFM), ultraviolet-visible (UV-vis) spectroscopy and photoluminescence (PL) spectroscopy were used for characterization of nanofilms. For Cr₂O₃ nanofilms, the average particle size determined from XRD and NC-AFM measurements was approximately 70 nm. Structure analyses of nanofilms demonstrate that the single phase Cr₂O₃ on silicon substrate is of high a crystalline structure with a dominant in hexagonal (1 1 0) orientation. The morphologic analysis of the films indicates that the films formed from hexagonal nanoparticles are with low roughness and uniform. UV-vis absorption measurements indicate that the band gap of the Cr₂O₃ film is 3.08 eV. The PL measurement shows that the Cr₂O₃ nanofilm has a strong and narrow ultraviolet emission, which facilitates potential applications in future photoelectric nanodevices. Au/Cr₂O₃/p-Si metal/interlayer/semiconductor (MIS) diodes were fabricated for investigation of the electronic properties such as current-voltage and capacitance-voltage. Ideality factor and barrier height for Au//Cr₂O₃/p-Si diode were calculated as 2.15 eV and 0.74 eV, respectively. Also, interfacial state properties of the MIS diode were determined. The interface-state density of the MIS diode was found to vary from 2.90 × 10¹³ eV⁻¹ cm⁻² to 8.45 × 10¹² eV⁻¹ cm⁻².     

Upconversion luminescence from Er-N codoped of ZnO nanowires prepared by ion implantation method

Nitrogen and erbium co-doped of ZnO nanowires (NWs) are fabricated by ion implantation and subsequent annealing in air. The incorporation of Er³⁺ and N⁺ ions is verified by energy dispersive X-ray spectroscopy (EDS) and Raman spectra. The samples exhibit upconversion photoluminescence around ∼550 nm and ∼660 nm under an excitation at 980 nm. It is discovered that the N-doped can drastically increase the upconversion photoluminescence intensity by modifying the local structure around Er³⁺ in ZnO matrix. The enhancement of the PL intensity by the N-doped is caused by the formation of ErO_6−xN_x octahedron complexes. With the increase of the annealing temperature (T_a), the Er³⁺ ions diffuse towards the surface of the NWs, which benefits the red emission and evokes the variation of intensity ratio owing to the existence of some organic groups.     

Effect of growth temperature on characteristics of Cr-doped ZnO nanorods by magnetron sputtering

Cr-doped ZnO nanostructures, in well-aligned Zn_0.92Cr_0.06O nanorods array, were synthesized by radio frequency (RF) magnetron sputtering deposition at different temperatures. The effects of growth temperature on the structure and optical properties of Zn_0.92Cr_0.06O nanorods were investigated in terms of scanning electron microscope (SEM), X-ray diffraction (XRD), Raman spectra, X-ray photoelectron spectroscopy (XPS) and spectrophotometer. With increase the growth temperature, Zn_0.94Cr_0.06O nanorods have a strong improved crystalline quality. High growth temperature enhances the build-in electric field in the depletion region in the grain of the nanorods, which trap free carriers from the bulk of the grains. XPS results shows that Cr³⁺ ions substitute Zn²⁺ ions, and no secondary phases in the sample are found, meanwhile the oxygen vacancies decrease with increasing growth temperature. The high growth temperature causes a significant increase in optical transmittance of the Zn_0.92Cr_0.06O nanorods, which can be attributed to the weakening of scattering and absorption of light because of the increase of grain size. The red shift of the optical band gap can be mostly likely related to the Burstein–Moss effect.     

Photoluminescence and absorption in sol-gel-derived ZnO films

Highly c-axis-oriented ZnO films were obtained on corning glass substrate by sol-gel technique. The characteristics of photoluminescence (PL) of ZnO, as well as the exciton absorption in the absorption (UV) spectra are closely related to the post-annealing treatment. The difference between PL peak position and the absorption edge, designated as Stokes shift, is found to decrease with the increase of annealing temperature. The minimum Stokes shift is about 150 meV. The decrease of Stokes shift is attributed to the decrease in carrier concentration in ZnO film with annealing. X-ray diffraction, surface morphology and refractive index results indicate an improvement in crystalline quality with annealing. Annealed films also exhibit a green emission centered at ∼520 nm with activation energy of 0.89 eV. The green emission is attributed to the electron transition from the bottom of the conduction band to the antisite oxygen O_Zn defect levels.     

Luminescent vacuum ultraviolet spectroscopy of Cr3+ ions in nanostructured aluminum oxide

Impurity Cr³⁺ centers in submicron and nanostructured Al₂O₃ crystals of different phase compositions at temperatures of 300 and 7.5 K were studied by a luminescent vacuum ultraviolet (VUV) spectroscopy method. Photoluminescence (PL) spectra and the energies of ²E, ⁴T₂, and ⁴T₁ excited states of Cr³⁺ ion depend on the type of crystalline samples phase. The PL excitation spectrum of R-line in α-Al₂O₃ nanoscale crystals is formed by intracenter transitions (2.5–5.5 eV region), by charge transfer band (6.9 eV) and by effective formation of impurity-bound excitons (9.0 eV region). Such impurity-bound excitons correspond to O₂p→Al₃s electron transition in surroundings of an impurity Cr³⁺ center. The efficiency of impurity-bound excitons formation decreases with the increase of the grain size above 100 nm. The size dependence is noticeably shown in PL excitation spectra in VUV region. Excitons bound to impurity centers do not appear in nanostructured δ+θ-Al₂O₃ crystals. The effect of the electron excitation multiplication is observed distinctly in nanostrucured α-Al₂O₃ at an excitation energy above 19 eV (more than 2E_g).     

Synthesis and luminescence properties of nanocrystalline Gd2O3:Eu by combustion process

The nanocrystalline Gd₂O₃:Eu³⁺ powders with cubic phase were prepared by a combustion method in the presence of urea and glycol. The effects of the annealing temperature on the crystallization and luminescence properties were studied. The results of XRD show pure phase can be obtained, the average crystallite size could be calculated as 7, 8, 15, and 23 nm for the precursor and samples annealed at 600, 700 and 800 °C, respectively, which coincided with the results from TEM images. The emission intensity, host absorption and charge transfer band intensity increased with increasing the temperature. The slightly broad emission peak at 610 nm for smaller particles can be observed. The ratio of host absorption to O²⁻-Eu³⁺ charge transfer band of smaller nanoparticles is much stronger compared with that for larger nanoparticles, furthermore, the luminescence lifetimes of nanoparticles increased with increasing particles size. The effects of doping concentration of Eu³⁺ on luminescence lifetimes and intensities were also discussed. The samples exhibited a higher quenching concentration of Eu³⁺, and luminescence lifetimes of nanoparticles are related to annealing temperature of samples and the doping concentration of Eu³⁺ ions.     

Effect of bi-layer ratio in ZnO/Al2O3 multilayers on microstructure and functional properties of ZnO nanocrystals embedded in Al2O3 matrix

Zinc oxide (ZnO) nanocrystals (NCs) embedded in alumina (Al₂O₃) matrix were produced via rapid thermal annealing (RTA) of pulsed laser deposited ZnO/Al₂O₃ multilayered nanostructures. The effect of the thickness ratio (R) between Al₂O₃ and ZnO in one bi-layer on the microstructure and functional properties of NCs has been investigated. Grazing incidence small angle X-ray scattering confirmed the formation of nanocrystals after RTA. Grazing incidence wide angle X-ray scattering studies revealed that ZnO NCs have a high crystalline quality with (100) as preferred orientation. Tensile strain of NCs decreases with increasing R and is correlated to the distribution of NCs. From Raman analysis, it is noticed that the phonon frequency of the E₂ mode, related to the ZnO wurtzite phase, in NCs is shifted towards that of bulk ZnO with increasing R. Photoluminescence studies revealed that the near edge peak position shifts from 382 nm to 371 nm as the ratio R changes from 1.5 to 4 and is attributed to the strain effect. The intensity of emission in the yellow–green region due to defects decreases significantly with increasing R. Current–voltage (I–V) characteristics of Al/ZnO NCs embedded in Al₂O₃/n-Si (100)/Al have shown a hysteresis behavior. The increasing width of the hysteresis with increasing R revealed that the origin of the hysteresis might be due to the existence of polar surface charges on well-separated NCs. The high-resistance and low-resistance states in I–V hysteresis curves seem to be governed by Fowler–Nordheim tunneling and Schottky emission mechanisms, respectively.     

Synthesis of Cr2O3/TNTs nanocomposite and its photocatalytic hydrogen generation under visible light irradiation

A novel Cr₂O₃/TNTs nanocomposite was prepared by loaded suitable amount of amorphous Cr₂O₃ on titanate nanotubes (TNTs) via hydrothermal reaction and impregnation process. XRD, SEM and TEM results demonstrated that the amorphous Cr₂O₃ nanoparticles were homogeneously dispersed on the surface of TNTs. The diffuse reflectance UV–visible absorption spectra exhibited that the spectral response of TNTs was extended to visible light region by coupled with Cr₂O₃. The 2.5Cr₂O₃/TNTs nanocomposite showed the highest activity of hydrogen generation by photocatalytic water-splitting under visible light irradiation (λ > 400 nm). The high activity of H₂ evolution for Cr₂O₃/TNTs nanocomposites was associated with the donor level in the forbidden band of TNTs semiconductor provided by dopant Cr³⁺ and a probably photocatalytic mechanism was proposed.     

Al和Sb共掺对ZnO有序阵列薄膜的结构和光学性能的影响

采用水热合成法在预先生长的ZnO种子层的玻璃衬底上制备出Al和Sb共掺ZnO纳米棒有序阵列薄膜. 通过X射线衍射、扫描电镜、透射电镜和选区电子衍射分析表明:所制备的薄膜由垂直于ZnO种子层的纳米棒组成, 呈单晶六角纤锌矿ZnO结构, 且沿[001]方向择优生长, 纳米棒的平均直径和长度分别为27.8 nm和1.02 μm. Al和Sb共掺ZnO纳米棒有序阵列薄膜的拉曼散射分析表明:相对于未掺杂ZnO薄膜的拉曼振动峰(580 cm^-1), Al和Sb共掺ZnO阵列薄膜的E₁(LO)振动模式存在拉曼位移. 当Al和Sb的掺杂量为3.0at%,4.0at%,5.0at%,6.0at%时, Al和Sb共掺ZnO阵列薄膜的拉曼振动峰的位移量分别为3,10,14,12 cm^-1. E₁ (LO) 振动模式位移是由Al和Sb掺杂ZnO产生的缺陷引起的. 室温光致发光结果表明:掺杂Al和Sb后, ZnO薄膜在545 nm处的发光强度减小,在414 nm处的发光强度增加. 这是由于掺杂Al和Sb后, ZnO薄膜中Zn_i缺陷增加, O_i缺陷减少引起的. 关键词： Al和Sb共掺ZnO薄膜 纳米棒有序阵列 结构表征 拉曼散射     

Microwave-assisted rapid synthesis of tetragonal Cu2SnS3 nanoparticles for solar photovoltaics

A simple and rapid process for the synthesis of Cu₂SnS₃ (CTS) nanoparticles by microwave heating of metal–organic precursor solution is described. X-ray diffraction and Raman spectroscopy confirm the formation of tetragonal CTS. X-ray photoelectron spectroscopy indicates the presence of Cu, Sn, S in +1, +4, ?2 oxidation states, respectively. Transmission electron microscopy divulges the formation of crystalline tetragonal CTS nanoparticles with sizes ranging 2–25 nm. Diffuse reflectance spectroscopy in the 300–2,400 nm wavelength range suggests a band gap of 1.1 eV. Pellets of CTS nanoparticles show p-type conduction and the carrier transport in temperature range of 250–425 K is thermally activated with activation energy of 0.16 eV. Thin film solar cell (TFSC) with architecture: graphite/Cu₂SnS₃/ZnO/ITO/SLG is fabricated by drop-casting dispersion of CTS nanoparticles which delivered a power conversion efficiency of 0.135 % with open circuit voltage, short circuit current and fill factor of 220 mV, 1.54 mA cm^?2, 0.40, respectively.