Structure and UV emission of nanocrystal ZnO films by thermal oxidation of ZnS films

ZnO films prepared by the thermal oxidation of the ZnS films through thermal evaporation are reported. The as-deposited ZnS films have transformed to ZnO films completely at 400 degrees C. The 400-700 degrees C annealed films with a preferential c-axis (002) orientation have a hexagonal wurtzite structure. The band gap of ZnO films shifts towards longer wavelength with the increase of the annealing temperature. The relationship between the band gap energy of ZnO films and the grain size is discussed. The shift of the band gap energy can be ascribed to the quantum confinement effect in nanocrystal ZnO films. The photoluminescence spectra of ZnO films show a dominant ultraviolet emission and no deep level or trap state defect emission in the green region. It confirms the absence of interstitial zinc or oxygen vacancies in ZnO films. These results indicate that ZnO film prepared by this simple thermal oxidation method is a promising candidate for optoelectronic devices and UV laser. (c) 2005 Elsevier BN. All rights reserved.

The effects of oxygen partial pressure on the optical absorption edge and the UV emission energy of ZnO films

The optical absorption edge and ultraviolet (UV) emission energy of ZnO films deposited by direct current (DC) reactive magnetron sputtering at room temperature have been investigated. With the oxygen ratio increasing, the structure of films changes from zinc and zinc oxide coexisting phase to single-phase ZnO and finally to the highly (002) orientation. Both the grain size and the stress of ZnO film vary with the oxygen partial pressure. Upon increasing the oxygen partial pressure in the growing ambient, the visible emission in the room-temperature photoluminescence spectra was suppressed without sacrificing the band-edge emission intensity in the ultraviolet region. The peaks of photoluminescence spectra were located at 3.06---3.15 eV. From optical transmittance spectra of ZnO films, the optical band gap edge was observed to shift towards shorter wavelength with the increase of oxygen partial pressure.

Annealing effects on electron-beam evaporated Al2O3 films

The effects of post-deposited annealing on structure and optical properties of electron-beam evaporated Al2O3 single layers were investigated. The films were annealed in air for 1.5 h at different temperatures from 250 to 400 degrees C. The optical constants and cut-off wavelength were deduced. Microstructure of the samples was characterized by X-ray diffraction (XRD). Profile and surface roughness measurement instrument was used to determine the rms surface roughness. It was found that the cut-off wavelength shifted to short wavelength as the annealing temperature increased and the total optical loss decreased. The film structure remained amorphous even after annealing at 400 degrees C temperature and the samples annealed at higher temperature had the higher rms surface roughness. The decreasing total optical loss with annealing temperature was attributed to the reduction of absorption owing to oxidation of the film by annealing. Guidance to reduce the optical loss of excimer laser mirrors was given. (c) 2004 Elsevier B.V. All rights reserved.

退火对电子束热蒸发Al2O3薄膜性能影响的实验研究

用电子束热蒸发方法镀制了Al2O3材料的单层膜，对它们在空气中进行了250～400℃的高温退火。对样品的透射率光谱曲线进行了测量，计算了样品的消光系数、折射率和截止波长。通过X射线衍射仪(XRD)测量分析了薄膜的微观结构，采用表面轮廓仪测量了样品的表面均方根粗糙度。结果发现随着退火温度的提高光学损耗下降，薄膜结构在退火温度为400℃时仍然为无定形态，样品的表面粗糙度随退火温度的升高而增加。引起光学损耗下降起主导作用的是吸收而不是散射，吸收损耗的下降主要是由于退火使材料吸收空气中的氧而进一步氧化，从而使薄膜

热舟蒸发LaF_3薄膜的紫外性能研究

研究了沉积温度对热舟蒸发氟化镧薄膜结构和光学性能的影响,沉积温度从200℃上升到350℃,间隔为50℃.采用分光光度计测量了样品的透射率和反射率光谱曲线,并在此基础上进行了光学损耗、光学常数以及带隙和截止波长的计算.采用表面轮廓仪进行了表面形貌和表面粗糙度的标定,采用X射线衍射(XRD)方法测量了不同沉积温度下样品的微结构.发现在短波长波段,随着沉积温度的升高,光学损耗增加,晶粒尺寸增大,表面粗糙度略有增加.不过散射损耗在光学损耗中所占比例均很小,光学损耗的增加主要由吸收损耗引起.随着沉积温度的升高,折射率与消光系数增大,带隙变小,相对应的截止波长向长波方向移动.

真空紫外光学薄膜及薄膜材料

概述了真空紫外(VUV)波段光学薄膜及薄膜材料的研究进展,金属Al膜因到短至80nm还能提供较高的反射率而得到普遍关注,在高真空和30nm/s左右沉积速率下沉积了保护层的金属Al膜在157nm处反射率可达90%。介质氧化物薄膜机械应力小,环境稳定性比氟化物薄膜好,在190nm以上波段应用较广泛,但在180nm以下波段吸收大大增加而应由氟化物薄膜取代。氟化物薄膜带宽大、吸收系数小,沉积了致密SiO2保护层的氟化物高反膜,在中心波长180nm处可得到接近99%的反射率,而且膜系的稳定性和抗激光损伤也大大提高。氟化物减反膜在157nm处可得到0.1%以下的反射率;到目前为止氟化物薄膜最好的沉积工艺是电阻热蒸发。

Annealing effects on the optical and structural properties of Al2O3/SiO2 films as UV antireflection coatings on 4H-SiC substrates

Al2O3/SiO2 films have been prepared by electron-beam evaporation as ultraviolet (UV) antireflection coatings on 4H-SiC substrates and annealed at different temperatures. The films were characterized by reflection spectra, ellipsometer system, atomic force microscopy (AFM), X-ray diffraction (XRD) and Xray photoelectron spectroscopy (XPS), respectively. As the annealing temperature increased, the minimum reflectance of the films moved to the shorter wavelength for the variation of refractive indices and the reduction of film thicknesses. The surface grains appeared to get larger in size and the root mean square (RMS) roughness of the annealed films increased with the annealing temperature but was less than that of the as-deposited. The Al2O3/SiO2 films maintained amorphous in microstructure with the increase of the temperature. Meanwhile, the transition and diffusion in film component were found in XPS measurement. These results provided the important references for Al2O3/SiO2 films annealed at reasonable temperatures and prepared as fine anti-reflection coatings on 4H-SiC-based UV optoelectronic devices. (c) 2008 Elsevier B.V. All rights reserved.

HfO2的纯度对紫外多层膜反射率的影响

用辉光放电质谱法和二次离子质谱仪测定了两种HfO2材料及它们相应的单层膜中的杂质含量，结果发现，无论是在体材料中还是在用电子束蒸发技术沉积的材料单层薄膜中，ZrO2都是这两种HfO2材料中最主要的杂质。而且，这两种HfO2材料中Zr含量的差别远远大于Ti、Fe含量的差别，这说明Zr含量的差别正是引起两种HfO2膜层光学性能差别的原因。用这两种不同纯度的HfO2材料与同一纯度的SiO2材料组合，沉积形成266nm的紫外反射镜，实验结果表明这两种反射镜的反射率分别在99.85% 和 99.15%左右。这个结果与依据单层膜得出的光学常数所设计的结果符合的很好。

水体中有机物的紫外光降解研究

当前，水资源污染越来越严重，人类的健康面临着巨大的威胁。高级氧化技术作为一 种经济、高效、无二次污染的水体处理方法，一直是水污染控制与治理领域研究的热点。 本文以环境中典型的有机污染物苯酚和水体中主要有机物腐殖酸为研究对象，利用自 制的紫外光（ultraviolet，UV）离线降解装置，采用紫外-可见光谱法和总有机碳（TOC） 分析法分别研究水相中苯酚、腐殖酸的紫外光降解情况，系统地考察不同初始pH值、初始 浓度、光照时间、光照强度、反应容器等因素对光降解效果的影响。为了模拟实际水体条 件和提高光降解效率，在体系中分别加入NaCl、Na2CO3、NaNO3、NaNO2和双氧水等化学 成分，探讨这些化学物质对苯酚、腐殖酸的紫外光降解效率和降解途径的影响。最后，首 次构建了石英螺旋管内壁负载TiO2膜的在线降解装置，结合UV/H2O2/TiO2联用体系，进行 海水中有机物的光降解研究。 紫外可见光谱分析表明：光降解速率随初始pH 值的降低而提高，相同条件下苯酚在 酸性溶液中降解速率高于碱性溶液，说明苯酚分子比酚氧离子容易光降解；硝酸钠和亚硝 酸钠有利于苯酚的光降解，说明它们在紫外光下容易分解生成自由基；在苯酚水溶液中加 入双氧水，光照15 min 后，光降解效率达到97%。各种介质中苯酚的降解速率大小依次为： 1.5 mmol/L 过氧化氢溶液 ＞ 1.0 mmol/L 硝酸钠的海水 ＞ 海水 ＞ 纯水 ＞ 0.5 mol/L 氯化钠溶液。然而，TOC 数据显示氯化钠的存在对苯酚的矿化有促进作用；同光谱的降解 速率相比，矿化速率要小。 腐殖酸的光降解效率随初始质量浓度的减小而提高，当质量浓度为10 mg/L时，光照 30 分钟后，降解效率高达到88%；初始pH值对腐殖酸的降解效率影响很大，腐殖酸在碱 性条件下比在中性和酸性条件更容易光降解；硝酸钠等盐分对中性和碱性溶液中腐殖酸的 光降解没有明显促进作用，但对酸性溶液中腐殖酸的光降解促进作用明显。采用UV/H2O2联 合降解时，腐殖酸降解效率得到显著提高。 相比离线降解方式，采用石英螺旋管在线降解苯酚和腐殖酸，降解效率均提高了15 倍 以上；海水经过在线降解后，紫外可见光光谱吸光度值缓慢下降；经过多次在线光降解后， 在290 nm波长处出现强烈吸收峰，再次光照后很快消失。这种现象表明海水中可能存在着 粒

Effects of solar UV radiation on diurnal photosynthetic performance and growth of Gracilaria lemaneiformis (Rhodophyta)

Previous studies on diurnal photosynthesis of macroalgal species have shown that at similar levels of photosynthetically active radiation (PAR, 400-700nm) the photosynthetic rate is lower in the afternoon than in the morning. However, the impacts of solar ultraviolet radiation (UVR, 280-400nm) have been little considered. We investigated the diurnal photosynthetic behaviour of the economically significant red alga Gracilaria lemaneiformis in the absence or presence of UV-A+B or UV-B with a flow-through system. While UV-A and UV-B, respectively, inhibited noontime Pmax by 22% and 14% on the sunny days, UV-A during sunrise (PAR below about 50Wm-2) increased the net photosynthesis by about 8% when compared with PAR alone. UV-A + PAR also resulted in higher apparent photosynthetic efficiency in the morning than in the afternoon period than PAR alone. Nevertheless, integrated daytime photosynthetic production under solar PAR alone was higher than with either PAR + UV-A+B or PAR + UV-A. Relative growth rate in the long term (9 days) matched the integrated photosynthetic production in that UV-A led to 9-15% and UV-B to 19-22% reduction, respectively. UV-absorbing compounds were found to be higher in the thalli exposed to PAR+UV-A+B than under PAR alone, reflecting a protective response to UVR.

Vertical mixing within the epilimnion modulates UVR-induced photoinhibition in tropical freshwater phytoplankton from southern China

1. The importance of vertical mixing in modulating the impact of UVR on phytoplankton photosynthesis was assessed in a tropical, shallow lake in southern China from late winter to mid-spring of 2005. 2. Daily cycles of fluorescence measurements (i.e. photosynthetic quantum yield, Y) were performed on both 'static' and in situ samples. Static samples were of surface water incubated at the surface of the lake under three radiation treatments - PAB (PAR + UVR, 280-700 nm), PA (PAR + UV-A, 320-700 nm) and P (PAR, 400-700 nm). In situ samples were collected every hour at three different depths - 0, 0.5 and 1 m. 3. The general daily pattern was of a significant decrease in Y from early morning towards noon, with partial recovery in the afternoon. Samples incubated under static conditions always had lower Y than those under in situ conditions at the same time of the day. 4. Under stratified conditions, no overall impact of UVR impact could be detected in situ when compared with the static samples. Further rapid vertical mixing not only counteracted the impact of UVR but also stimulated photosynthetic efficiency. 5. Based on these measurements of fluorescence, the mixing speed of cells moving within the epilimnion was estimated to range between 0.53 and 6.5 cm min(-1). 6. These data show that mixing is very important in modulating the photosynthetic response of phytoplankton exposed to natural radiation and, hence, strongly conditions the overall impact of UVR on aquatic ecosystems.

Effects of solar UV radiation on germination of conchospores and morphogenesis of sporelings in Porphyra haitanensis (Rhodophyta)

The effects of ultraviolet radiation (UVR 280-400 nm) on the germination of Porphyra haitanensis conchospores and on the growth and morphogenesis of the subsequent sporelings were investigated by culturing the released conchospores under natural sunlight from 29 September to 6 October 2005. Germination increased with time and was faster when UV-B was excluded using cut-off filters. There were significant negative effects of UV-B radiation on growth and cell division of sporelings, with decreases up to 18% for thallus length, between 6 and 18% for thallus width, up to 29% for thallus area, and between 6 and 14% for cell size as compared to PAR-controls. UV-A had a significant positive effect on morphogenesis, enhancing the formation of sporelings with cells dividing transversely; on the other hand, UV-B delayed the formation of such sporelings. We also tested the effects of solar UVR on the growth of P. haitanensis juveniles and found no significant effects. Our results indicate that UV-A has an important role in the germination and morphogenesis of the species, but on the other hand, sporelings of P. haitanensis are more sensitive to UV-B radiation than juveniles.

Solar UV radiation drives CO2 fixation in marine phytoplankton: A double-edged sword

Photosynthesis by phytoplankton cells in aquatic environments contributes to more than 40% of the global primary production (Behrenfeld et al., 2006). Within the euphotic zone (down to 1% of surface photosynthetically active radiation [PAR]), cells are exposed not only to PAR (400-700 nm) but also to UV radiation (UVR; 280-400 nm) that can penetrate to considerable depths (Hargreaves, 2003). In contrast to PAR, which is energizing to photosynthesis, UVR is usually regarded as a stressor (Hader, 2003) and suggested to affect CO2-concentrating mechanisms in phytoplankton (Beardall et al., 2002). Solar UVR is known to reduce photosynthetic rates (Steemann Nielsen, 1964; Helbling et al., 2003), and damage cellular components such as D1 proteins (Sass et al., 1997) and DNA molecules (Buma et al., 2003). It can also decrease the growth (Villafane et al., 2003) and alter the rate of nutrient uptake (Fauchot et al., 2000) and the fatty acid composition (Goes et al., 1994) of phytoplankton. Recently, it has been found that natural levels of UVR can alter the morphology of the cyanobacterium Arthrospira (Spirulina) platensis (Wu et al., 2005b). On the other hand, positive effects of UVR, especially of UV- A (315-400 nm), have also been reported. UV- A enhances carbon fixation of phytoplankton under reduced (Nilawati et al., 1997; Barbieri et al., 2002) or fast-fluctuating (Helbling et al., 2003) solar irradiance and allows photorepair of UV- B-induced DNA damage (Buma et al., 2003). Furthermore, the presence of UV-A resulted in higher biomass production of A. platensis as compared to that under PAR alone (Wu et al., 2005a). Energy of UVR absorbed by the diatom Pseudo-nitzschia multiseries was found to cause fluorescence (Orellana et al., 2004). In addition, fluorescent pigments in corals and their algal symbiont are known to absorb UVR and play positive roles for the symbiotic photosynthesis and photoprotection (Schlichter et al., 1986; Salih et al., 2000). However, despite the positive effects that solar UVR may have on aquatic photosynthetic organisms, there is no direct evidence to what extent and howUVR per se is utilized by phytoplankton. In addition, estimations of aquatic biological production have been carried out in incubations considering only PAR (i. e. using UV-opaque vials made of glass or polycarbonate; Donk et al., 2001) without UVR being considered (Hein and Sand-Jensen, 1997; Schippers and Lurling, 2004). Here, we have found that UVR can act as an additional source of energy for photosynthesis in tropical marine phytoplankton, though it occasionally causes photoinhibition at high PAR levels. While UVR is usually thought of as damaging, our results indicate that UVR can enhance primary production of phytoplankton. Therefore, oceanic carbon fixation estimates may be underestimated by a large percentage if UVR is not taken into account.

Effects of solar UV radiation on morphology and photosynthesis of filamentous cyanobacterium Arthrospira platensis

To study the impact of solar UV radiation (UVR) (280 to 400 nm) on the filamentous cyanobacterium Arthrospira (Spirulina) platensis, we examined the morphological changes and photosynthetic performance using an indoor-grown strain (which had not been exposed to sunlight for decades) and an outdoor-grown strain (which had been grown under sunlight for decades) while they were cultured with three solar radiation treatments: PAB (photosynthetically active radiation [PAR] plus UVR; 280 to 700 nm), PA (PAR plus UV-A; 320 to 700 nm), and P (PAR only; 400 to 700 nm). Solar UVR broke the spiral filaments of A. platensis exposed to full solar radiation in short-term low-cell-density cultures. This breakage was observed after 2 h for the indoor strain but after 4 to 6 h for the outdoor strain. Filament breakage also occurred in the cultures exposed to PAR alone; however, the extent of breakage was less than that observed for filaments exposed to full solar radiation. The spiral filaments broke and compressed when high-cell-density cultures were exposed to full solar radiation during long-term experiments. When UV-B was screened off, the filaments initially broke, but they elongated and became loosely arranged later (i.e., there were fewer spirals per unit of filament length). When UVR was filtered out, the spiral structure hardly broke or became looser. Photosynthetic 0, evolution in the presence of UVR was significantly suppressed in the indoor strain compared to the outdoor strain. UVR-induced inhibition increased with exposure time, and it was significantly lower in the outdoor strain. The concentration of UV-absorbing compounds was low in both strains, and there was no significant change in the amount regardless of the radiation treatment, suggesting that these compounds were not effectively used as protection against solar UVR. Self-shading, on the other hand, produced by compression of the spirals over adaptive time scales, seems to play an important role in protecting this species against deleterious UVR. Our findings suggest that the increase in UV-B irradiance due to ozone depletion not only might affect photosynthesis but also might alter the morphological development of filamentous cyanobacteria during acclimation or over adaptive time scales.

UV-sensitive P compounds: Release mechanism, seasonal fluctuation and inhibitory effects on alkaline phosphatase activity in a shallow Chinese freshwater lake (Donghu Lake)

Filtrable phosphorus compounds in a shallow Chinese freshwater lake (Donghu Lake) were fractionated by Sephadex G-25 gel-filtration chromatography. Some portions of those compounds released soluble reactive phosphorus upon irradiation with low dose ultraviolet light. Catalase and a hydroxyl radical scavenger (mannitol) markedly prevented photosensitive phosphorus release. The observed effects may be explained by the action of oxidizing reagents such as hydroxyl radicals, produced in photochemical reactions between UV irradiation and humic substances in the water. There was a strong seasonality in UV-sensitive P (UVSP) release. Michaels constants (K-m) of total alkaline phosphatase in the lake water showed a direct positive relation to UVSP. Plot of K-m against the UVSP/phosphomonoester ratio reveals a strong relationship between the two variables. These results suggest that in some situations UVSP may be a competitive inhibitor of alkaline phosphatase activity in the lake. The competitive inhibition of fractionated UVSP on alkaline phosphatase reagent (Sigma) apparently supports this hypothesis.