An XPS study of CrOx on a thin alumina film and in alumina supported catalysts

We have investigated chromium layers evaporated onto a thin alumina film at room temperature. The oxidation and reduction behavior of this model catalyst was compared to atomic layer deposition (ALD) and impregnated alumina supported catalysts using X-ray photoelectron spectroscopy (XPS) with a detailed analysis method utilizing asymmetric peak shapes to represent both metallic and oxidic states. The ALD and impregnated catalysts were measured after calcination in air and after reduction with several gases at 850 K. Both catalysts show Cr³⁺ and Cr⁶⁺ species after calcination and mostly Cr³⁺ after reduction. The chromium layers deposited in vacuum show initially small partial oxidation due to the interaction with the oxygen terminated alumina film. These model catalysts can be oxidized in vacuum to Cr³⁺ species but not to higher oxidation states. The model catalysts were also subjected to calcination and reduction treatments after deposition in vacuum. Under these conditions the model systems exhibit similar oxidation/reduction behavior as the supported catalysts. Photoreduction of Cr⁶⁺ during the measurements was also studied and found to be very slow having a negligible effect on the results.     

Photoluminescence of f-centers in films of anodic alumina

Results are reported from a study of the optical properties of porous alumina films obtained by anodizing in a water solution of sulfuric acid and modified by thermal annealing in air at T ≥ 850°C. A comparative analysis of the data shows that the near-UV and visible photoluminescence of alumina anodized in a sulfuric acid solution is caused primarily by oxygen divacancies (F₂, F₂⁺ _2^{+} , and F₂^{2 +} _2^{2 + } centers), while sulfate ions have little effect on the luminescence properties of anodic alumina in this spectral range.     

Microstructure and tribological behavior of pulsed laser deposited a-CNx films

The a-CN_x films were deposited onto high-speed steel substrate by pulsed laser deposition at different nitrogen pressures. The tribological properties of the films in humid air and in vacuum were investigated using a ball-on-disk tribometer under various loads. The composition, microstructure and morphology of the films, wear tracks and paired balls were characterized by energy dispersive X-ray analysis (EDXA), X-ray photoelectron spectrum (XPS), Raman spectroscopy and scanning electron microscopy (SEM). With increasing the deposition pressure, the fraction of sp³ C bond reduces, the fraction of trapped nitrogen increases and the friction coefficient of the films declines both in humid air and vacuum. The friction coefficient of a-CN_x film decreases with increasing normal load. The tribological performances of the films in humid air are better than those of in vacuum. A transferred graphite-like tribo-layer is observed from a-CN_x film to the paired ball for both environments.     

Growth and post-annealing effect on the properties of the new sulfosalt SnSb2S4 thin films

In this work, the effect of the thermal annealing atmosphere on the structural, optical and electrical properties of the sulfosalt SnSb₂S₄ films obtained by thermal vacuum evaporation was studied. The samples are annealed at different atmospheres in the temperature range 50−275 °C for 1 h. It is observed that SnSb₂S₄ films exhibit a dramatic change in their electrical properties at transition temperatures of about 150 °C, 170 °C and 200 °C after an annealing process under air, nitrogen and vacuum atmospheres, respectively. The electrical resistivity measurements suggest that obtained films show ‘semiconducting’ behavior with resistivities between 10 and 100 Ω cm; the annealed films present rather lower resistivities between 10⁻² and 10⁻³ Ω cm and exhibit obvious p⁺-type semiconductor behavior with a dominant crystalline component.     

Thermal and chemical passivation of gallium-arsenide films deposited from ablation plasma

The electric and photoelectric properties of gallium-arsenide films deposited on a polycrystalline corundum substrate from the ablation plasma formed by a high-power ion beam are investigated. It is ascertained that vacuum and air annealing (in the former case, P = 10^?2 Pa and T = 300–1200 K) and sulfide chemical passivation in an alcoholic solution affect the characteristics of the dark conductivity and photo-conductivity of the film surfaces. The optimal conditions for thermal and chemical treatment, at which the most stable changes in film the properties are attained, are determined. Enhancement in the stability of the electrical and photoelectric characteristics of films, which is achieved after thermal treatment, arises from the annealing of defects and their clusterization. Sulfide passivation leads to changes in the characteristics and increases the stability of properties under air oxidation.     

不同退火条件对纳米多孔氧化铝薄膜光致发光的影响

以草酸为电解液,采用二次阳极氧化法制备出了纳米多孔氧化铝薄膜,经不同退火温度和退火气氛处理氧化铝薄膜后,通过分析其光致发光光谱得出：相同的退火气氛中, 退火温度T≤600 ℃ 时,T=500 ℃具有最大的光致发光强度;退火温度T≥700 ℃时,随着退火温度的升高,样品的发光强度增大。在不同的退火气氛中,多孔氧化铝薄膜随着退火温度的升高,发光峰位改变不同,即在空气中退火处理后,随着退火温度的升高,发光峰位蓝移,而在真空中退火处理后,发光峰位并不随退火温度的升高而变化;通过对1 100 ℃高温退火处理后的氧化铝薄膜的光致发光曲线的高斯拟合,可以看出,经退火处理后的多孔氧化铝,主要存在三个发光中心,发光曲线在350～600 nm范围内对应三个发射峰, 发射波长分别为387,410,439 nm。相同的退火温度下,空气中退火得到的氧化铝薄膜的光致发光强度大于真空中退火处理后的氧化铝薄膜。基于实验结果,结合X射线色散能谱(EDS)、红外反射光谱等表征手段,探讨了多孔氧化铝薄膜的发光机制,并对经过不同退火条件得到的多孔氧化铝薄膜的光致发光特性的改变做出了合理的解释。     

Effect of annealing on the opto-electronic properties of Cu0.9In1.0Se2.0 films

The influence of annealing on the structure and opto-electronic properties of Cu_0.9In_1.0Se_2.0 films prepared by solution growth technique has been studied. The films annealed at 500–520°C in air, vacuum (10^?4 torr), In-vapour and Se-vapour show polycrystalline chalcopyrite structure with orientation perpendicular to the (220) plane. Films annealed in Se-vapour at 500°C for 30 min have maximum grain size (560 Å), minimum optical energy gap, maximum absorption coefficient, lowest resistivity, maximum photosensitivity and thus are suitable for photovoltaic applications. Annealing in In-vapour or in vacuum changesp-type CuInSe₂ inton-type which possibly arises due to the increase in Se vacancies.     

Photocatalytic oxidation of natural organic adsorbates on anatase TiO2 films observed by infrared adsorption spectroscopy with a multiple internal reflection geometry

Photocatalytic oxidation of organic adsorbates on anatase TiO₂ films has been examined in different atmospheres of humid air, dry air and vacuum. The photocatalytic oxidation was observed by IR absorption spectroscopy (IRAS) with a multiple-internal-reflection (MIR) geometry. The photocatalytic oxidation is the fastest in the air at a humidity of 70% where oxygen and water vapor are consuming to produce OH radicals and O₂⁻ anions on the TiO₂ surface with the UV exposure. In the dry air, a rate of the photocatalytic oxidation is almost 30% of that in the humid air, where only O₂⁻ anions oxidize the organic adsorbates. In vacuum, on the other hand, it is negligible, which suggests that adsorbed H₂O molecules do not play an important role in the photocatalytic reaction. It is suggested that an addition of the water vapor is necessary to achieve the higher catalytic activity.     

脉冲激光沉积法在多孔铝衬底上生长的ZnO薄膜的结构与光学性质

ZnO是一种性质优良很有前途的紫外光电子器件材料,多孔铝是一种良好的模板型衬底,试图将二者结合起来以制备出一种全新的光电功能材料。制备了三种不同孔径多孔铝衬底,采用脉冲激光沉积法,在真空背景下,在多孔铝衬底上生长了氧化锌薄膜。利用扫描电子显微镜、X射线衍射和光致荧光对样品进行了测试和分析。研究表明:利用不同孔径的多孔铝衬底生长的氧化锌薄膜的结构和光学性质差异很大。样品A的光致发光主要是394nm的紫外发射和498nm的蓝绿光发射;样品B的光致发光主要是417nm的紫光发射和466nm蓝光发射;样品C的光致发光主要是415nm的紫光发射和495nm的蓝绿光发射。由于薄膜是富锌的,随着在空气中氧化的进行,光谱发生变化。利用固体能带理论对光谱进行了全面的分析。     

Deposition of nanostructured crystalline and corrosion resistant alumina film on bell metal at low temperature by rf magnetron sputtering

Aluminium oxide films deposited by rf magnetron sputtering for protective coatings have been investigated. The alumina films are found to exhibit grainy surface microstructure. The grain size, structure and density depend on different system parameters such as argon and/or oxygen flow rate and applied rf power etc. The effect of transition of the discharge from metallic to reactive mode on the surface characteristics of the alumina film is studied. X-ray diffractometry reveals that in poisoned mode of sputtering and under optimized power and pressure, crystalline alumina film can be grown. Different system conditions are optimized for corrosion resistant aluminium oxide films with good adhesion properties. Nanostructured alumina film is obtained at lower pressure (8 × 10⁻⁴ to 9 × 10⁻⁴ Torr) by rf reactive magnetron sputtering.     

The effect of vacuum annealing on graphene

The effect of vacuum annealing on the properties of graphene is investigated by using Raman spectroscopy and electrical measurement. Heavy hole doping on graphene with concentration as high as 1.5 × 10¹³ cm⁻² is observed after vacuum annealing and exposed to an air ambient. This doping is due to the H₂O and O₂ adsorption on graphene, and graphene is believed to be more active to molecular adsorption after annealing. Such observation calls for special attention in the process of fabricating graphene‐based electronic devices and gas sensors. On the other hand, because the quality of graphene remains high after the doping process, this would be an efficient and controllable method to introduce heavy doping in graphene, which would greatly help on its application in future electronic devices. Copyright © 2009 John Wiley & Sons, Ltd.     

Origin of ferromagnetism in iron implanted rutile single crystals

⁵⁷Fe doped titanium oxide monocrystals, prepared by ion implantation at different temperatures and subsequent thermal treatment, were characterized by conversion electron Mössbauer spectrometry, synchrotron radiation x-ray diffraction and superconducting quantum interference device magnetometry. After implantation at room temperature Fe is present in divalent state. Upon annealing in high vacuum Fe^2?+? is reduced to metallic Fe for the most part. After implantation at 623 K most iron is in metallic state. During annealing on air Fe is gradually oxidized from Fe^2?+? to Fe^3?+?. Depending on preparation conditions and thermal treatment the role of different nanosized secondary phases is discussed in terms of their influence on the magnetic properties of Fe:TiO₂. α-Fe nanoparticles are found to be responsible for ferromagnetism observed in TiO₂.     

Change of sheet resistance of high purity alumina ceramics implanted by Cu and Ti ions

High purity alumina ceramics (99% Al₂O₃) was implanted by copper ion and titanium ion in a metal vapour vacuum arc (MEVVA) implanter, respectively. The influence of implantation parameters was studied varying ion fluence. The samples were implanted by 68 keV Cu ion and 82 keV Ti ion with fluences from 1 × 10¹⁵ to 1 × 10¹⁸ ions/cm², respectively. The as-implanted samples were investigated by scanning electron microscopy (SEM), glancing X-ray diffraction (GXRD), scanning Auger microscopy (SAM), and four-probe method. Different morphologies were observed on the surfaces of the as-implanted samples and clearly related to implantation parameters. For both ion implantations, the sheet resistances of the alumina samples implanted with Cu and Ti ion fluences of 1 × 10¹⁸ ions/cm², respectively, reached the corresponding minimum values because of the surface metallization. The experimental results indicate that the high-fluence ion implantation resulted in conductive layer on the surface of the as-implanted high purity alumina ceramics.     

Ca2GeO4 ∶Eu3+ 的电子结构和紫外-真空紫外发光特性的研究

采用高温固相法合成了发光材料Ca₂GeO₄ ∶Eu³⁺ ,并详细研究了其紫外-真空紫外发光特性. 发现并解释了Eu³⁺ 离子在空气中的自还原以及在不同波长激发下的颜色转换现象. Ca₂GeO₄ ∶Eu³⁺ 在163—230和301,466 nm处具有强激发带,表明Ca₂GeO₄ ∶Eu³⁺ 关键词： 2GeO₄ ∶Eu³⁺')" href="#">Ca₂GeO₄ ∶Eu³⁺ 光致发光机理 空气中自还原 颜色转换     

Wettability of ZnO: A comparison of reactively sputtered; thermally oxidized and vacuum annealed coatings

We have studied the wettability of sputter deposited ZnO, thermally oxidized Zn-ZnO and vacuum annealed ZnO coatings. The X-ray diffraction patterns showed the formation of hexagonal-wurtzite structure of ZnO, which was further confirmed by micro-Raman spectroscopy data. The X-ray photoelectron spectroscopy data indicated that the sputter deposited ZnO coatings were more stoichiometric than thermally oxidized Zn-ZnO and vacuum annealed ZnO coatings. The wettability measurements indicated that water contact angles of 158.5° and 155.2° with sliding angles of 2° and 4° were achieved for thermally oxidized Zn-ZnO and vacuum annealed ZnO coatings, respectively. The superhydrophobicity observed in thermally oxidized Zn-ZnO and vacuum annealed coatings is attributed to the nanorod cluster like morphology along with the presence of high fraction of micron scale air pockets. The water droplet on such surfaces is mostly in contact with air pockets rather than solid surface, leading to high contact angle. Whereas, the sputter deposited ZnO coatings exhibited a maximum water contact angle of 110.3°. This is because the sputter deposited ZnO coatings exhibited a densely packed nanograin-like microstructure without any air pockets. The work of adhesion of water was very low for thermally oxidized Zn-ZnO (5.06 mJ/m²) and vacuum annealed ZnO coatings (6.71 mJ/m²) when compared to reactively sputtered ZnO coatings (90.41 mJ/m²). The apparent surface free energy (SFE) for these coatings was calculated using Neumann method and the SFE values for sputter deposited ZnO, thermally oxidized Zn-ZnO and vacuum annealed ZnO coatings were 32.95, 23.21 and 18.78 mJ/m², respectively.     

Preparation and properties of alumina composites modified by electric field-induced alignment of carbon nanotubes

Catalytic chemical vapor deposition (CVD) grown multi-walled carbon nanotubes (MWNTs) are treated with HF and deionized water and are then placed into alumina ceramics for improvement of both electrical conductivity and mechanical properties. In particular, an alternating current (ac) electric field is applied during the coagulation of the alumina slurries to induce the formation of aligned MWNT networks in the alumina matrix. The coagulated alumina matrix composite bases filled with 2 wt. % ac electric field-induced aligned MWNTs, are then sintered by hot pressing. The electrical conductivities of the prepared composites in directions both parallel and perpendicular to the MWNTs alignment, reach values of 6.2×10^-2 S m^-1 and 6.8×10^-9 S m^-1, respectively, compared with that of 4.5×10^-15 S m^-1 for pristine alumina ceramics. The fracture toughness and flexing strengths of the prepared composites in the two directions are 4.66±0.66 MPa m^0.5, 390±70 MPa, and 3.65±0.46 MPa m^0.5, 191±5 MPa, respectively, compared with 3.78±0.66 MPa m^0.5 and 302±50 MPa for pristine alumina, 4.09±0.15 MPa m^0.5 and 334±60 MPa for alumina filled with 2 wt. % MWNTs prepared without the effect of an electric field, respectively. The results indicate that the electric field leads to anisotropic behaviour. The properties of the composites along the direction of the MWNTs alignment are much improved with the addition of a small amount of CVD grown MWNTs. PACS 61.46.Fg; 61.66.Fn     

A close correlation between induced ferromagnetism and oxygen deficiency in Fe doped In2O3

We report on the reversible manipulation of room temperature ferromagnetism in Fe (5%) doped In₂O₃ polycrystalline magnetic semiconductor. The X-ray diffraction and photoemission measurements confirm that the Fe ions are well incorporated into the lattice, substituting the In³⁺ ions. The magnetization measurements show that the host In₂O₃ has a diamagnetic ground state, while it shows weak ferromagnetism at 300 K upon Fe doping. The as-prepared sample was then sequentially annealed in hydrogen, air, vacuum and finally in air. The ferromagnetic signal shoots up by hydrogenation as well as vacuum annealing and bounces back upon re-annealing the samples in air. The sequence of ferromagnetism shows a close inter-relationship with the behavior of oxygen vacancies (V_o). The Fe ions tend to a transform from 3+ to 2+ state during the giant ferromagnetic induction, as revealed by photoemission spectroscopy. A careful characterization of the structure, purity, magnetic, and transport properties confirms that the ferromagnetism is due to neither impurities nor clusters but directly related to the oxygen vacancies. The ferromagnetism can be reversibly controlled by these vacancies while a parallel variation of carrier concentration, as revealed by resistance measurements, appears to be a side effect of the oxygen vacancy variation.     

汞扩散泵——镉捕集阱高真空系统

我们在二级玻璃汞扩散泵的真空系统上使用了室温的镉膜阱,证明镉膜阱能有效地捕集汞蒸气,使被抽容器达到气压力10^-5—10^-7毫米汞数量级的高真空。我们较系统地试验了镉膜的条件对于极限气压的影响,实验结果表明,新蒸发的镉膜效果最好;将镉膜在10^-2毫米汞的气压下搁置10小时后对于极限气压的影响不大;但若将其在大气下搁置10小时,则极限气压约升高一个数量级;进一步延长在大气中的暴露时间(达300天),对极限气压无更大的影响。初步的寿命试验表明,扩散泵工作140小时之后,极限气压才较显著地上升。降低镉膜阱的温度、增加镉膜阱的数目和被抽容器的高温烘烤都是提高真空度的有效途径;在实验中考虑了这些因素,我们曾获得了气压低达10^-9毫米汞数量级的超高真空。     

注入Ar+的蓝宝石晶体退火前后光致发光谱的分析

对注入Ar⁺后不同晶面取向的蓝宝石晶体在不同退火条件下的光致发光谱进行了分析.分析结果表明:三种晶面取向的蓝宝石样品经Ar⁺注入后,其光致发光谱中均出现了新的位于506nm处的发光峰;真空和空气气氛下的退火均对样品在506nm处的发光有增强作用,不同晶面取向的样品发光增强程度不同,且发光增强至最大时的退火温度也不同,空气气氛下的退火使样品发光增强程度更为显著.由此可以看出,退火气氛、退火温度和晶面取向均对样品发光峰强度有影响. 关键词： 2O₃')" href="#">Al₂O₃ 离子注入 退火 光致发光谱     

Volume and surface oxidation of basalt

Natural, Fe²⁺-rich basalt glass (quenched lava) was heat treated as glass pieces and glass powder in air, in 6.0 Ar and in a 9×10^?6 mbar vacuum below temperatures of significant crystallization to access volume and surface oxidation by ⁵⁷Fe Mössbauer spectroscopy. While no oxidation occurs upon heating in vacuum, the amount of Fe³⁺ formed in powder (surface oxidation) is about 10 times higher than in pieces (volume oxidation), and surface oxidation is of the same order in air and Ar. This effect is assigned to chemisorption of water or CO₂. Crystalline basalt, investigated by wet chemistry, includes five glass pieces treated above T of crystallization in air and in 6.0 Ar, and three lava samples of increasing depth up to 9 cm of lava lobes. The high Fe₂O₃ of all these crystalline samples is explained as a stabilization of Fe³⁺ due to the change of the local electronic environment in the course of crystallization; volume oxidation therefore appears to be independent on the environmental atmosphere.