Preparation and Photocurrent Performance of Highly Ordered Titania Nanotube Implanted with Ag/Cu Metal Ions

Ag/Cu-doped titania nanotubes （Ag/TiNT, Cu/TiNT） are prepared by a metal vapor vacuum arc implanter. A scanning electronic microscope is employed for microstruetural characterization. The photo-current performance of doped titania nanotubes under UV and visible light is tested by an electrochemical workstation CS300UA, the results show that the absorption edge of both Ag/TiNT and Cu/TiNT samples shifts to the visible light region and the band gap becomes narrower. Ag/TiNT possesses better photo-current ability than Cu/TiNT under UV and visible light. Titania doped with Ag and Cu metal ions is also studied based on the linearized augmented planewave method implemented by WIEN2k package, the result becomes better with the experimental performance.     

第一性原理计算N掺杂对InNbO4电子结构的影响

宽带隙（3.83 eV）半导体光催化材料InNbO4在紫外光作用下具有分解水和降解有机物的性能。最近实验发现了N掺杂InNbO4具有可见光下分解水制氢的活性。为了从理论上解释这一实验现象，本文采用基于密度泛函理论的第一性原理计算了N掺杂对InNbO4的能带结构、态密度和光学性质的影响。分析能带结构可得，N掺杂后在InNbO4的价带（O 2p）上方形成N 2p局域能级，导致电子跃迁所需的能量减小。吸收光谱表明，N掺杂后InNbO4的光吸收边出现了红移，实现了可见光吸收。     

第一性原理计算N掺杂对InNbO_4电子结构的影响

宽带隙(3.83 e V)半导体光催化材料InNbO_4在紫外光作用下具有分解水和降解有机物的性能.最近实验发现了N掺杂InNbO_4具有可见光下分解水制氢的活性.为了从理论上解释这一实验现象,本文采用基于密度泛函理论的第一性原理计算了N掺杂对InNbO_4的能带结构、态密度和光学性质的影响.分析能带结构可得,N掺杂后在InNbO_4的价带(O 2p)上方形成N 2p局域能级,导致电子跃迁所需的能量减小.吸收光谱表明,N掺杂后InNbO_4的光吸收边出现了红移,实现了可见光吸收.     

Mg掺杂ZnO纳米晶的低温共沉淀法制备及光学性质

采用共沉淀(co-precipitation)法制备了Mg掺杂ZnO纳米晶,分别用X射线衍射(XRD)、傅立叶变换红外光谱(FTIR)、紫外可见吸收(UV-Vis)光谱、光致发光(PL)光谱、透射电镜(TEM)、电子顺磁共振(EPR)等分析手段对样品进行了表征。探究了Mg离子在ZnO纳米晶中的存在状态,ZnO纳米晶颗粒尺寸和发射光谱随Mg掺杂浓度的变化,并对其发光机理进行了分析。结果表明:Mg离子在ZnO晶格中以部分晶格位,部分间隙位的方式存在,没有形成MgO表面壳层结构;随Mg掺杂浓度的增大,ZnO纳米晶的颗粒尺寸变小,发射光的光强增大。发射光的最佳激发波长为342nm,中心波长为500nm,荧光量子产率为22.8%。实验分析表明:Mg离子的掺杂在ZnO纳米晶中引入了锌空位(VZn),间隙位的镁离子(IMg),提供了新的复合中心,从而增强了ZnO纳米晶的光致发光。     

Carbon-nanodot-coverage-dependent photocatalytic performance of carbon nanodot/TiO_2 nanocomposites under visible light

Carbon nanodots(CDs) with visible absorption band and TiO_2 are integrated to enhance the photosensitivity of TiO_2.The CD/TiO_2 nanocomposites show obvious CD-coverage-dependent photocatalytic performance. The CD/TiO_2 nanocomposites with moderate CD coverge exhibit the highest photocatalytic activity after being irradiated with visible light, which is more excellent than that of TiO_2. Too little CD coverage could result in poor visible light absorption, which limits the photocatalytic performance of CD/TiO_2 nanocomposites. While, too much CD coverage weakens the photocatalytic activity of CD/TiO_2 nanocomposites by restraining the extraction of conduction band electrons within TiO_2 to generate active oxygen radicals and the electron transfer(ET) process from CDs to TiO_2. These results indicate that rational regulation of CD coverage and the realization of efficient ET process are important means to optimize the photocatalytic performance of CD/TiO_2 nanocomposites.     

Cd、Sr掺杂Mg2Ge电子结构和光学性质的第一性原理研究

此文用基于密度泛函理论(DFT)的第一性原理计算方法,分别研究了本征、掺Cd、掺Sr的Mg₂Ge的能带结构、电子态密度和光学性质.研究结果表明,本征Mg₂Ge是一种间接带隙半导体,带隙值为0.228eV.Sr的掺入使其变成带隙为0.591 eV的直接带隙半导体,Cd掺杂Mg₂Ge后表现出半金属性质.掺杂后的主要吸收峰减小,吸收谱范围增加.在可见光能量范围内,掺杂的Mg₂Ge有更低的反射率,对可见光的利用率增强.此外,掺杂还提高了高能区的光电导率.     

稀土(La/Ce/Pr/Nd)掺杂锐钛矿相TiO_2磁性及光催化活性的第一性原理研究

采用密度泛函理论下的平面波赝势方法,建立了未掺杂锐钛矿TiO_2和La/Ce/Pr/Nd单掺杂的锐钛矿TiO_2模型.几何优化后,通过计算形成能分析了掺杂结构的稳定性;通过自旋电子态密度的计算分析了各个掺杂模型的磁性状态,并采用比较磁性基态能量的方法对分析结果加以验证;讨论了各稀土元素掺杂对锐钛矿能带结构和吸收光谱的影响.结果表明:La/Pr掺杂的锐钛矿TiO_2具有亚铁磁性,Nd掺杂的锐钛矿具有反铁磁性,Ce掺杂锐钛矿为顺磁体;Ce掺杂对锐钛矿能带结构影响较小,吸收光谱红移不明显,而La/Nd掺杂则能有效提升锐钛矿对可见光的吸收系数,Pr掺杂能使锐钛矿TiO_2在红外光区出现吸收峰.     

第一性原理计算Mo浓度对Mo掺杂BiVO4光催化性能的影响

本文利用基于密度泛函理论的第一性原理研究了不同浓度的Mo掺杂BiVO₄的V位的电子结构、光学性质和光催化性能.缺陷形成能的计算结果说明BiMo_xV_1-xO₄(x=0.0625, 0.125, 0.25)三种掺杂体系都是可以稳定存在的.电子结构计算结果表明：BiMo_xV_1-xO₄(x=0, 0.0625, 0.125, 0.25)四种体系的带隙分别为2.123 eV,2.142 eV,2.160 eV和2.213 eV.掺杂BiVO₄体系的带隙值均大于本征BiVO₄,且带隙随着Mo浓度的增加而增大. BiMo_xV_1-xO₄(x=0.0625, 0.125, 0.25)三种掺杂体系的能带结构全部向低能量区域移动,导致掺杂体系导带底越过费米能级,Mo掺杂BiVO₄后具...     

The effect of Mn-doped ZnSe passivation layer on the performance of CdS/CdSe quantum dot-sensitized solar cells

ZnSe as a surface passivation layer in quantum dot-sensitized solar cells plays an important role in preventing charge recombination and thus improves the power conversion efficiency(PCE).However, as a wide bandgap semiconductor, ZnSe cannot efficiently absorb and convert long-wavelength light.Doping transition metal ions into ZnSe semiconductors is an effective way to adjust the band gap, such as manganese ions.In this paper, it is found by the method of density functional theory calculation that the valence band of ZnSe moves upward with manganese ions doping, which leads to acceleration of charge separation, wider light absorption range, and enhancing light harvesting.Finally, by using ZnSe doped with manganese ions as the passivation layer, the TiO_2/CdS/CdSe co-sensitized solar cell has a PCE of 6.12%, and the PCE of the solar cell increases by 9% compared with the undoped one(5.62%).     

氮流量在高氢氛围中对富硅氮化硅薄膜材料结构及其发光特性的影响

采用等离子体增强化学气相沉积技术,以N₂掺入到SiH₄和H₂的沉积方式,分别在玻璃和N型单晶硅片(100)衬底上制备富硅氮化硅薄膜。通过紫外-可见光吸收光谱、傅里叶变换红外吸收光谱(FTIR光谱)、拉曼光谱和光致发光谱(PL谱)分别表征掺氮硅薄膜材料的带隙、结构及其发光特性的变化。结果表明：在氢气的氛围中,随着氮气流量的增加,氢原子能够对薄膜缺陷起到抑制作用,并使较低的SiH₄/N₂流量比下呈现富硅态,但却不利于硅团簇的形成。随着氮原子的掺入,Si—N键的含量增大,带隙增大,薄膜内微结构的无序度也增大,薄膜出现了硅与氮缺陷相关的缺陷态发光;随着氮原子进一步增加,出现了带尾态发光,进一步讨论了发光与结构之间的关联。这些结果有助于采用PECVD制备富硅氮化硅对材料发光与结构特性的优化。     

TiO2纳米管的力学和电子学性质

基于密度泛函理论研究了纤铁矿和锐钛矿型TiO₂纳米管的原子结构、稳定性、Young模量以及电子能带结构.计算结果显示：在纳米管直径较小时,锐钛矿型TiO₂纳米管的稳定性要好于纤铁矿型纳米管,随着管径的增大,纤铁矿型纳米管变得比锐钛矿型纳米管要更稳定.纤铁矿型TiO₂纳米管具有比锐钛矿型纳米管更大的Young模量,力学性能比较优异.另外,通过对电子能带结构的研究发现,手性对TiO₂纳米管的电子结构影响较大,纤铁矿（0,n）型和锐钛矿（n,0）型纳米管为间接带隙半导体,而纤铁矿（n,0）型和锐钛矿（0,n）型纳米管却具有直接带隙. 关键词： 2纳米管')" href="#">TiO₂纳米管 Young模量 间接带隙 直接带隙     

La-Ce共掺杂锐钛矿TiO2的缺陷形成能和电子结构分析

采用基于密度泛函的第一性原理研究了稀土元素La、Ce共掺杂锐钛矿相TiO₂的缺陷形成能,缺陷电荷转变能级以及电子结构.研究发现,富氧状态下La、Ce掺杂以及La-Ce共掺的缺陷形成能均为负值,而贫氧状态下La、Ce掺杂形成能为正,表明La、Ce的掺杂TiO₂只能在氧气氛制备条件下进行;替代Ti掺杂缺陷电荷转变能级计算结果表明:0/1-的缺陷电荷转变能级分别位于VBM上面0.522 eV及2.440 eV处;与纯锐钛矿相TiO₂相比,La、Ce单掺杂以及La-Ce共掺杂均能减小TiO₂的禁带宽度,但共掺杂体系的禁带宽度更窄,因此共掺杂体系将更有利于提高TiO₂对可见光的响应能力和光催化性能.     

I掺杂金红石TiO$lt;sub$gt;2$lt;/sub$gt;(110)面的第一性原理研究

利用基于密度泛函理论的第一性原理研究了I掺杂金红石TiO₂（110）表面的形成能和电子结构,分析了不同掺杂位置的结构对TiO₂光催化性能的影响. 计算表明,氧化环境下I最容易替代掺杂表面五配位的Ti,而还原环境下最容易替代掺杂表面的桥位氧. I替位Ti或I替位O都能降低禁带宽度,可能使TiO₂吸收带出现红移现象或产生在可见光区的吸收,其中I替位桥位氧的禁带宽度最小. 吸收光谱表明,I掺杂不仅能提高TiO₂可见光响应,同时可增加紫外光的吸收能量,提高其可见光及紫外光下的光催化性能. 关键词： 第一性原理 I掺杂 2(110)')" href="#">金红石相TiO₂(110) 光催化     

Electronic structure and the optical and photocatalytic properties of anatase doped with vanadium and carbon

The electronic structures of undoped anatase and anatase doped with carbon and vanadium have been calculated using the ab initio tight-binding linear muffin-tin orbital (TB-LMTO) method in the LSDA + U approximation. It has been shown that the doping of TiO₂ leads to the formation of narrow bands of the C and Vimpurity states in the band gap. The calculations of the imaginary part of the dielectric function have made it possible to estimate the intensity of the optical absorption. It has been established that the doping with vanadium and carbon leads to optical absorption in the visible range and to an increase in the absorption in the ultraviolet range up to 4 eV. This should result in an increase in the photocatalytic activity on the surface of the doped anatase. The experimental determination of the photocatalytic activity of whiskers of the anatase doped with carbon and vanadium in the reaction of hydroquinone oxidation has confirmed the increase in the activity of the doped materials under exposure to ultraviolet, visible, and blue light. The phenomenon of dark catalysis in the anatase doped with carbon and vanadium has been interpreted within the concept of low-energy electronic excitatio ns between the impurity levels of carbon.     

Photocatalysts of Cr Doped TiO2 Film Prepared by Micro Arc Oxidation

通过微弧氧化法在Na3PO4+K2Cr2O7电解液中制备了系列铬掺杂二氧化钛薄膜. X射线和扫描电镜显示薄膜的主要晶相为锐钛矿型二氧化钛,且表面为多孔结构. 在可见光照射下,薄膜对降解亚甲基蓝和分解水有着较好的光催化性能,这主要是由铬的掺杂引起的.由于铬的掺杂,一方面在二氧化钛中形成了Cr3+/Cr4+离子对,另一方面在带隙中形成了氧的空位能级. 前者降低了电子-空穴的复合几率,而后者在二氧化钛的禁带中形成了新的能级. 新能级的形成使得由二氧化钛价带跃迁至氧空位能级所需的光子能量减少. 另外探讨了微弧氧化形成掺杂二氧化钛薄膜的机制.     

可见光响应SO2－4／Ce-TiO2的光谱特征及催化性能

采用溶胶‐凝胶法制备了Ce掺杂 T iO2,经 H2 SO4处理得到酸化Ce掺杂 T iO2。利用X射线衍射（XRD）、傅里叶变换红外光谱（FTIR）、吡啶吸附红外光谱（Py‐FTIR）、紫外‐可见光漫反射光谱（UV‐Vis）及X射线光电子能谱（XPS）技术对样品的性质进行了表征,以罗丹明B（RhB）在样品上的可见光催化降解为模型反应,评价了所制备样品的光催化性能。XRD测试结果表明,铈掺杂使 TiO2产生晶格缺陷、粒径减小,有利于光生电荷的转移,继而提高催化剂的活性;FTIR谱图说明SO2－4以桥式双齿配位吸附形式存在;Py‐FTIR谱图显示,酸化铈掺杂TiO2样品表面同时存在Br?nsted和Lewis酸位,但以Lewis酸为主。Lewis酸中心的缺电子性质有利于样品表面的光生电子与光生空穴分离,从而改善催化剂的活性;UV‐Vis结果表明,Ce掺杂减小了TiO2的带隙能,引入的杂能级能够捕获导带上的光生电子和价带上的光生空穴,降低光生电子‐空穴对的复合几率;同时还可以使能量较小的光子激发杂能级上捕获的电子,拓宽光响应范围;XPS分析表明SO2－4／Ce‐TiO2样品上同时存在Ce3＋／Ce4＋的混合价态,Ce3＋／Ce4＋氧化‐还原转换有助于TiO2受光激发后产生的光生电子和空穴的分离,从而提高光量子效率。酸化Ce掺杂TiO2对RhB的可见光催化降解反应有很好的活性,实验结果证明,H2 SO4酸化和Ce掺杂的协同作用改善了样品的可见光响应,促进了其可见光催化反应活性。     

Amorphous BeN as a new solid host for rare‐earth‐related luminescent materials

Beryllium‐nitride (BeN) thin films were prepared by sputtering a Be target in an atmosphere of pure nitrogen. The films were doped with samarium simply by placing a piece of Sm metal on the surface of the Be target. Under these deposition conditions the films present an amorphous structure and an optical bandgap of approx. 4 eV. They also exhibit visible light emission due to Sm³⁺ ions as a result of either photon or electron excitation. The present experimental results show that amorphous BeN films are suitable, and efficient, III‐nitride hosts for rare‐earth doping purposes. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

GGA+U方法研究C-Al掺杂GaN的电子结构和光学性质

本文用密度泛函理论的第一性原理,研究了C单掺、Al单掺、C-Al共掺GaN体系的电子结构及光学性质.通过分析发现,与本征GaN相比,掺杂后体系都发生了晶格畸变,其中C-Al共掺GaN体系,较容易形成且禁带宽度明显减小,形成了P型半导体,显著降低了电子跃迁所需要的能量;另外,该共掺体系的静介电常数最大,极化能力最强,介电虚部的主峰向低能区域偏移,并且吸收光谱在可见光范围内产生了红移现象,这都体现了C-Al共掺可以拓展GaN体系对可见光的响应范围.因此,C-Al共掺将有望提高GaN体系的光催化性能.     

Ab initio calculations of electronic structure of anatase TiO2

This paper presents the results of the self-consistent calculations on the electronic structure of anatase phase of TiO2. The calculations were performed using the full potential-linearized augmented plane wave method (FP-LAPW)in the framework of the density functional theory (DFT) with the generalized gradient approximation (GGA). The fullyoptimized structure, obtained by minimizing the total energy and atomic forces, is in good agreement with experiment.We also calculated the band structure and the density of states. In particular, the calculated band structure prefers an indirect transition between valence and conduction bands of anatase TiO2, which may be helpful for clarifying theambiguity in other theoretical works.     

光电变色器件用纳米晶氧化钛薄膜的微结构与特性

纳米晶TiO2薄膜在光电变色器件中具有很重要的作用。它的微结构直接影响染料的吸附、光的散射以及电荷输运的特性。因此，探索TiO2薄膜的微结构(如粒径、表面形貌和厚度等)及光电性能是非常有意义的。采用电子束蒸发工艺制备了光电变色器件用纳晶TiO2薄膜，利用原子力显微镜、X射线衍射、俄歇电子能谱等手段对纳米晶TiO2薄膜的表面形貌、结晶状态及组分进行了分析。从理论上研究和讨论了纳米晶TiO2薄膜晶粒尺寸对光电性能的影响，并用量子限制效应解释了吸收光谱峰值波长随粒径减小而发生蓝移的现象。