双层Nb掺杂TiO_2薄膜的导电性研究

采用射频磁控溅射的方法通过改变氧分压和基体温度在非晶超白玻璃上沉积了一系列Nb掺杂Ti O_2薄膜,富氧状态下的薄膜为锐钛矿相且绝缘,少氧状态下的薄膜为金红石相但电阻率太大。采用双层膜的结构,首先将在非晶基体上沉积一系列在富氧状态下得到的的锐钛矿相Nb掺杂Ti O_2薄膜为种子层,然后在种子层上外延一层少氧状态下的Nb掺杂Ti O2薄膜为表层,得到的薄膜具有良好的导电性。     

磁控反应溅射TiO2薄膜的实验研究

应用直流和中频交流程序自动控制磁控溅射设备，利用金属Ti靶、纯Fe靶制备出了有一定厚度的质量较好的不同氧流量的Fe掺杂TiO2薄膜，TiO2薄膜被沉积在玻璃基底上。薄膜的制备用程序控制。通过在TiO2薄膜中形成一定的结构，并利用各种分析测试手段对其性能进行了测试，初步探讨了不同氧流量对TiO2薄膜的影响。实验表明程序自动控制不同氧流量Fe掺杂TiO2薄膜的特性有了很大改变。     

不同工艺条件对FePt-AlN纳米薄膜磁性影响的研究

利用磁控溅射方法,在加热的单晶MgO(100)基片上制备了以AlN为母体的FePt薄膜,再经过真空热处理后,得到了具有垂直磁各向异性且无磁交换耦合作用的FePt薄膜;同时,研究了掺杂AlN含量、薄膜的厚度及退火温度对薄膜的磁性能的影响.结果表明,非磁性相AlN的添加能够降低磁交换耦合作用,但同时也会破坏薄膜的垂直磁各向异性.降低薄膜厚度,有利于改善薄膜的垂直磁各向异性,FePt-AlN薄膜的厚度为6nm且掺杂AlN含量达到40%时,经650℃热处理1h后薄膜具有良好垂直磁各向异性、适中矫顽力且无磁交换耦合作用.     

背电极ZnO:Al薄膜与n-a-Si:H膜接触特性的研究

本文分别采用电子束蒸发和磁控溅射的方法在n型掺杂(n-Si:H)膜上沉积了不同掺杂量和不同厚度的掺Al的Zn O(Zn O:Al)薄膜。通过I-V测试仪测试了两种方法制备的Zn O:Al薄膜与n-Si:H膜的接触特性,结果显示对于电子束蒸发制备的Zn O:Al薄膜,当掺杂浓度为2.5%时n-a-Si:H/Zn O:Al的接触电阻最小,在厚度变化不大的情况下,n-a-Si:H/Zn O:Al的接触电阻随着Zn O:Al厚度的增加而增大。而磁控溅射制备的Zn O:Al薄膜,n-a-Si:H/Zn O:Al的接触电阻随着厚度的增加而不断减小。     

溶胶凝胶法制备Cu掺杂ZnO纳米薄膜及其表征

采用溶胶-凝胶法制备了不同Cu掺杂浓度的ZnO薄膜,并通过X射线衍射仪、扫描电子显微镜、紫外可见分光光度计和伏安特性测试等研究了Cu掺杂量对薄膜微观结构、表面形貌及光电特性的影响。结果表明:所得Cu掺杂ZnO薄膜为六角纤锌矿多晶结构,有CuO杂质相生成。随Cu掺杂量的增加,薄膜晶粒长大,且样品粒度均匀,平均粒径约53 nm。Cu掺杂ZnO薄膜具有良好的透光性,在可见光范围内的平均透射率超过80%,最大可达90%以上。Cu掺杂浓度为0.001%时,所得ZnO薄膜的导电性明显优于其他掺杂条件下的样品。     

锰掺杂对PbZr0.5Ti0.5O3铁电薄膜电学性能的影响

采用Sol-gel方法在生长有LNO3的Si(100)衬底上制备了掺Mn的PbZr0.5Ti0.5O3铁电薄膜(PMZT)。PMZT薄膜具有优良的铁电性。在外加电场下观察到了非对称剩余极化翻转行为。这种剩余极化的翻转不对称随着锰掺杂浓度的增加而变大,从而表明极化过程中产生的内建偏压电场是由Mn的掺杂引起的。当薄膜厚度保持不变时候,PMZT薄膜的剩余极化(Pr)和平均矫顽电场(Ec)随着锰掺杂浓度的增大而减小。在低频下,PMZT薄膜的介电常数随着锰的掺杂浓度的增加而减小。瞬时电流随着时间的呈指数衰减,最后到达饱和的稳态值。样品的漏电流密度随着电压的增加而近似地线性增加,显示出欧姆特性。在相同电压下,漏电流密度随着Mn掺杂浓度的增加而增加。     

CO_2气体反应磁控溅射制备Ti-O薄膜成分和结构研究

室温下采用反应磁控溅射的方法,利用CO2作碳源和氧源制备了碳掺杂Ti-O薄膜。X射线衍射(XRD)、光射线电子能谱(XPS)和拉曼光谱用于表征薄膜的成分和结构。采用紫外-可见(UV-Vis)分光光度计测量了薄膜的吸光度并通过作图计算得到其带隙宽度。结果表明,用CO2作碳源和氧源,可得到C掺杂的Ti-O薄膜。当掺杂碳时,钛氧膜中金红石相特征峰显著减弱,且碳以取代O原子的形式掺杂在薄膜中并促使TiO相的出现。当反应气体为CO2和O2共存时,钛原子优先与氧原子结合并抑制TiO相的形成。碳的掺入能有效降低TiO2带隙宽度,使薄膜的吸收边扩展到可见光区,提高对可见光的吸收。     

基底温度对直流溅射Nb掺杂TiO2薄膜性能的影响

采用陶瓷靶直流磁控溅射,以玻璃为基底制备2.5wt%Nb掺杂TiO2薄膜,控制薄膜厚度在300~350 nm,研究了不同基底温度下所制得薄膜的结构、形貌和光学特性.XRD分析表明,基底温度为150℃、250℃和350℃时,薄膜分别为非晶态、锐钛矿(101)和金红石相(110)结构.基底温度250℃时,锐钛矿相薄膜的晶粒尺寸最大,约为32 nm.薄膜表面形貌的SEM分析显示,薄膜粗糙度和致密度随基底温度升高得到改善.薄膜的平均可见光透过率在基底温度为250℃以内约为70%,随基底温度升高至350℃,平均透过率下降为59%,金红石相的存在不利于可见光透过.Nb掺杂TiO2薄膜的光学带宽在3.68~3.78 eV之间变化.基底温度为250℃时,锐钛矿相薄膜的禁带宽度最大,为3.78 eV.     

反应磁控溅射法制备F掺杂ZnO(FZO)薄膜的结构和透明导电性能

以Zn/ZnO/ZnF2混合物为靶材,在衬底温度(Ts)为150℃和300℃、溅射气氛为Ar+O2和Ar+H2下反应溅射制备F掺杂ZnO(FZO)薄膜,研究气体流量、Ts以及溅射气氛对薄膜结构及透明导电性能的影响.结果表明:对于Ar+O2下制备的FZO薄膜,Ts=300℃时有利于制备出具有(002)择优取向、结晶度高、压应力低且透明导电性能较好的薄膜.对于Ar+H2下制备的薄膜,Ts增大到300℃虽然提高了薄膜结晶度和透光性,降低了压应力,但薄膜厚度明显降低,薄膜导电性能变差.比较两种气氛下制备的FZO薄膜,发现Ar+H2下制备的薄膜可在150℃和0.8～3.2 mL·min-1的H2流量范围内得到更好的透明导电性能(电阻率为3.5×10-3Ω·cm,可见光平均透光率为87％).讨论Ar+H2气氛时H等离子的刻蚀作用与H掺杂、A r+O 2气氛时O离子的轰击作用与薄膜氧缺陷的变化、Ts升高时沉积原子反应活性与迁移能力增强以及Eg与载流子浓度的关系.     

溶胶-凝胶法制备AZO薄膜的研究进展

综述了采用溶胶-凝胶法制备AZO薄膜的进展,阐述了影响AZO薄膜光电特性的主要工艺参数,分析了陈化时间、热处理工艺、铝掺杂量、催化剂种类及薄膜厚度因素等对AZO薄膜结构、光电性能的影响,指出了溶胶-凝胶法制备AZO薄膜的优势与不足,展望了未来的研究方向.     

钴掺杂Sr_4Fe_6O_(13)混合导体氧化物结构及透氧测定

用湿化学法合成了Ｓｒ４ＣｏｘＦｅ６－ｘＯ１３±δ系列混合导体氧化物,对其相结构与透氧性能进行了研究．钴离子的引入导致材料中钙钛矿型杂相的出现,Ｘ＝２．０时材料中还产生了ＣｏＯ杂相,ｘ＝２．６时材料呈现钙钛矿型结构．Ｓｒ４Ｆｅ４Ｃｏ２Ｏ１３±δ的相结构还与焙烧温度及环境气氛中的氧浓度密切相关．随着氧浓度的降低,材料从纯相Ｓｒ４Ｆｅ６Ｏ１３结构（纯氧气气氛下）转变为Ｓｒ４Ｆｅ６Ｏ１３结构、钙钛矿型结构和ＣｏＯ共存（空气气氛下）,直至转变为针镍矿结构、 Ｓｒ４Ｆｅ６Ｏ１３结构和 ＣｏＯ共存． Ｓｒ４Ｆｅ６Ｃｏ１３±δ导体膜在ａｉｒ／Ｈｅ氧浓差梯度下的透氧量为 １．５×１０８ｍｏｌ／ｃｍ２·ｓ（８５０℃）,在６５０～８５０℃范围内透氧活化能为７０ｋＪ／ｍｏｌ．     

Modifying the oxygen adsorption properties of YBaCo<Subscript>4</Subscript>O<Subscript>7</Subscript> by Ca,Al, and Fe doping

The doping effect of Ca, Al, and Fe on the oxygen adsorption properties of YBaCo₄O₇ was investigated by thermogravimetry (TG) method. It was found that the original YBaCo₄O₇ oxygen adsorption properties can be modified greatly by Ca, Al, and Fe doping. Ca doping in Y sites eliminates the oxygen adsorption at low temperature (~300 °C) but the oxygen adsorption properties at high temperature is almost unchanged. Minor Al doping in Co sites eliminates the oxygen adsorption hump at high temperature, but the hump at low temperature is preserved. Fe appearance in YBaCo₃Al_1−x Fe _x O₇ seems to weaken the effect of Al doping, so the oxygen hump at high temperature emerges again. The doping effect was discussed based on elements valence, binding energy between cations and oxygen ions, and distortion of crystal structure.     

Thermal expansion and electrical conductivity of CaTi<Subscript>0.9</Subscript>M<Subscript>0.1</Subscript>O<Subscript>3−δ</Subscript> (M = Fe,Cu, Al)

The thermal expansion of CaTi_0.9M_0.1O_3?δ (M = Fe, Cu, Al) samples has been measured, and their lattice parameters have been refined in space group Pnma. The three materials are shown to be mixed conductors, p-type at high oxygen partial pressures and n-type at low oxygen pressures. At intermediate oxygen partial pressures, the conductivity varies little. The acceptor dopants studied are shown to raise the conductivity of calcium titanate in the order Al < Cu < Fe.     

（BiAl）YIG薄膜的生长感生磁各向异性

从理论和实验上分析了Ｆｅ＾３＋和Ｆｅ＾２＋对（ＢｉＡ）ＹＩＧ薄膜的生长感各向异性的贡献，掺Ｂｉ导致的生长磁感生各向异性，来源于Ｅｉ＾３＋改变了Ｆｅ＾３＋的零场劈裂，其大小取决于Ｂｉ＾３＋含量及在十二面体位的择优分布，高价离子和氧空位形成的Ｆｅ＾２＋在八面体位的择优分布，对生长感生磁各向异性也有贡献。     

Migration kinetics of oxygen vacancies in Mn-modified BiFeO₃ thin films

Migration kinetics of oxygen vacancies in BiFe(0.95)Mn(0.05)O(3) thin film were investigated by the temperature -dependent leakage current as well as the electric field and temperature-dependent impedance spectroscopy. The BiFe(0.95)Mn(0.05)O(3) is of an abnormal leakage behavior, and an Ohmic conduction is observed regardless of varied temperatures and electric fields. The temperature-dependent impedance spectroscopy under different resistance states is used to illuminate different leakage behavior between BiFe(0.95)Mn(0.05)O(3) and pure BiFeO(3). The impedance spectroscopy under a high resistance state shows that the first ionization of oxygen vacancies is responsible for the dielectric relaxation and electrical conduction of BiFe(0.95)Mn(0.05)O(3) in the whole temperature range of 294 to 474 K; the BiFeO(3) exhibits similar dielectric relaxation and electrical conduction behavior in the low-temperature range of 294-374 K, whereas the short-range motion of oxygen vacancies was involved in the high-temperature range of 374-474 K. The impedance spectroscopy under a low resistance state demonstrates that the dielectric relaxation and conduction mechanisms almost keep unchanged for BiFe(0.95)Mn(0.05)O(3), whereas the hopping electrons of Fe(2+)-V(O)(?)-Fe(3+) and Fe(2+)-Fe(3+) are responsible for its dielectric relaxation and conduction mechanism of BiFeO(3). Different impedance spectroscopy under low and high resistance states confirms that an abnormal leakage behavior of BiFe(0.95)Mn(0.05)O(3) is related to different migration kinetics of oxygen vacancies, obviously differing from that of BiFeO(3).     

Enhanced Sonodynamic Cancer Therapy through Iron-Doping and Oxygen-Vacancy Engineering of Piezoelectric Bismuth Tungstate Nanosheets

Sonodynamic therapy (SDT) is regarded as a new-rising strategy for cancer treatment with low invasiveness and high tissue penetration, but the scarcity of high-efficiency sonosensitizers has seriously hindered its application. Herein, the iron-doped and oxygen-deficient bismuth tungstate nanosheets (BWO-Fe NSs) with piezotronic effect are synthesized for enhanced SDT. Due to the existence of oxygen defects introduced through Fe doping, the bandgap of BWO-Fe is significantly narrowed so that BWO-Fe can be more easily activated by exogenous ultrasound (US). The oxygen defects acting as the electron traps inhibit the recombination of US-induced electrons and holes. More importantly, the dynamically renewed piezoelectric potential facilitates the migration of electrons and holes to opposite side and causes energy band bending, which further promotes the production of reactive oxygen species. Furthermore, Fe doping endows BWO-Fe with Fenton reactivity, which converts hydrogen peroxide (H₂O₂) in tumor microenvironment into hydroxyl radicals (•OH), thereby amplifying the cellular oxidative damage and enhancing SDT. Both in vitro and in vivo experiments illustrate their high cytotoxicity and tumor suppression rate against refractory breast cancer in mice. This work may provide an alternative strategy to develop oxygen-deficient piezoelectric sonosensitizers for enhanced SDT via doping metal ions.     

Cr掺杂Ba0.5Sr0.5Co0.8Fe0.1Cr0.1O3-δ钙钛矿型膜的透氧性能研究

采用固相反应法合成了钙钛矿型Ba0.5Sr0.5Co0.8Fe0.2-xCrxO3-δ(x=0.00,0.10)透氧膜粉体。利用XRD和SEM研究了Ba0.5Sr0.5Co0.8Fe0.2-xCrxO3-δ(x=0.00,0.10)的晶体结构和烧结性能,考察了在700~850℃范围内Ba0.5Sr0.5Co0.8Fe0.2-xCrxO3-δ(x=0.00,0.10)膜片的氧渗透性能。结果表明,它们均显示出优良的透氧性能,850℃时的透氧量分别为1.05mL/(min.cm2)、0.85mL/(min.cm2)。透氧稳定性的研究表明,Cr掺杂Ba0.5Sr0.5-Co0.8Fe0.1Cr0.1O3-δ在800℃时显示出较高的稳定性,证实用Cr离子部分取代Ba0.5Sr0.5Co0.8Fe0.2O3-δ的Fe离子能明显提高钙钛矿的结构稳定性。     

Phosphorus-doped Fe7Ss@C nanowires for efficient electrochemical hydrogen and oxygen evolutions: Controlled synthesis and electronic modulation on active sites

Developing low-cost,efficient,and stable non-precious-metal electrocatalysts with controlled crystal structure,morphology and compositions are highly desirable for hydrogen and oxygen evolution reactions.Herein,a series of phosphorus-doped Fe7S8 nanowires integrated within carbon (P-Fe7S8@C) are rationally synthesized via a one-step phosphorization of one-dimensional (1D) Fe-based organicinorganic nanowires.The as-obtained P-Fe7S8@C catalysts with modified electronic configurations present typical porous structure,providing plentiful active sites for rapid reaction kinetics.Density functional calculations demonstrate that the doping Fe7S8 with P can effectively enhance the electron density of Fe7S8 around the Fermi level and weaken the Fe-H bonding,leading to the decrease of adsorption free energy barrier on active sites.As a result,the optimal catalyst of P-Fe7S8-600@C exhibits a relatively low overpotential of 136 mV for hydrogen evolution reaction (HER) to reach the current density of 10 mA/cm2,and a significantly low overpotential of 210 mV for oxygen evolution reaction (OER) at 20mA/cm2 in alkaline media.The work presented here may pave the way to design and synthesis of other prominent Fe-based catalysts for water splitting via electronic regulation.     

Electroanalytical performance of carbon films with near-atomic flatness

Physicochemical and electrochemical characterization of carbon films obtained by pyrolyzing a commercially available photoresist has been performed. Photoresist spin-coated on to a silicon wafer was pyrolyzed at 1,000 degrees C in a reducing atmosphere (95% nitrogen and 5% hydrogen) to produce conducting carbon films. The pyrolyzed photoresist films (PPF) show unusual surface properties compared to other carbon electrodes. The surfaces are nearly atomically smooth with a root-mean-square roughness of <0.5 nm. PPF have a very low background current and oxygen/carbon atomic ratio compared to conventional glassy carbon and show relatively weak adsorption of methylene blue and anthraquinone-2,6-disulfonate. The low oxygen/carbon ratio and the relative stability of PPF indicate that surfaces may be partially hydrogen terminated. The pyrolyzed films were compared to glassy carbon (GC) heat treated under the same conditions as pyrolysis to evaluate the electroanalytical utility of PPF. Heterogeneous electron-transfer kinetics of various redox systems were evaluated. For Ru(NH3)6(3+/2+), Fe(CN)6(3-/4-), and chlorpromazine, fresh PPF surfaces show electron-transfer rates similar to those on GC, but for redox systems such as Fe3+/2+, ascorbic acid, dopamine, and oxygen, the kinetics on PPF are slower. Very weak interactions between the PPF surface and these redox systems lead to their slow electron-transfer kinetics. Electrochemical anodization results in a simultaneous increase in background current, adsorption, and electron-transfer kinetics. The PPF surfaces can be chemically modified via diazonium ion reduction to yield a covalently attached monolayer. Such a modification could help in the preparation of low-cost, high-volume analyte-specific electrodes for diverse electroanalytical applications. Overall, pyrolysis of the photoresist yields an electrode surface with properties similar to a very smooth version of glassy carbon, with some important differences in surface chemistry.     

刷镀铁工艺研究与应用

刷镀铁与刷镀镍相比具有成本低、硬度高的优点.研究了刷镀铁镀液中主盐、配位体、缓冲剂、抗氧化剂、表面活性剂等添加剂的种类、浓度及电压、pH值、阳极等工艺条件对镀层性能的影响,确定了镀液配方和工艺.结果表明,在优化的镀液配方及工艺条件下,可获得了良好的镀铁层,镀层硬度为450～500 HV.采用铁屑和三氯化铁配制镀液,成本低、配制速度快、浓度易控制、对环境无污染、所得镀层硬度高、结合力好.