聚对苯撑纳米复合提升ZnO基热电材料性能

以溶胶-凝胶法合成了PPP@Zn_1-xCo_xO纳米复合热电材料(x=0, 0.025), 再以放电等离子烧结制备成块体, 并对其热电性能进行了研究。由透射电镜照片发现, PPP纳米颗粒尺寸在200 nm以下。热电性能分析表明, 随着PPP添加量的增加, 赛贝克系数先增大后减小。电导率随PPP含量增加而大幅度提高。与ZnO块体材料相比, 溶胶-凝胶法合成的PPP@Zn_1-xCo_xO纳米复合热电材料的热导率大幅度降低, 在640 K时, 9wt% PPP的纳米复合热电材料热导率降低至5.4 W/(m·K)。电导率的增加和热导率的降低, 导致热电性能大幅度提高, 9wt%PPP@Zn_0.975Co_0.025O纳米复合热电材料在870 K时具有最大ZT值(0.16), 是Zn_0.975Co_0.025O材料的8倍。     

Fe2W型铁氧体BaFe2-x2+CoxFe163+O27(x=0.0~0.8)的微观结构和磁性

用固相法制备Fe₂W型铁氧体BaFe_2-x²⁺Co_xFe₁₆³⁺O₂₇(x=0.0~0.8),采用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、红外光谱仪(FT-IR)和振动样品磁强计(PPMS-VSM)等手段分析其物相组成、结构和磁性并使用Reitveld拟合分析晶体结构,研究了Co²⁺部分取代Fe²⁺的Fe₂W型铁氧体的微观结构和磁性。结果表明：所有样品都是纯相铁氧体BaFe_2-x²⁺Co_xFe₁₆³⁺O₂₇。样品具有W铁氧体结构,晶粒呈良好的六角形结构且分布均匀。用 Co取代能明显提高Fe₂W型铁氧体300 K的饱和磁化强度(M_s)。     

Zn3-xMnxTeO6的晶体结构与吸收光谱和磁性研究

本工作主要研究Mn ²⁺离子掺杂的类刚玉系氧化物Zn₃TeO₆(0<x≤2.0)的晶体结构与光学性质和磁性的变化。Zn_3-xMn_xTeO₆粉末样品通过固相反应合成。Mn掺杂量的相图表明, x<1.0时保持单斜(C2/c)结构, 1.0≤x≤1.6为单斜(C2/c)和三方六面体混合相(R-3), x≥1.8时完全转变为R-3相, 且x=2.0时形成ZnMn₂TeO₆, Te-O和Mn/Zn-O键长增大, 八面体发生更大畸变。X射线粉末衍射结构精修也表明R-3相中Zn/MnO₆为畸变八面体。随着Mn ²⁺掺杂含量的增加, Zn_3-xMn_xTeO₆系列化合物不仅结构发生变化, 其颜色也由浅变深。紫外吸收光谱中随着掺杂浓度的增加, 400~550 nm处的吸收增强, 样品的光学带隙也由3.25 eV (x=0.1)逐渐减小到2.08 eV (x=2.0), 分析表明, 可见区吸收的增强是源于MnO₆八面体中Zn/MnO₆八面体中Mn ²⁺离子的d-d跃迁, 导致样品由浅黄色逐渐变为暗黄色。 磁性测试表明, 固溶体的反铁磁转变温度随着Mn ²⁺掺杂量的提高而逐渐增加, 且掺入的Mn ²⁺离子以高自旋态 存在。     

Mn和Fe掺杂对尖晶石氧化物Co2MnO4结构和磁性的影响

以金属盐及柠檬酸为原料, 采用溶胶-凝胶法制备了尖晶石氧化物Co_2-xMn_1+xO₄和Co_2-xFe_xMnO₄系列, 通过XRD、FT-IR及PPMS等手段研究了Co₂MnO₄及系列掺杂样品的成相、结构、磁性等特征。结果表明, Co_2-xMn_1+xO₄系列在x<0.6时, 呈单相立方结构, 晶格常数和磁性随着Mn掺杂量的增加而增大, x≥0.6时逐渐向四方结构转化, 磁性下降, 并呈现磁化强度不易饱和的特征; Co_2-xFe_xMnO₄系列样品在x<1.75成分范围内均可保持立方结构, 且晶格常数和磁性都随着x增大而提高。这些变化主要是由于掺杂原子尺度及磁矩均大于原有元素, 掺杂后样品内部的磁性相互作用有所增强。     

Si3N4掺杂氮化对Sr3SiO5:Eu2+荧光粉发光性能的影响

采用高温固相法制备Si₃N₄掺杂氮化Sr_2.99SiO_5-6xN_4x:0.01Eu²⁺荧光粉。采用XRD、EDS和SEM测试结果表明: N^3-进入Sr₃SiO₅基质晶格中取代部分O^2-离子, 形成了单一相Sr_2.99SiO_5-6xN_4x:0.01Eu²⁺固溶体。PL&PLE荧光光谱测试结果显示, Sr_2.99SiO_5-6xN_4x:0.01Eu²⁺荧光粉在344nm紫外光的激发下发射出红橙光, 属于Eu²⁺离子典型的 4f⁶5d¹→4f⁷电子跃迁。随着N浓度的增加, Sr_2.99SiO_5-6xN_4x:0.01Eu²⁺荧光粉发射光谱和激发光谱的强度明显增强。热稳定性测试结果表明, Si₃N₄掺杂氮化能够显著提高Sr₃SiO₅:Eu²⁺荧光粉的热稳定性。通过Arrhennius模型拟合结果表明横向穿越过程(crossover)引起的Sr₃SiO₅:Eu²⁺荧光粉氮化前后的温度猝灭。     

A/B位双取代钛酸铋钠基压电陶瓷性能研究

采用固相烧结方法制备了Bi、Co同时取代化学计量比钛酸铋钠基(Bi_0.5+x/2Na_0.5-x/2)_0.94Ba_0.06Ti_1-xCo_xO₃无铅压电陶瓷, 研究了材料中A/B位缺陷对其电滞回线和电致应变的影响。结果表明陶瓷具有均一的赝立方结构, 随着掺杂量的增加, 材料铁电-弛豫相转变温度降低, 应变增加。同时材料在疲劳过程中伴随着弛豫相的增多, 在较低电场下产生较大的应变(0.458%), 逆压电常数d₃₃^*达到770 pm/V。介电温谱和电滞回线上反常变化与化学计量比陶瓷中产生的A/B位缺陷偶极子密切相关, 并表明这种缺陷偶极子是以氧空位为媒介形成的。     

La掺杂对磁控溅射CaB6薄膜的影响

利用直流磁控溅射的方法制备掺La和未掺La的Ca_1-xLa_xB₆ (x = 0, 0.01, 0.02, 0.03)薄膜。利用原子力显微镜对薄膜的表面形貌及厚度进行表征。掺La的薄膜的厚度约为未掺杂的两倍; La的掺杂会使薄膜的晶粒尺寸变大。利用X射线光电子能谱对薄膜表面的化学组成进行检测。薄膜中Ca/La比接近理论值, 没有检测到其它的铁磁性杂质及元素, 尤其是Fe。Ca_0.98La_0.02B₆薄膜具有最大的室温饱和磁化强度, 强度值为84.54 emu/cm³。同时薄膜的饱和磁化强度值随薄膜厚度的增加而降低。在Ca_1-xLa_xB₆薄膜中, B₆空位是薄膜磁性的主要来源, 其它类型的缺陷例如晶界等, 同样影响着薄膜磁性的大小。     

非金属S掺杂对NaTaO3可见光下光催化性能的影响

以Ta₂O₅为前驱体, Na₂S₂O₃为S源, 采用水热法成功合成了新型S掺杂NaTaO₃, 并以甲基橙为目标降解物,研究S元素掺杂对提高纳米NaTaO₃的可见光光催化机理和反应历程。采用场发射扫描电镜(SEM)、X射线光电子能谱(XPS)、紫外-可见漫反射光谱仪(UV-Vis DRS)和X射线衍射仪(XRD)等对所得样品进行分析。实验结果表明, 掺入S元素后, NaTaO₃晶体的表面电荷和表面形貌没有发生明显变化。UV-Vis漫反射光谱分析结果表明S^2-部分取代晶格中的O^2-离子形成Ta-S-Ta键, 掺杂后的NaTaO_3-xS_x样品的光响应范围拓展至可见光区域。光降解实验结果表明, S掺杂NaTaO₃在可见光下其光催化活性明显高于纯相NaTaO₃。这是因为在NaTaO_3-xS_x晶体内S^2-离子取代了部分O^2-离子形成掺杂态。GC-MS实验结果表明, NaTaO_3-xS_x样品能够在可见光条件下将甲基橙(质荷比m/z=304)降解至m/z=156, 226和276的化合物, 随着降解时间增加, 可继续降解至m/z=156或m/z=212的化合物, 并最终转化为无机小分子(SO₄^2-, NO₃^-和NH₄⁺)。而且, NaTaO_3-xS_x在光降解过程中非常稳定, 重复使用10次后光催化活性因催化剂损失而略微下降。     

硬脂酸盐熔融法合成(Y,Lu)AG:Ce荧光粉及荧光性能研究

采用硬脂酸盐熔融新方法合成了[(Y_1-xLu_x)_1-yCe_y]₃Al₅O₁₂固溶体荧光粉(x=0’0.5, y=0.005’0.03), 并通过XRD、SEM、BET和PL-PLE等方法对该荧光粉进行了表征。结果表明, 纯相石榴石在800℃的低温下即可生成, 而不经过YAM和YAP中间相。煅烧所得[(Y_1-xLu_x)_1-yCe_y]₃Al₅O₁₂ 荧光粉具有良好的均一性和分散性, 并在455 nm蓝光激发下于544 nm附近呈现最强黄光发射。粉体的发光强度随煅烧温度升高而增大, 归因于结晶度提高和表面缺陷减少。发现Ce³⁺的荧光猝灭浓度为1.5%, 猝灭机制为Ce-Ce间的交换相互作用和晶格缺陷。发现发射峰位随Ce³⁺含量增加而红移, 而最强激发峰和发射峰随Lu³⁺含量增大而蓝移, 归因于Ce³⁺离子5d激发态能级重心移动和晶体场劈裂的共同作用。     

硼含量对碳硼化合物结构、力学影响行为研究

利用低压化学气相沉积技术, 以BCl₃-C₃H₆-H₂为反应气体制备了不同掺硼量的热解碳薄膜B_xC_1-x(x=0.05, 0.10, 0.16, 0.30, 0.50), 并研究了硼含量对B_xC_1-x微观结构及力学性能的影响。B_0.1C_0.9展现了高度结晶的类石墨结构, 其中大部分B取代石墨层中的C。随着B含量上升, B主要形成B-C键, B_xC_1-x结构向无定型转变。纳米压痕测试结果显示, B_0.1C_0.9的弹性模量和硬度较低, 载荷位移曲线显示其力学变形接近弹性变形, 随着B含量增加, 碳化硼生成量增加, 其弹性模量和硬度显著提升, 载荷位移曲线表现出典型的脆性材料力学行为。     

Nano-polycrystalline vanadium oxide thin films prepared by pulsed laser deposition

Nano-polycrystalline vanadium oxide thin films have been successfully produced by pulsed laser deposition on Si(100) substrates using a pure vanadium target in an oxygen atmosphere. The vanadium oxide thin film is amorphous when deposited at relatively low substrate temperature (500 degrees C) and enhancing substrate temperature (600-800 degrees C) appears to be efficient in crystallizing VOx thin films. Nano-polycrystalline V3O7 thin film has been achieved when deposited at oxygen pressure of 8 Pa and substrate temperature of 600 degrees C. Nano-polycrystalline VO2 thin films with a preferred (011) orientation have been obtained when deposited at oxygen pressure of 0.8 Pa and substrate temperatures of 600-800 degrees C. The vanadium oxide thin films deposited at high oxygen pressure (8 Pa) reveal a mix-valence of V5+ and V4+, while the VOx thin films deposited at low oxygen pressure (0.8 Pa) display a valence of V4+. The nano-polycrystalline vanadium oxide thin films prepared by pulsed laser deposition have smooth surface with high qualities of mean crystallite size ranging from 30 to 230 nm and Ra ranging from 1.5 to 22.2 nm. Relative low substrate temperature and oxygen pressure are benifit to aquire nano-polycrystalline VOx thin films with small grain size and low surface roughness.     

PLD工艺制备高质量ZnO/Si异质外延薄膜

采用脉冲激光沉积工艺在不同条件下以Si(111)为衬底制备了Zno薄膜.通过对不同氧压下(0～50Pa)沉积的样品的室温PL谱测试表明,氧气氛显著地提高了薄膜的发光质量,在50Pa氧气中沉积的ZnO薄膜具有最强的近带边UV发射.XRD测试说明在氧气氛中得到的薄膜结晶质量较差,没有单一的(002)取向.利用-低温(500℃)沉积的ZnO薄膜作缓冲层,得到了高质量的ZnO外延膜.与直接沉积的ZnO膜相比,生长在缓冲层上的ZnO膜展现出规则的斑点状衍射花样,而且拥有更强的UV发射和更窄的UV峰半高宽(98meV).对不同温度下沉积的缓冲层进行了RHEED表征,结果表明,在600～650℃之间生长缓冲层,有望进一步改善ZnO外延膜的质量.     

Al-doped ZnO films by pulsed laser deposition at room temperature

Polycrystalline Al-doped ZnO films with good photoluminescence property were successfully deposited on quartz glass substrates by pulsed laser deposition (PLD) at room temperature. The films were obtained by ablating a metallic target (Zn:Al 3 wt%) at various laser energy densities (1.0-2.1 J/cm²) in oxygen atmosphere (9 Pa). The structure of the films was characterized by XRD. Ultraviolet photoluminescence centered at 359-361 nm was observed in the room temperature PL spectra of the Al-doped ZnO films.     

Observation of Room Temperature Ferromagnetism in Conducting and Insulating Cu doped ZnO Thin Films

With pulsed laser deposition, the Cu_0.04Zn_0.96O thin films are grown at 600 °C under three different oxygen pressures, namely PO₂ = 0.00, 0.02, and 1.00 Pa. X-ray diffraction shows single-phase material for the samples grown under PO₂ = 0.00 and 1.00 Pa and CuO secondary phase for the PO₂ = 0.02 Pa grown sample. The observation of satellite structures in the Cu 2p core level X-ray photoelectron spectroscopy (XPS) spectra suggest the presence of Cu²⁺ and CuO secondary phases in the samples grown at PO₂ = 0.02 and 1.00 Pa. The sample grown under vacuum (PO₂ = 0.00 Pa) shows mixed Cu oxidation state of 1 + or 2 + . The sample grown without oxygen is n-type and those grown with oxygen are highly insulating. The insulating sample grown at PO₂ = 0.02 Pa shows highest magnetization due to possible collective behavior of Cu²⁺ – O _v – Cu²⁺ network in the form of bound magnetic polaron (BMP) and ferromagnetic superexchange interaction coming from uncompensated surface spins of the Cu ions in the CuO secondary phase. Both delocalized electrons (～3.32 × 10¹⁸) due to oxygen deficient defects and reduced amount of effective Cu²⁺ ions discredit the BMP model for this vacuum grown sample, and magnetism is suggested due to O _v and presence of possible CuO secondary phase.     

Dependence of ferromagnetic properties on growth oxygen partial pressure in boron-doped ZnO thin films

Boron-doped ZnO films were prepared by pulsed laser deposition technique. Magnetic, electrical, and optical properties of Zn_1?x B _x O films have been studied. It is found that the magnetic properties of the Zn_1?x B _x O films are sensitive to growth oxygen partial pressure. The films deposited under a high oxygen partial pressure of about 10?Pa appear to be ferromagnetic insulators at room temperature (RT). However, when the oxygen partial pressure decreases to 1.2?Pa, the films are non-ferromagnetic conductors at RT. Zn vacancies, which can be controlled by the oxygen partial pressure, are shown to be essential for realizing ferromagnetism (FM); on the other hand, the n-type nature of ZnO has no contribution to the FM observed in the B-doped ZnO films.     

Study of ZnO layers growth by pulsed laser deposition from Zn and ZnO targets

The article deals with structural properties of ZnO thin layers prepared on Si (111) by pulsed laser deposition at different pressures (1-35 Pa) of ambient oxygen in the deposition chamber. The growth temperature was 400 °C and a pulsed Nd:YAG laser was used at a wavelength of 355 nm. Two parallel sets of samples deposited by ablation of different targets (a sintered ceramic pellet of ZnO and a pure metallic Zn target) were examined. The samples were characterized by different analytical methods: scanning electron microscope (SEM), secondary ion mass spectroscopy (SIMS), and X-ray diffraction (XRD). The prepared layers exhibited columnar structure and uniform preferred c-axis orientation. The results showed that deposition of the high quality of ZnO films fabricated from both targets is comparable, except for those obtained at low (1 Pa) pressures.     

射频磁控溅射沉积高质量ZnO薄膜的工艺研究

在室温下利用射频磁控溅射法在硅(100)基片上制备ZnO薄膜,利用X射线衍射(XRD)和扫描电子显微镜(SEM)对其结晶性能进行分析。研究了制备条件对薄膜沉积速率的影响。分析了薄膜沉积速率对薄膜结晶状况的影响及源气体中的氧气和氩气的流量比对薄膜结晶状况的影响。研究结果表明,薄膜的生长速率强烈依赖于射频功率和工作气压,薄膜的结晶性能强烈依赖于薄膜的沉积速率和反应气体中氧气和氩气的流量比。制备高结晶质量的ZnO薄膜的最佳工艺参数为靶到衬底的距离为4cm,输入功率为250W,源气体中氩气和氧气的流量比n(Ar)∶n(O2)为5∶20,溅射工作气压为2Pa。在最佳工艺条件下所制备的薄膜表面平整致密,接近单晶,在可见光区的透射率高达90%。     

射频磁控反应溅射制备Al2O3薄膜的工艺研究

采用射频磁控反应溅射法,以高纯Al为靶材,高纯O2为反应气体,在不锈钢和单晶Si基片上成功地制备了氧化铝(Al2O3)薄膜,并对氧化铝薄膜的沉积速率、结构和表面形貌进行了研究.结果表明,沉积速率随着射频功率的增大先几乎呈线性增大而后缓慢增大;随着溅射气压的增加,沉积速率先增大,在一定气压时达到峰值后继续随气压增大而减小,同时随着靶基距的增大而减小;随着氧气流量的不断增加,靶面溅射的物质从金属态过渡到氧化物态,沉积速率也随之不断降低.X射线衍射图谱表明薄膜结构为非晶态;用原子力显微镜对薄膜表面形貌观察,薄膜微结构为柱状.     

低温生长Zn1-xCoxO(x=0.33)薄膜的微结构和磁性

用电子束反应蒸镀法在低温生长了Zn1-xCoxO薄膜.Co含量x高达0.33的Zn1-xCoxO薄膜仍具有类ZnO的纤锌矿结构,没有杂质相,Co的化合价为 2.场冷和零场冷M-T及M-H曲线表明,Zn1-xCoxO(x=0.33)薄膜在低温下具有铁磁性;随着温度的升高,其剩磁和矫顽力均逐渐下降,在65 K以上趋于零,显示出超顺磁性.Zn1xCoxO薄膜的低温铁磁性起源于Co2 离子之间的双交换相互作用及载流子诱导的sP d交换耦合作用,而从低温(＜65 K)铁磁态到高温(＞65 K)超顺磁态的转变可归因于薄膜的纳米晶小尺寸效应.     

SnO2-x薄膜非化学计量比对气敏性能的影响

采用反应磁控溅射法制备SnO2薄膜经常出现化学计量比的失衡问题。通过控制溅射过程中的氧分压制备不同化学计量比的SnO2-x薄膜,研究非化学计量比对薄膜结构、成分以及气敏性能的影响。XRD结果表明氧分压对材料结构和取向的影响非常显著。薄膜的O／Sn和表面化学成分通过XPS进行确定,分析发现氧分压的增加促使薄膜接近化学计量比,但表面化学吸附氧含量在0．33Pa氧分压下达到最大。气敏性能测试表明,非化学计量比主要影响薄膜表面的化学吸附氧数量,从而影响导电性和气体敏感性。氧分压对薄膜化学吸附氧的影响趋势与对气敏性能的影响趋势一致。0．33Pa氧分压下制备的薄膜拥有最多的表面吸附氧,同时对氢气的灵敏度高达45．6％。另外,在0．2～0．5Pa氧分压下制备的薄膜对氢气具有较好的选择性。