氮流量对六方氮化硼(hBN)薄膜结构和力学性能的影响

目的 研究磁控溅射过程氮气(N2)流量对六方氮化硼(hBN)薄膜结构和力学性能的影响,为设计新型结构hBN薄膜提供新思路。方法 利用中频电源磁控溅射硼靶,调节不同N2流量(6、12、18、24、30、36 mL/min),沉积4 h后得到hBN薄膜,使用表征工具分析N2流量对hBN薄膜的组成、微观结构、表面形貌以及力学性能的影响。最后使用透射电子显微镜和选区电子衍射对所制备薄膜的纳米晶粒尺寸和晶体点阵结构进行分析。结果 XRD结果显示,薄膜物相主要为hBN。XPS结果说明,所制备薄膜为富硼hBN薄膜。薄膜的硬度和弹性模量随N2引入量的增加呈现先下降、后上升的趋势,最大硬度可达7.21 GPa,对应弹性模量为116.78 GPa。薄膜最低的硬度值为1.2 GPa,弹性模量为32.68 GPa。薄膜弹性破坏应变(H/E^*)和塑性变形抗力(H³/E^*2)随N2引入量的增加也呈现先上升、后下降的趋势,硬度最高薄膜对应的H/E^*值为6.414 ´ 10^–2,H³/E^*2值为29.27 ´ 10^–3 GPa,最低硬度值对应的H/E^*值为3.819 ´ 10^–2,H³/E^*2值为1.77 ´ 10^–3 GPa。透射结果显示,当N2引入量从6 mL/min逐渐增加到36 mL/min时,薄膜微观结构由结晶较差的卷曲结构过渡到局部纳米晶结构,最后形成结晶性较好的卷曲结构,并再次证明所制备薄膜为hBN。结论 在中频磁控溅射沉积hBN薄膜时,通过调整N2流量可以有效调节薄膜的特殊组成,使结构发生转变,进而影响薄膜的力学性能。     

Co掺杂ZnO薄膜的制备及其红外反射性能研究

目的 提高真空保温管道中红外反射层的红外反射性能。方法 以四水合醋酸钴和二水合乙酸锌为金属离子源,利用溶胶-凝胶法制备了不同Co掺杂量的ZnO溶胶(Zn1–xCoxO,x=0, 0.02, 0.04, 0.06, 0.08, 0.10)。进一步采用提拉法在镜面316L不锈钢表面制备薄膜,经450 ℃退火处理3 h后得到所需样品。利用热重-差示扫描量热法(TG-DSC)表征Zn1–xCoxO凝胶在热处理时发生的干燥、晶化过程。利用X射线衍射仪(XRD)分析表征不同Co掺杂量的薄膜中的物相组成。利用场发射扫描电子显微镜(FE-SEM)观察薄膜表面的微观形貌。利用能谱仪分析(EDS)热处理后薄膜表面的元素分布情况。利用UV-Vis-NIR分光光度计测试涂层的红外反射性能。结果 所得的Zn1–xCoxO溶胶在基体表面铺展良好,经热处理后晶粒分布均匀,表面致密无明显缺陷;涂敷Zn1–xCoxO薄膜后,样品红外反射性能得到明显改善,由纯基体的0.6355提升至最佳值0.8131(其中,x=0.06)。同时,XRD结果表明掺杂并未导致样品物相的改变,薄膜材料仍然保持稳定的六角纤锌矿结构,但随着Co掺杂量的提高,样品在(101)晶面发生择优取向。经28 d 400 ℃有氧热处理后,试样仍能保持0.8018的较高反射率。结论 通过在红外反射层表面涂敷Zn1–xCoxO薄膜,不但可有效提高其红外反射率,还可对内部金属基体起到良好的保护作用,从而提高热力管道的隔热性能和使用寿命。     

MgO基外延BiFeO3薄膜的结构和铁电光伏性能

目的 深入研究BiFeO3(BFO)薄膜的结晶结构、生长取向及测试温度对其介电和铁电光伏性能的影响。方法 采用偏轴磁控溅射法,分别以单晶(001)MgO基片和外延La0.5Sr0.5CoO3(LSCO)薄膜作为衬底与底电极,构架Pt/BFO/LSCO/MgO异质结构的铁电电容器。采用XRD衍射仪表征LSCO和BFO薄膜的结构与生长取向,探究Pt/BFO/LSCO/MgO异质结构电容器的介电和铁电光伏性能,重点研究测试温度对其性能的综合影响。结果 X射线衍射(XRD)和Phi扫描结果表明,MgO基BFO与LSCO薄膜均为结晶良好的钙钛矿结构,且满足(00l)取向的外延生长。不同电压和频率下的介电测试表明,BFO铁电薄膜具有较强的铁电性,正负矫顽电压分别为3.36、–1.12 V,但存在明显的介电色散现象,呈现先减小、后增大的趋势。在~100 kHz时,介电损耗最小,为0.016;在8 MHz时,增加到了0.212。这主要由于不同频率下各种类型电荷的弛豫竞争机制所致。光伏性能测试表明,在室温(20 ℃)、光强250 mW/cm²紫光垂直照射下,开路电压(VOC)和短路电流(JSC)分别为0.32 V和0.21 mA/cm²。进一步提高测试温度(分别为40、60、80、100 ℃)发现,BFO铁电薄膜VOC呈先缓慢、后快速减小,而JSC呈先快速上升、后下降的趋势,并在临界温度80 ℃处展现了更快的光伏响应速度,VOC和JSC分别为0.30 V和0.96 mA/cm²。能带分析表明,底电极LSCO与上电极Pt间大的功函数差(~1 eV)使得BFO薄膜中存在较强的内建电场,这有利于分离光生载流子,从而极大提高了BFO薄膜的铁电光伏效应。结论 BFO是一种具有重要潜在应用价值的优良环保光伏候选材料,提供了一种提高BFO铁电光伏器件性能的切实可行策略。     

硅基ZnO纳米棒阵列异质结太阳能电池的水热合成及其光伏性能

通过低温水热法,在图案化的p型硅衬底上合成氧化锌（ZnO）纳米棒阵列薄膜,制备出具有p-Si/n-ZnO纳米棒（NR）阵列结构的异质结太阳能电池（HSCs）。通过直流磁控溅射技术,分别在前后面板溅射沉积ITO和Al膜接触电极层。研究ZnO籽晶层的退火温度、ZnO纳米棒阵列水热合成的时间等因素对ZnO纳米棒阵列的晶体结构、表面形貌和光学性能的影响。p-Si/n-ZnO纳米棒阵列HSCs的最佳短路电流密度和总能量转换效率分别为11.475 mA·cm^-2和2.0%。相比p-Si/n-ZnO薄膜HSCs,p-Si/n-ZnO纳米棒阵列HSCs的光伏性能得到了有效提高。     

纳米柱状多孔WO3- x /TiO2 薄膜的电致变色性能

采用反应磁控溅射在掠射角度α=0°和α=80°的条件下制备氧化钨（WO_3-x）薄膜,然后在其表面沉积二氧化钛（TiO₂）。利用X射线衍射仪（XRD）、场发射扫描电镜（FE-SEM）和X射线光电子能谱仪（XPS）对WO_3-x/TiO₂薄膜的晶体结构、表面/断面形貌以及表面化学成分进行表征。在三电极体系1 mol/L LiClO₄/PC溶液中,采用电化学工作站和紫外-可见分光光度计测试了WO_3-x/TiO₂薄膜的电致变色性能。XRD结果表明,WO_3-x/TiO₂薄膜为非晶态结构,与掠射角度无关。当掠射角度为80°时,获得了纳米柱状多孔薄膜。从 W 4f和Ti 2p的XPS谱图确认氧化钨为亚化学计量比的WO_3-x,而氧化钛为满足化学计量比的TiO₂。与致密薄膜相比,纳米柱状多孔薄膜需要较低的驱动电压且具有较快的响应速度。纳米柱状多孔薄膜的电荷容量为83.78 mC,是致密薄膜电荷容量30.83 mC的2倍以上。在±1.2 V驱动电压下,注入和脱出离子扩散速率分别为D_in=5.69×10^-10 cm²/s和D_de= 5.08×10^-10 cm²/s。与纯WO₃薄膜相比,WO_3-x/TiO₂薄膜的电致变色循环稳定性更好。纳米柱状多孔薄膜在可见光范围内具有较大的光调制幅度,因此其光密度变化（ΔOD）大于致密薄膜。     

工作气压对Y掺杂HfO2结构及电学性能的影响

目的 基于Y掺杂高纯铪靶和钛靶的反应磁控溅射方法,在Si(100)基底上沉积掺杂Y氧化铪薄膜,以及TiN/X-HfO2/TiN三层异质结构,探究Y掺杂对氧化铪基异质结构铁电性的影响。方法 针对反应磁控溅射制备的Y掺杂HfO2薄膜和异质结构,分别采用白光干涉仪、掠入射X射线衍射(GIXRD)、X 光电子能谱仪(XPS)和铁电分析仪,对薄膜的沉积速率、退火后薄膜的晶体结构、掺杂元素组分及含量,以及HfO2基异质结薄膜P-E电滞回线和I-V曲线进行测量。结果 在相同工艺条件下,薄膜的沉积速率随着工作气压的增大呈先增大后减小的趋势,在工作气压为1.1 Pa时沉积速率达到最高值。XRD结果表明,薄膜经过退火后存在正交相(o相)和单斜相(m相)。当工作气压为0.7 Pa时,所制备HYO薄膜在28°~30°内代表o(111)相的衍射峰最强,具有最佳的铁电性。随着工作气压的增大,代表m(111)相的衍射峰强度逐渐下降。采用XPS分析了薄膜中各元素的化学状态和含量,在工作气压为0.7 Pa时,Y的掺杂浓度(物质的量分数)为5.6%,铁电分析结果表明,在工作气压从0.7 Pa增至1.3 Pa的过程中,Y掺杂的HfO2基异质结的电滞回线逐渐收缩。在工作气压为0.7 Pa时,剩余极化强度Pr的最大值为14.11 µC/cm²,矫顽场Ec约为1 MV/cm。结论 利用Y掺杂高纯铪靶反应磁控溅射制备的掺杂铁电薄膜,在工作气压0.7 Pa下得到的薄膜经过700 ℃退火后具备良好的铁电性能。     

AgI/BiPO4异质结的原位制备及光催化性能

采用水热合成法制备了磷酸铋(BiPO4),通过沉淀法成功将AgI负载于BiPO4表面制备了AgI/BiPO4异质结。采用X射线衍射仪(XRD)、紫外-可见漫反射光谱(UV-Vis DRS)等对AgI/BiPO4异质结结构和组成进行了表征;用表面光电压谱(SPS)对异质结光催化剂的光生电荷分离特性进行了研究;考察了AgI/BiPO4异质结光催化剂对模拟污染物罗丹明B的催化降解性能。结果表明,当AgI/BiPO4摩尔比为1.2%时,异质结光催化剂的光生电子-空穴分离速率最高,对罗丹明B的光催化降解性能最好。光催化过程中主要活性自由基为超氧自由基.O2^-,h⁺空穴和.OH自由基是起次要作用的活性自由基。     

氮气流量对VNbMoTaWNx薄膜作为PEMFC不锈钢双极板改性层性能的影响

目的 降低SS316L表面的接触电阻,提高耐腐蚀性能。方法 采用非平衡场磁控溅射离子镀技术在SS316L不锈钢表面制备VNbMoTaW和不同氮气流量的VNbMoTaWNx薄膜。使用场发射扫描电镜、XRD衍射仪、XPS光电子能谱仪、电化学工作站、接触电阻测试装置,研究了改性涂层的组成和结构对接触电阻和耐腐蚀性能的影响。结果 扫描电子显微镜结果表明,所有薄膜表面致密且连续、与基体结合良好。随着氮气流量的增加,氮化物相逐渐增多、柱状晶结构减少、薄膜更加致密紧凑。XRD结果表明,未通氮气的高熵合金薄膜具有高熵合金体心立方结构,并沿(110)晶面方向生长。随着氮气流量的增加,氮化物相逐渐增多,薄膜晶体结构开始从体心立方结构转变为面心立方结构。结合XPS分析结果可知,VNbMoTaWNx薄膜表面主要由金属氮化物和少量高熵合金BCC相组成,并且随着氮气流量的增加,金属氮化物相逐渐增多。与单层VNbMoTaW薄膜相比,VNbMoTaWNx薄膜具有更好的耐腐蚀性和导电性能。氮流量为12 mL/min的高熵合金氮化物薄膜具有最优异的综合性能。表面改性后的薄膜接触电阻大幅度降低,在1.4 MPa的压力下,与碳纸的接触电阻仅为12.2 mΩ.cm²,接近美国能源部(DOE)的技术目标。由动电位极化曲线测得VNbMoTaWNx-12 mL/min在模拟PEMFC阴极环境下的腐蚀电流密度为0.040 μA/cm²,与SS316L基体相比,薄膜的耐腐蚀性得到了很大提升。在0.6 V恒电位模拟阴极环境下,VNbMoTaWNx-12 mL/min的电流密度稳定在1.01 μA/cm²,接近美国能源部1 μA/cm²的目标。结论 VNbMoTaW和不同氮气流量的VNbMoTaWNx薄膜能显著提高SS316L基体的耐腐蚀性和导电性能。     

ZnO基薄膜载流子传输特性研究

通过对ZnO基薄膜的载流子传输特性研究,实现对ZnO基薄膜电学性能的控制,解决氧化锌薄膜中难于实现有效受主掺杂的困难,提供一种制备p型ZnO膜及其同质p-n结材料的新方法,以满足制备ZnO基短波长光电子器件的需要.采用超声喷雾热解法,以醋酸锌水溶液为前驱体,分别以醋酸铵和硝酸铟为氮(N)源和铟(In)源,在单晶硅衬底上沉积了氮-铟(N-In)共掺杂ZnO薄膜.采用X射线衍射(XRD)、扫描电镜(SEM)、霍尔(Hall)效应、塞贝克(Seebeck)效应等分析方法,研究了N-In共掺杂对ZnO薄膜的晶体结构、电学和光学性能的影响规律.研究结果表明:所得ZnO基薄膜结构均匀致密,表面光滑平整.在优化工艺下制备了氮铟共掺杂的p型ZnO薄膜,电阻率约为1.0×10-3Ω·cm,载流子浓度约为1.0×1019/cm3.通过在p型ZnO薄膜上沉积未掺杂的n型ZnO薄膜,制备了ZnO同质p-n结薄膜.I-V曲线清楚表明了ZnO同质p-n结的正向导通、反向截止的整流效应.     

AZ91D镁合金耐腐蚀性膜层的腐蚀行为

目的 为了获得耐蚀性能更加优异的AZ91D镁合金。方法 研究了铸态、半固态、成膜铸态及成膜半固态AZ91D,在模拟生理盐水(0.9%NaCl)和模拟海水(3.5%NaCl)中的腐蚀特征,并引入分形理论表征其腐蚀程度及均匀性。通过对不同状态AZ91D进行NaCl溶液腐蚀、电化学腐蚀,运用扫描形貌(SEM)和能谱(EDS)分析各状态AZ91D的腐蚀形貌,引入分形理论对各状态AZ91D的腐蚀形貌进行计算及分析。结果 在同一腐蚀时间,各状态AZ91D在模拟海水中出现更多的腐蚀区域,成膜铸态及半固态的腐蚀最早出现于膜层组织的裂纹处。在电化学实验中,随着电解液NaCl质量分数升高至3.5%,未成膜铸态及半固态的腐蚀电位分别从–1.4111 V和–1.4323 V下降为–1.5066 V和–1.5089 V,电流密度分别从6.270×10^–10 A/m²和9.847×10^–10 A/m²上升为4.863×10^–9 A/m²和 8.396×10^–9 A/m²;成膜铸态及半固态的腐蚀电位分别从–1.3884 V和–1.3430 V下降为–1.4856 V和–1.4331 V,电流密度分别从5.854×10^–10 A/m²和8.592×10^–10 A/m²下降为2.050×10^–11 A/m²和1.189×10^–11 A/m²。结论 在分形计算中,随着腐蚀液浓度或腐蚀时间的上升,铸态及半固态AZ91D的腐蚀倾向和腐蚀速率提高;膜层的腐蚀倾向提高,腐蚀速率降低。同时,各状态AZ91D的分形维数DH随腐蚀程度的增加而增大,Δa值随腐蚀均匀性的降低而增大。     

Preparation and characterization of ZnO/Cu/ZnO transparent conductive films

ZnO/Cu/ZnO transparent conductive thin films were prepared by RF sputtering deposition of ZnO target and DC sputtering deposition of Cu target on n-type (001) Si and glass substrates at room temperature. The morphology, structure, optical, and electrical properties of the multilayer films were characterized by field emission scanning electron microscope (FESEM), X-ray diffraction (XRD), UV/Vis spectrophotometer, and Hall effect measurement system. The influence of Cu layer thickness and the oxygen pressure in sputtering atmosphere on the film properties were studied. ZnO/Cu/ZnO transparent conductive film fabricated in pure Ar atmosphere with 10 nm Cu layer thickness has the best performance: resistivity of 2.3×10-4 Ω·cm, carrier concentration of 6.44×1016cm-2 , mobility of 4.51cm2·(V·s)-1 , and acceptable average transmittance of 80 % in the visible range. The transmittance and conductivity of the films fabricated with oxygen are lower than those of the films fabricated without oxygen, which indicates that oxygen atmosphere does not improve the optical and electrical properties of ZnO/Cu/ ZnO films.     

Photoluminescence behavior and visible light photocatalytic activity of ZnO,ZnO/ZnS and ZnO/ZnS/α-Fe2O3 nanocomposites

In order to achieve effective, economic, and easily achievable photocatalyst for the degradation of dye methyl orange (MeO), ZnO, ZnO/ZnS and ZnO/ZnS/α-Fe₂O₃ nanocomposites were prepared by simple chemical synthetic route in the aqueous medium. Phase, crystallinity, surface structure and surface behavior of the synthesized materials were determined by X-ray diffraction (XRD) and Brunauer–Emmett–Teller analysis (BET) techniques. XRD study established formation of good crystalline ZnO, ZnO/ZnS and ZnO/ZnS/α-Fe₂O₃ nanomaterials. By using intensity of constituent peaks in the XRD pattern, the compositions of nanocomposites were determined. From the BET analysis, the prepared materials show mesoporous behavior, type IV curves along with H4 hysteresis. The ZnO/ZnS/α-Fe₂O₃ composite shows the largest surface area among three materials. From the UV–visible spectra, the band gap energy of the materials was determined. Photoluminescence spectra (PL) were used to determine the emission behavior and surface defects in the materials. In PL spectra, the intensity of UV peak of ZnO/ZnS is lowered than that of ZnO while in case of ZnO/ZnS/α-Fe₂O₃, the intensity further decreased. The visible emission spectra of ZnO/ZnS increased compared with ZnO while in ZnO/ZnS/α-Fe₂O₃ it is further increased compared with ZnO/ZnS. The as-synthesized materials were used as photocatalysts for the degradation of dye MeO. The photo-degradation data revealed that the ZnO/ZnS/α-Fe₂O₃ is the best photocatalyst among three specimens for the degradation of dye MeO. The decrease of intensity of UV emission peak and the increase of intensity of visible emission cause the decrease of recombination of electrons and holes which are ultimately responsible for the highest photocatalytic activity of ZnO/ZnS/α-Fe₂O₃.     

Improved resistive switching stability of Pt/ZnO/CoO x /ZnO/Pt structure for nonvolatile memory devices

For Pt(Ag)/ZnO single-layer/Pt structure,random 10 formation and rupture of conductive filaments composed by oxygen vacancies or metallic ions often cause dispersion problems of resistive switching(RS)parameters,which is disadvantageous to devices application.In this study,ZnO/CoOx/ZnO(ZCZ)tri-layers were utilized as the switching layers to investigate their RS properties as compared with ZnO-based single-layer devices.It is interestingly noted that Pt/ZCZ/Pt devices show quite stable bipolar RS behaviors with little resistance value fluctuations compared to Ag/ZCZ/Pt devices and Pt(Ag)/ZnO/Pt devices,which minimize the dispersion of the resistances of RS.This highly stable RS effect of Pt/ZCZ/Pt structure would be promising for high density memory devices.     

Formation of ZnO Nanotubes from Zn/ZnO cables by thermal evaporation

Various types of nanostructures were synthesized by the simple thermal evaporation of ZnO powders at 1300 °C. Three types of nanostructure were formed as the substrate temperature increased from 100 °C to 300 °C: Zn-core/ZnO-shell nanocables (120 °C to 150 °C), Zn-ZnO core-shell nanocables connected to mesoporous ZnO (200 °C to 260 °C), and ZnO nanotubes (260 °C to 300 °C). The formation process of the ZnO nanotubes, which were formed at the highest temperature (260 °C to 300 °C), involved the solidification of liquid Zn droplets, surface oxidation, and the sublimation of the Zn. This result was demonstrated experimentally as well as via microstructural analysis using XRD, field-emission scanning electron microscopy (FE-SEM), and transmission electron microscopy (TEM) equipped with an energy dispersive X-ray spectrometer (EDS).     

Properties of multilayer ZnO:Ga/Ag/ZnO:Ga coatings applied by magnetron sputtering

The methods of van der Pau, spectrometry, and atomic force microscopy were used to study the optical and electrophysical properties of multilayer ZnO:Ga/Ag/ZnO:Ga coatings applied by magnetron sputtering. The effect of the thickness of the coating layer was studied with respect to the surface resistance, transparency, and reflection of the multilayer structure in the visible and infrared wavelength ranges. The coating surface morphology and moisture resistance was studied. The ZnO:Ga/Ag/ZnO:Ga coatings were shown to have a high transparency (T = 90%) in the visible range, high reflection coefficient in the IR range (R = 93%), and low surface resistance (R_s = 4.88 Ohm/sq). The moisture resistance studies showed the highest moisture resistance of ZnO:Ga (25 nm) / Ag (15 nm) / ZnO:Ga (75 nm) coatings, which are not changed by testing and can be used for the effective protection of silver films against degradation.     

Effects of Oxide-Modified Spherical ZnO on Electrical Properties of Ag/ZnO Electrical Contact Material

Silver-zinc oxide (Ag/ZnO) electrical contact material is widely used as contacts of the medium duty switching devices. Effects of modified ZnO on properties of Ag/ZnO electrical contact material were investigated in this work. NiO and CuO were introduced to modify spherical ZnO by a chemical solution nano-coating method. Ag/ZnO contacts prepared using the modified spherical ZnO were produced by powder metallurgy (PM) method in a muffle furnace in temperature ranges from 750 to 900 °C. Results show that electrical conductivity, stability of relative density, and Vickers’ hardness of Ag/ZnO electrical contact material can be improved by the addition of NiO because of the formation of NiO solid solution Zn_0.2Ni_0.8O. The addition of CuO to Ag/ZnO electrical contact material makes arcing energy and mass loss lower. Since this is attractive for a longer service life, using NiO and CuO co-modified ZnO as a second phase may be a promising way to improve properties of Ag/ZnO electrical contact material. Hence, the presented results could also be useful for the design of a new Ag/ZnO electrical contact material.     

Enhanced photocatalytic activity of new photocatalyst Ag/AgCl/ZnO

A new composite photocatalyst Ag/AgCl/ZnO was fabricated by a two-step synthesis method under the hydrothermal condition. The sample was characterized by XRD, TG-DSC, SEM, TEM, DRS and XPS. The results showed that the samples were composed of Ag, AgCl and ZnO, and the particle size was in the range of 100 nm-1 μm. Methyl orange (MO) was used as a representative dye pollutant to evaluate the photocatalytic activity of Ag/AgCl/ZnO. The photocatalytic activity of Ag/AgCl/ZnO catalyst was higher than that of the pure ZnO catalyst. It was found that the Ag/AgCl/ZnO structure changed to Ag/ZnO gradually after several repeated experiments. However, the photocatalytic ability of the sample was not reduced. Finally, a possible photocatalytic mechanism was proposed.     

Influence of ZnO content and annealing temperature on the dielectric properties of ZnO/Al2O3 composite coatings

ZnO/Al₂O₃ coatings were prepared by atmospheric plasma spraying (APS) using ZnO powders and Al₂O₃ powders as starting materials. The dielectric properties of these coatings were discussed. Both the real part of permittivity and the energy loss increase greatly with increasing ZnO content over the frequency range 8.2-12.4 GHz, which can be ascribed to orientation polarization and relaxation polarization due to a higher ZnO content. The frequency-dependent maximum of the loss tangent is found to obey Debye theory. In addition, annealing temperature which leads to the change of ZnO content also plays an important role in the dielectric performance.