非晶硅太阳电池窗口层材料掺硼非晶金刚石的研究

以固态掺杂方式利用过滤阴极真空电弧技术制备掺硼非晶金刚石薄膜, 获得性能优良的宽带隙p型半导体材料, 再利用等离子增强化学气相沉积技术制备p-i-n结构非晶硅太阳电池的本征层和n型层, 最终制成以掺硼非晶金刚石薄膜为窗口层的非晶硅太阳电池. 利用Lambda950紫外-可见光分光光度计表征薄膜的光学带隙, 并测试电池开路电压、短路电流、填充因子以及转化效率等参数, 再分析电池的光谱响应特性. 实验表明, 掺硼非晶金刚石薄膜的光学带隙(～2.0eV)比p型非晶硅更宽, 以掺硼非晶金刚石薄膜用作非晶硅太阳电池的窗口层, 能够改善电池的光谱响应特征, 并提高转化效率达10%以上.     

退火温度对金属催化四面体非晶碳转变为石墨烯过程的影响

设计了金属催化剂Ni/四面体非晶碳(ta-C)/基底三层结构,使用磁过滤阴极真空电弧设备制备了ta-C薄膜,用电子束蒸镀技术制备Ni薄膜,并对其进行快速热处理调控非晶碳转变石墨烯的过程,重点研究了热处理温度对石墨烯生长的影响。结果表明,沉积态的ta-C和Ni层均表面平整、均匀致密,其中Ni薄膜呈(111)晶面择优取向生长,为石墨烯的高质量生长提供了条件。同时,退火温度显著影响了非晶碳的石墨烯转变,当退火温度高于400℃时Ni表面能生成多层石墨烯,在500℃保温15 min可制备出质量较高的多层石墨烯。     

膜厚对四面体非晶碳膜机械性能的影响

采用过滤阴极真空电弧技术以相同的工艺条件在p(100)单晶硅衬底上制备了不同厚度的四面体非晶碳薄膜,并利用表面轮廓仪测试薄膜的厚度和应力,利用纳米压入仪测试薄膜的硬度、杨氏模量和临界刮擦载荷.试验表明,在一定的扫描波形条件下,薄膜大约以0.7 nm/s的沉积速率稳定生长.随着膜厚的增加,薄膜的应力持续降低,当膜厚超过30nm时,应力将低于5GPa;当膜厚超过300nm时,硬度和杨氏模量分别将近70GPa和750GPa,已经十分接近体金刚石的性能指标.另外,随着膜厚增加所产生的应力变化,也导致了可见光拉曼光谱非对称宽峰的峰位逐渐向低频偏移.     

不同厚度四面体非晶碳薄膜的拉曼表征和内应力

为了探讨膜厚对四面体非晶碳薄膜拉曼结构表征和内应力的影响规律，进而确定应力与拉曼光谱之间的关系，采用过滤阴极真空电弧技术以相同的工艺条件在P（100）单晶抛光硅衬底上制备了从3nm～350nm不同厚度的四面体非晶碳薄膜。利用表面轮廓仪和原子力显微镜测试膜厚，表面轮廓仪确定曲率半径并计算薄膜应力，共聚焦拉曼光谱表征薄膜的结构细节。实验发现，随着膜厚的增加，四面体非晶碳薄膜的应力持续下降，当膜厚超过30nlll时，应力的下降趋势变得平缓，并保持在小于5GPa的较低水平。随着膜厚的增加，可见光拉曼光谱中衬底硅的一阶和二阶谱峰强度逐渐降低，在50nm～80nm膜厚范围，半高宽最窄，峰强最高，能够最有效地获得拉曼结构信息。随着膜厚的增加和应力的下降，非晶碳一阶谱峰的峰位表现为逐渐向低频偏移。     

脉冲磁过滤阴极弧等离子体制备四面体非晶碳膜

介绍了脉冲磁过滤阴极电弧法制备四面体非晶碳膜(tetrahedral amorphous carbon即ta-C),并对制得的薄膜表面形貌、硬度、电阻等进行了测试.结果表明,脉冲磁过滤阴极电弧法制备的ta-C膜有优良的性能.拉曼光谱分析显示,制得的薄膜为非晶结构,有明显的sp3结构特征,符合ta-C膜的特征峰.     

氟化非晶碳膜结构的Raman和FTIR研究

利用反应射频磁控溅射法,以单晶Si片为衬底,在不同功率下制备了氟化非晶碳膜样品,并进行了不同温度的退火处理。采用拉曼光谱、傅里叶变换红外光谱和原子力显微镜对样品的结构进行了表征。通过谱线Lorentzian分峰拟合方法,分析比较了不同功率下制备的氟化非晶碳膜sp杂化结构,得到了薄膜生长过程功率控制与结构的关系,功率增大、退火温度升高,膜内sp2相对含量增加。退火温度达到350℃时,薄膜中石墨结构明显增加。     

激光热处理对类金刚石薄膜结构的影响

用真空阴极过滤电弧法沉积了厚度为2 nm的类金刚石(DLC)薄膜,研究了激光加热退火时薄膜结构和表面粗糙度的变化,分析了激光加热功率对薄膜结构的影响。结果表明,当激光功率小于200 mW时,DLC薄膜的结构基本保持不变;激光功率增大到300 mW,薄膜中少量的sp3键转变为sp2键,但薄膜的表面形貌基本保持不变。随着激光功率增大到400mW,薄膜中sp3键向sp2键的转变量增大;当激光功率达到500 mW时,薄膜中大量的sp3键转变为sp2键,sp2六原子环含量迅速增大,薄膜表面粗糙度开始明显增大,出现凹凸不平的表面形貌。     

掺磷四面体非晶碳薄膜电极的电化学伏安特性

采用过滤阴极真空电弧技术, 以高纯磷烷气体为掺杂源制备掺磷四面体非晶碳(ta-C:P)薄膜. 利用X射线光电子能谱和激光拉曼光谱表征薄膜的成分和结构, 采用循环伏安和微分脉冲伏安分析薄膜的电化学行为. 结果表明, 磷的掺入没有引起薄膜非晶结构的明显变化, 只是促进了sp²杂化碳原子的团簇. 经过酸预处理的ta-C:P薄膜在硫酸溶液中有宽的电势窗口和低的背景电流; 对Cl^-有催化活性; 薄膜表面电子传输速度快; 对水溶液中Cu²⁺和Cd²⁺有检测活性. 因此具有良好导电性的ta-C:P薄膜适于作为电极并有望用于污水中重金属离子的分析检测等领域.     

退火温度对Ge/SiO2多层膜的结构和光学性能的影响

采用磁控溅射技术在石英衬底上制备出(Ge/SiO2)15多层膜,并在不同温度下对其进行退火处理。XRD和Raman结果表明:溅射态的薄膜为非晶态,当退火温度为500℃时开始出现明显的结晶衍射峰,随后晶化率明显增大,当600℃后,薄膜的晶化率几乎不变。FESEM和小角度X射线衍射结果表明:溅射态薄膜的层与层之间存在明显的界面,具有良好的周期性,升高退火温度,晶粒尺寸增大,但仍保持周期性结构。薄膜的紫外-可见光吸收光谱表明:随着退火温度的升高,吸收边发生红移,光学带隙从溅射态的1.86eV减小到600℃时的1.59eV。     

硼掺杂四面体非晶碳薄膜的光学特性研究

采用过滤阴极真空电弧技术制备了不同硼含量的掺杂四面体非晶碳薄膜(ta-C:B)。使用椭偏仪和紫外-可见光分度计测试了薄膜的折射率、消光系数、透过率和反射率。结果表明,硼含量小于2.13%时,硼含量增加,薄膜折射率缓慢增大;消光系数基本保持不变。当硼含量继续增加到3.51%和6.04%时,折射率分别迅速增加至2.65和2.71,相应的消光系数增大至0.092和0.154;而薄膜的光学带隙从2.29eV缓慢减小至1.97eV,后又迅速降至1.27eV。同时ta-C:B膜的透过率逐渐减小,反射率逐渐增大,表明硼的掺入降低了薄膜的透光性能。ta-C:B膜光学性能的变化,除了与sp3杂化碳的含量有关外,还取决于薄膜中sp2杂化碳的空间分布特点。     

非晶金刚石薄膜的拉曼光谱研究

碳离子的能量是影响非晶金刚石薄膜结构和性质最关键的工艺参数．采用磁过滤真空溅射离子技术,研究不同衬底偏压Ｖ_ｂ（即不同碳离子能量）下制备的非晶金刚石薄膜的拉曼光谱和表面形貌．结果表明：－５０Ｖ≤Ｖ_ｂ≤－１０Ｖ时,样品表面均匀、光滑,拉曼谱是对称且很宽的散射带;Ｖ_ｂ＞－１０Ｖ或Ｖ_ｂ＜－５０Ｖ时,已有晶团出现,表面粗糙度明显增加,拉曼谱明显地分裂为１５８０ｃｍ^－１的Ｇ带和１３５０ｃｍ^－１的Ｄ带．     

磁过滤阴极弧制备四面体非晶碳膜热稳定性研究

为研究磁过滤阴极弧制备的四面体非晶碳(tetrahedral amorphous carbon, ta-C)膜在自然环境中使用的热稳定性, 将ta-C膜在空气中退火3h, 退火温度分别为200、400和500℃. 用XPS和Raman谱对膜的微观结构进行表征. 结果表明, 在400及400℃以下退火, XPS谱C1_s峰和Raman谱都没有明显变化. 当退火温度为500℃时, C1_s峰峰形仍然没有变化; Raman峰I_D/I _G增大, G峰峰位未变, 峰的对称性变好. 分析显示膜中石墨颗粒长大, 但没有发生石墨化. 说明磁过滤阴极弧制备的ta-C膜因不含氢和结构致密而表现出良好的热稳定性. 另外, 在退火温度为500℃时, 样品边缘已经氧化挥发.     

Infrared and raman spectroscopic studies of optically transparent zirconia (ZrO2) films deposited by plasma-assisted reactive pulsed laser deposition

Plasma-assisted pulsed laser deposited zirconia (ZrO(2)) films were studied by Fourier transform infrared (FT-IR) and Raman spectroscopy for structural characterization and thermal stability in combination with optical characterization by spectroscopic ellipsometry and optical transmission measurements. Only the monoclinic ZrO(2) phase was positively identified from the infrared and Raman spectra of the as-deposited ZrO(2) films, which show excellent optical transparency from the ultraviolet to the near infrared as revealed by optical characterization. The as-deposited ZrO(2) films are free of any SiO(x) interfacial layer when deposited on silicon. The prepared ZrO(2) films exhibit good thermal stability in their structural, optical, and interfacial properties up to 900 °C. Upon annealing above 1100 °C, a silicon oxide interfacial layer forms due to the oxidation of the silicon substrate surface by the oxygen diffused from the oxide film to the silicon substrate at high temperatures.     

SiNx薄膜中硅纳米粒子的制备及表征

通过等离子增强化学气相沉积(PECVD)法, 以氨气和硅烷为反应气体, P型单晶硅和石英为衬底, 低温下(200℃)制备了含硅纳米粒子的非化学计量比氮化硅(SiN_x)薄膜. 经高温(范围500~950℃)退火处理优化了薄膜结构. 室温下测试了不同温度退火后含硅纳米粒子SiN_x薄膜的拉曼(Raman)光谱、光致发光(PL)光谱及傅立叶变换红外吸收(FTIR)光谱, 对薄膜材料的结构特性、发光特性及其键合特性进行了分析. Raman光谱表明. SiN_x薄膜内的硅纳米粒子为非晶结构. PL光谱显示两条与硅纳米粒子相关的光谱带, 随退火温度的升高此两光谱带峰位移动方向相同. 当退火温度低于800℃时, PL光谱峰位随退火温度的升高而蓝移. 当退火温度高于800℃时, PL光谱峰位随退火温度的升高而红移. 通过SiNx薄膜的三种光谱分析发现薄膜的光致发光源于硅纳米粒子的量子限制效应. 这些结果对硅纳米粒子制备工艺优化和硅纳米粒子光电器件的应用有重要意义.     

Stabilization of absorber stacks containing Zr or Ti compounds on Ag

A family of selective photothermal absorber stacks based on succesively deposited thin films of silver and a substoichiometric nitride, carbonitride, oxynitride or oxycarbonitride of zirconium or titanium has been investigated by the Bureau of Mines. The spectral selectivities are quite promising, especially because of very low infrared emittances at elevated temperatures. Long-wave emittances of 0.035 to 0.050 at 600 K and ratios of short-wave absorptance to long-wave emittance near 20 are common. However, improvements of absorptance and thermal stability are being sought. One problem that has been observed is a tendency for the silver reflecting films to deteriorate after a period of time at temperatures above 600 K. It appears feasible to counteract the deterioration and to stabilize the silver films with a light undercoating of metallic oxide. Oxides of Cr, Ti, Zr and stainless steel have been tried with encouraging results. Another study concerned the thermal stability of absorbing semiconductor films. The absorbing films oxidize slightly in air at 400 K, but titanium compounds are more stable in air than zirconium compounds. In a good vacuum, most absorbing films are reasonably stable at temperatures up to about 800 K, and carbon apparently enhances the stability. A zirconium carbonitride film had the best combination of absorptance and thermal stability among the absorbers examined.     

金刚石自支撑膜的高温红外透过性能

由于金刚石具有低吸收和优异的力学与导热性能使其成为长波(8~12μm)红外光学窗口材料的重要选择。对于许多极端条件的应用,化学气相沉积(CVD)金刚石自支撑膜的高温光学性质至关重要。应用直流电弧等离子喷射法制备光学级金刚石自支撑膜进行变化温度的红外光学透过性能研究,采用光学显微镜、X射线衍射、激光拉曼和傅里叶变换红外-拉曼光谱仪检测CVD金刚石膜的表面形貌、结构特征和红外光学性能。结果表明:在27℃时金刚石膜长波红外8~12μm之间的平均透过率达到65.95%,在500℃时8~12μm处的平均透过率为52.5%。透过率下降可分为3个阶段。对应于透过率随温度的下降,金刚石膜的吸收系数随温度的升高而增加。金刚石自支撑膜表面状态的变化,对金刚石膜光学性能的影响显著大于内部结构的影响。     

退火温度对CsI(Tl)薄膜微观结构和闪烁性能的影响

采用真空热蒸发法制备了CsI(Tl)薄膜, 然后进行了不同温度的真空热处理．用X射线衍射仪、扫描电子显微镜、X射线荧光光谱仪及正电子寿命谱仪对CsI(Tl)薄膜样品进行了分析, 并测得了样品的光产额．结果表明, 该CsI(Tl)薄膜沿(200)晶面择优取向生长．经过较低温度退火, CsI薄膜中的Tl⁺离子向薄膜表面扩散, 薄膜中缺陷数量增加, 且尺寸较大, 光产额略微增高．经过250℃退火, 薄膜中低温退火所形成缺陷得到恢复, 薄膜缺陷尺寸变小, 且数目减少, 具有较好的结晶状态, 光产额提高．经过400℃退火, 薄膜结构发生显著变化, 薄膜中缺陷大幅增加, 结晶状态变差, Ti+含量减少, 光产额急剧下降．     

Stability of NiO membranes on photostructurable glass substrates for micro solid oxide fuel cells

NiO thin films with thicknesses in the range of 100 to 900 nm were deposited by spray pyrolysis onto photostructurable glass substrates and, ultimately, free-standing membranes with diameters of 100, 200 and 300 µm were fabricated using these thin films. The membranes are intended to act as simplified anodes or anode current collectors in micro solid oxide fuel cells (µSOFCs) and their differential pressure and thermal stability were characterized. The membranes tolerated a differential pressure between 13,700 and 158,600 Pa. Smaller membranes showed more pressure tolerance than larger membranes. A membrane diameter of 100 µm and a film thickness of 400-500 nm turned out to be a promising geometry for µSOFC membranes. All membranes survived temperatures higher than the intended operating temperature of µSOFCs (350-600 °C). We attribute the good thermal stability to the match of the thermo-mechanical properties of the substrate and the NiO thin films for the lower temperature regime and the substrate softening at higher temperatures releasing stresses in the thin films. Furthermore, the thermal expansion of the substrate is close to thermal expansion of materials used in SOFCs and circular geometries can be realized using wet etching.     

Thermal stability of multilayer graphene films synthesized by chemical vapor deposition and stained by metallic impurities

Thermal stability is an important property of graphene that requires thorough investigation. This study reports the thermal stability of graphene films synthesized by chemical vapor deposition (CVD) on catalytic nickel substrates in a reducing atmosphere. Electron microscopies, atomic force microscopy, and Raman spectroscopy, as well as electronic measurements, were used to determine that CVD-grown graphene films are stable up to 700?°C. At 800?°C, however, graphene films were etched by catalytic metal nanoparticles, and at 1000?°C many tortuous tubular structures were formed in the film and carbon nanotubes were formed at the film edges and at catalytic metal-contaminated sites. Furthermore, we applied our pristine and thermally treated graphene films as active channels in field-effect transistors and characterized their electrical properties. Our research shows that remnant catalytic metal impurities play a critical role in damaging graphene films at high temperatures in a reducing atmosphere: this damage should be considered in the quality control of large-area graphene films for high temperature applications.     

Si(111)衬底上多层石墨烯薄膜的外延生长

利用固源分子束外延(SSMBE)技术, 在Si(111)衬底上沉积碳原子外延生长石墨烯薄膜, 通过反射式高能电子衍射(RHEED)、红外吸收谱(FTIR)、拉曼光谱(RAMAN)和X射线吸收精细结构谱(NEXAFS)等手段对不同衬底温度(400、600、700、800℃)生长的薄膜进行结构表征. RAMAN和NEXAFS结果表明: 在800℃下制备的薄膜具有石墨烯的特征, 而 400、600和700℃生长的样品为非晶或多晶碳薄膜. RHEED和FTIR结果表明, 沉积温度在600℃以下时C原子和衬底Si原子没有成键, 而衬底温度提升到700℃以上, 沉积的C原子会先和衬底Si原子反应形成SiC缓冲层, 且在800℃沉积时缓冲层质量较好. 因此在Si衬底上制备石墨烯薄膜需要较高的衬底温度和高质量的SiC缓冲层.