原子层沉积制备氧化锌纳米薄膜的光学性质研究

采用原子层沉积技术(ALD),以二乙基锌和水为前驱体,在衬底温度分别为110和190 ℃的条件下制备了致密的氧化锌纳米薄膜。采用X射线光电子能谱,荧光光谱和椭偏仪等表征手段对薄膜的成分和光学性质进行了研究。结果表明,随着沉积温度的增加,氧化锌薄膜内—OH含量降低,说明氧化锌薄膜生长过程中的化学反应更加完全;另外,沉积温度增加后,薄膜在365 nm处的激子发射峰出现了明显的增强,同时可见光区的荧光发射峰消失,表明薄膜内的缺陷态减少。随着成膜质量的提高,氧化锌薄膜的电子迁移率从25提高至32 cm2·(V·S)-1。椭偏测量的拟合结果表明,在375～800 nm的波长范围内,氧化锌薄膜的折射率逐渐从2.33降至1.9,呈现出明显的色散现象;另外,不同温度下制备的氧化锌薄膜光学带隙均为3.27 eV左右,这说明沉积温度对薄膜的带隙没有明显影响。     

等离子增强原子层沉积低温生长GaN薄膜

采用等离子增强原子层沉积技术在低温下于单晶硅衬底上成功生长了Ga N多晶薄膜,利用椭圆偏振仪、低角度掠入射X射线衍射仪、X射线光电子能谱仪对薄膜样品的生长速率、晶体结构及薄膜成分进行了表征和分析.结果表明,等离子增强原子层沉积技术生长Ga N的温度窗口为210—270?C,薄膜在较高生长温度下呈多晶态,在较低温度下呈非晶态;薄膜中N元素与大部分Ga元素结合成N—Ga键生成Ga N,有少量的Ga元素以Ga—O键存在,多晶Ga N薄膜含有少量非晶态Ga_2O_3.     

等离子增强原子层沉积低温生长AlN薄膜

采用等离子增强原子层沉积技术在单晶硅基体上成功制备了AlN晶态薄膜, 利用椭圆偏振仪、原子力显微镜、小角掠射X射线衍射仪、高分辨透射电子显微镜、 X射线光电子能谱仪对样品的生长速率、表面形貌、晶体结构、薄膜成分进行了表征和分析, 结果表明, 采用等离子增强原子层沉积制备AlN晶态薄膜的最低温度为200 ℃, 薄膜表面平整光滑, 具有六方纤锌矿结构与(100)择优取向, Al_2p与N_1S的特征峰分别为74.1 eV与397.0 eV, 薄膜中Al元素与N元素以Al-N键相结合, 且成分均匀性良好. 关键词： 氮化铝 等离子增强原子层沉积 低温生长 晶态薄膜     

原子层沉积制备铱薄膜的特性研究

以乙酰丙酮铱[Ir(acac)3]和高纯氧为前驱体,采用原子层沉积(ALD)方法在基板温度为340℃的石英玻璃和硅基板上制备了金属铱薄膜。采用反射光谱测试仪、X射线电子能谱(XPS)、X射线衍射(XRD)、扫描电子显微镜(SEM)和原子力显微镜(AFM)等手段对不同厚度薄膜的微结构、表面形貌和光学性能进行了研究。结果表明,原子层沉积制备的Ir薄膜中元素纯度较高(大于95%),表面粗糙度低,并呈现多晶纳米颗粒。同时,Ir薄膜在紫外波段表现出较好的光学特性,可以用于制作Ir金属紫外光栅等光学器件。     

原子层沉积制备Ta_2O_5薄膜的光学特性研究

以乙醇钽[Ta(OC2H5)5]和水蒸气为前驱体,采用原子层沉积(ALD)方法分别在基板温度为250℃和300℃的K9和石英衬底上制备了Ta2O5光学薄膜。采用分光光度计、X射线光电子能谱(XPS)、X射线衍射(XRD)、扫描电子显微镜(SEM)和原子力显微镜(AFM)等手段对薄膜的光学特性、微结构和表面形貌进行了研究。结果表明,用ALD方法制备的Ta2O5薄膜在刚沉积和350℃退火后均为无定形结构,而250℃温度下沉积的薄膜其表面粗糙度低,聚集密度很高,光学均匀性优,在中紫外到近红外均表现出很好的光学特性,可以作为高折射率材料很好地应用于光学薄膜中。     

气相沉积法生长不同结构ZnO纳米线及其发光

用Zn粉、Zn／In2O3／C粉作为不同锌源,通过气相沉积法在空气或N2／O2混合气氛下生长出多种形貌的ZnO纳米线（如：四脚状、多脚状、梳子状、绒棒状,以及纳米棒、纳米丝、纳米带等多种形貌）,直径约为50-1000nm,长度约为1—20μm。测量了样品的XRD谱、扫描电镜、透射电镜和选区电子衍射像,证明这些样品都是六方纤锌矿结构的ZnO单晶。四脚状样品的PL光谱显示样品存在近紫外峰（380nm）和绿峰（500nm）两个发射带,半峰全宽分别约为15,90nm,其峰值强度比其他方法（如溶液法）制得样品的峰值强。样品的尺寸对光谱强度有一定影响,但对谱峰位置并无影响。用He-Cd激光器的325nm激光对四脚状样品进行发射光谱分析,发现其近紫外激子发光大大增强而绿色缺陷发光相对较弱,近紫外的峰值位于383nm,半峰全宽约为16nm;绿峰峰值位于515nm,半峰全宽约为76nm。     

原子层沉积金属氧化物缓冲层制备高性能大面积钙钛矿太阳电池

研制具有较大活性面积的钙钛矿太阳电池对领域面向产业化的发展具有重要意义.当前,大面积钙钛矿太阳电池的性能与小面积钙钛矿太阳电池之间仍存在较大差距.本文提出一种在透明导电薄膜衬底上预先原子层沉积TiO₂薄层的策略,有效避免了衬底局部突起与钙钛矿吸光层直接接触导致的漏电现象,提升了小面积器件制备工艺的重复一致性.改善的电子输运和光管理过程也提高了小面积器件的效率.更重要的是,本文基于原子层沉积的TiO₂开展了0.5 cm²大面积钙钛矿太阳电池的研究,通过优化TiO₂层的厚度,研制出光电转换效率高达24.8%的冠军器件(第三方认证效率24.65%),器件的制备工艺也表现出较好的重复性.此外,原子层沉积了TiO₂缓冲层的电池器件在氮气氛围下存储1500 h后仍然能够保留初始性能的95%以上.总之,在粗糙衬底上预先原子层沉积TiO₂薄层可以有效抑制局部漏电通道的产生,有利于制备高性能的大面积钙钛矿太阳电池.     

通过氧源调控原子层沉积的SnOx层实现高效稳定的钙钛矿太阳能电池

原子层沉积的SnO_x薄膜具有良好的均匀性和致密性,常被用于提升倒置平面结构钙钛矿太阳能电池的稳定性。而SnO_x薄膜的特性对器件能量转换效率(Power conversion efficiency,PCE)有着重要影响。本文通过氧源(H₂O、O₃)调控SnO_x薄膜的能级和导电性,提升器件PCE。结果表明,O₃作为单一氧源的SnO_x薄膜(记为O₃-SnO_x)具有较优的能级排列;而只有H₂O作氧源的SnO_x薄膜(记为H₂O-SnO_x)具有较高的电导率。而采用O₃和H₂O混合氧源制备的SnO_x(记为MIX-SnO_x),则兼顾了能级匹配和良好的导电性,有效提升器件的PCE,达到20.9%。不仅如此,得益于SnO_x     

原子层沉积与聚焦离子束切片法制备X射线波带片

针对X射线波带片对大高宽比的应用需求,采用原子层沉积法在光滑的金属丝表面生长膜厚可高精度控制的多层膜环带结构,再利用聚焦离子束切片技术获得大高宽比的多层膜X射线波带片。采用复振幅叠加法设计了以Al₂O₃/HfO₂分别为明环和暗环材料的X射线波带片,实验上利用原子层沉积在直径为72μm的金丝表面交替沉积了10.11μm的Al₂O₃/HfO₂多层膜,环带数为356,总直径为92.22μm,最外环宽度为25 nm。通过聚焦离子束切割得到高为1.08μm、高宽比达43∶1的X射线多层膜菲涅耳波带片。该波带片应用于上海光源(BL08U1A)软X射线成像线站时,在1.2 keV X射线下实现聚焦成像功能,展现出利用该技术制备多层膜X射线波带片的潜力。     

低温原子层沉积氧化铝作为有机电致发光器件的封装薄膜

为了克服传统的原子层深沉积反应温度高于有机材料的玻璃化温度对有机电致发光器件性能产生破坏的缺点,使用低温原子层沉积的方法沉积了Al2O3薄膜,成功地实现了对OLED的薄膜封装。实验中为了抑制环境温度对ALD薄膜均匀性的影响,增加了每个反应周期的抽气时间,从而可以充分地排出反应副产物,抑制了空位的形成,使得薄膜具有较高的均匀性和致密性。微观形貌分析、钙测试以及寿命测试表明,通过增加ALD的PGT,低温制备的薄膜与高温制备的薄膜的均匀性差别较小,且制备过程对OLED器件的光电性能无明显影响。低温制备的薄膜水汽透过率(WVTR)可以达到8.6×10-4g/(m2·d),能够有效地提高有机电致发光器件的寿命。     

Double‐layer channel structure based ZnO thin‐film transistor grown by atomic layer deposition

A double channel structure has been used by depositing a thin amorphous‐AlZnO (a‐AZO) layer grown by atomic layer deposition between a ZnO channel and a gate dielectric to enhance the electrical stability. The effect of the a‐AZO layer on the electrical stability of a‐AZO/ZnO thin‐film transistors (TFTs) has been investigated under positive gate bias and temperature stress test. The use of the a‐AZO layer with 5 nm thickness resulted in enhanced subthreshold swing and decreased V_th shift under positive gate bias/temperature stress. In addition, the falling rate of the oxide TFT using a‐AZO/ ZnO double channel had a larger value (0.35 eV/V) than that of pure ZnO TFT (0.24 eV/V). These results suggest that the interface trap density between dielectric and channel was reduced by inserting a‐AZO layer at the interface between the channel and the gate insulator, compared with pure ZnO channel. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Characteristics and properties of metal aluminum thin film prepared by electron cyclotron resonance plasma-assisted atomic layer deposition technology

Metal aluminum (Al) thin films are prepared by 2450-MHz electron cyclotron resonance plasma-assisted atomic layer deposition on glass and p-Si substrates using trimethylaluminum as the precursor and hydrogen as the reductive gas. We focus our attention on the plasma source for thin-film preparation and annealing of as-deposited films related to the surface square resistivity. The square resistivity of as-deposited Al film is greatly reduced after annealing and almost reaches the value of bulk metal. Through chemical and structure analysis we conclude that the square resistivity is determined by neither contaminant concentration nor surface morphology, but by both crystallinity and crystal size in this process.     

Fill factor controlled nanoimprinted ZnO nanowires based on atomic layer deposition

Enhanced diffraction by sub-wavelength nanostructures to convert incident electromagnetic radiation into waveguide modes has applications in anti-reflective coatings for optoelectronic devices. We propose a metal oxide (ZnO) nanowire grid polarizer as such a nanostructure, fabricated by ultraviolet nanoimprint lithography and whose fill factor (FF) is controlled by atomic layer deposition. Using finite difference time domain simulations, we investigated the polarization-dependent optical transmittance of the structures and calculated the polarizing efficiency. Optical profiles such as electric and magnetic field intensity and current density distributions of specific FF nanopatterns were determined for the transverse magnetic and transverse electric modes. The effects of geometrical parameters including the wire-grid period, fill ratio, and spacing between the wire-grid layers on diffraction wavelength were characterized. Respective FF-controlled ZnO nanowire structures were fabricated and their experimental optical transmittances were measured for nanowire grid polarizer applications.     

Patterned deposition by plasma enhanced spatial atomic layer deposition

An atmospheric pressure plasma enhanced atomic layer deposition reactor has been developed, to deposit Al₂O₃ films from trimethyl aluminum and an He/O₂ plasma. This technique can be used for 2D patterned deposition in a single in‐line process by making use of switched localized plasma sources. It was observed that the sharpness of the patterns is primarily influenced by the concentration of reactive plasma species and by the dimensions of the plasma source. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Organic photovoltaics with high stability sustained for 100 days without encapsulation fabricated using atomic layer deposition

ZnO thin films with a rippled surface structure were used as electron‐collecting layers of inverted organic photovoltaics (OPVs). Using additional ultrathin layers of ZnO and TiO₂ fabricated using atomic layer deposition (ALD), not only the power‐conversion efficiency of the OPVs could be increased (up to 3.5%), but also the photovoltaic performance became nearly constant within 100 days without any additional encapsulations of the solar cells under ambient conditions.

     

Impact of substrate temperature and film thickness on the interfacial evolution during atomic layer deposition of HfO2 on InP

The effects of both the deposition temperature and the HfO₂ film thickness on the interfacial layer (IL) evolution were studied when tetrakis(ethylmethylamino)hafnium and H₂O based atomic layer deposition (ALD) was performed on InP substrates. While the self‐cleaning effect resulted in an IL‐free structure after formation of ～2 nm thick HfO₂ at 200 °C and 250 °C, substantial IL growth occurred at 300 °C, probably due to simultaneous InP oxidation. Following further growth to ～8 nm at 300 °C, the IL was almost removed and, in particular, a significant In incorporation into the HfO₂ film was observed, which was attributed to IL decomposition and subsequent out‐diffusion of the constituent elements. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Characteristics and properties of metal aluminum thin films prepared by electron cyclotron resonance plasma-assisted atomic layer deposition technology

Metal aluminum (Al) thin films are prepared by 2450 MHz electron cyclotron resonance plasma-assisted atomic layer deposition on glass and p-Si substrates using trimethylaluminum as the precursor and hydrogen as the reductive gas. We focus our attention on the plasma source for the thin-film preparation and annealing of the as-deposited films relative to the surface square resistivity. The square resistivity of as-deposited Al films is greatly reduced after annealing and almost reaches the value of bulk metal. Through chemical and structural analysis, we conclude that the square resistivity is determined by neither the contaminant concentration nor the surface morphology, but by both the crystallinity and crystal size in this process.     

基于多孔氧化铝和单原子沉积技术的颜色调控方法研究

本文通过建立多孔氧化铝(porous alumina,PA)的物理模型及理论分析,提出与发展了一种基于PA和单原子沉积(atomic layer deposition,ALD)技术的颜色调控新方法.以实验制备的PA样品为原型,对孔径相同、孔中心距相同但孔深不同的一系列PA模板进行了颜色调控的仿真,揭示了调控色随孔深变化的规律;通过控制在草酸溶液中的阳极氧化时间,实验制备出平均孔径40 nm、平均孔中心距100 nm、孔深分别为296 nm和373 nm的两个PA样品;之后采用ALD技术在它们表面均沉积一层 关键词： 多孔氧化铝 颜色调控 单原子沉积     

Permeation barrier properties of an Al2O3/ZrO2 multilayer deposited by remote plasma atomic layer deposition

We report the permeation barrier properties of Al₂O₃/ZrO₂ multi-layers deposited by remote plasma atomic layer deposition. Electrical Ca degradation tests were performed to derive the water vapor transmission rate (WVTR) of Al₂O₃, ZrO₂ and Al₂O₃/ZrO₂ multi-layers at 50 °C and 50% relative humidity (RH). Al₂O₃/ZrO₂ multi-layers exhibit better barrier properties than Al₂O₃ and ZrO₂ layers, and when more individual layers were deposited in the same total thickness, the WVTR value was reduced further, indicating a better barrier property. The WVTR of the Al₂O₃ and ZrO₂ layers were 9.5 × 10⁻³ and 1.6 × 10⁻² g/m² day, respectively, but when deposited alternatively with 1 cycle of each layer, the WVTR decreased to 9.9 × 10⁻⁴ g/m² day. X-ray diffraction results indicated that ZrO₂ has a monoclinic structure but Al₂O₃ and Al₂O₃/ZrO₂ multi-layers show an amorphous structure. Cross sectional Al₂O₃/ZrO₂ multi-layer structures and the formation of a ZrAl_xO_y phase are observed by transmission electron microscopy (TEM). X-ray photoelectron spectrometry (XPS) results indicate that Al₂O₃ and ZrO₂ contain 33.7% and 37.8%, respectively, Al–OH and Zr–OH bonding. However, the ZrAl_xO_y phase contained 30.5% Al–OH and Zr–OH bonding. The results of transmittance measurement indicate that overall, Al₂O₃, ZrO₂ and Al₂O₃/ZrO₂ multi-layers show high transmittance greater than 80% in the visible region.