原子层沉积HfO2薄膜的激光损伤特性分析

以目前激光惯性约束聚变中应用最广泛的高折射率材料二氧化铪(HfO2)为研究对象,在熔石英基底上分别采用TEMAH和HfCl4前驱体制备了HfO2薄膜,沉积温度分别为100,200和300 ℃。采用椭偏仪和激光量热计对薄膜的光学性能进行了测量分析,采用X射线衍射仪(XRD)对薄膜的微结构进行了测量。最后在小口径激光阈值测量平台上按照1-on-1测量模式对薄膜的损伤阈值进行了测试,并采用扫描电子显微镜（SEM）对损伤形貌进行了分析。研究表明,用同一种前驱体源时,随着沉积温度升高,薄膜折射率增加,吸收增多,损伤阈值降低。在相同温度下,采用有机源制备的薄膜更容易在薄膜内部形成有机残留,导致薄膜吸收增加,损伤阈值降低。采用HfCl4作为前驱体源在100℃制备氧化铪薄膜时,损伤阈值能够达到31.8 J/cm2 (1064 nm,3 ns)。     

退火对EBE,IBS和ALD沉积HfO2薄膜的抗激光损伤性能影响

结合自身实验条件采用电子束蒸发(EBE)、离子束溅射(IBS)和原子层沉积(ALD)三种工艺制备了HfO2薄膜,对其进行退火实验,采用1064 nm Nd:YAG激光测定了即时沉积和退火后各HfO2薄膜的抗激光损伤能力。研究发现,ALD HfO2薄膜的激光损伤阈值最高,EBE HfO2薄膜次之,IBS HfO2薄膜的损伤阈值最低;300℃退火对各工艺薄膜抗激光损伤能力的影响均为负面,500℃退火则会显著降低ALD HfO2薄膜的抗激光损伤能力。     

制备工艺对HfO_2薄膜抗激光损伤能力的影响

采用反应蒸镀法镀制了单层ＨｉＯ２薄膜,观察了薄膜表面主要的微结构缺陷, 研究了基片清洗工艺对薄膜损伤阈值的影响。测量了薄膜沉积前后表面粗糙度变化。结果表 明：沉积工艺可以改变粗糙度,并对薄膜抗激光损伤能力有较大的影响。     

光学玻璃基底原子层同质材料沉积薄膜光谱及激光诱导损伤特性研究

通过原子层沉积技术在熔石英玻璃表面制备了同质材料的单层SiO2薄膜,对光学薄膜的物理化学性质和强激光辐照下的激光诱导损伤性能进行了深入研究.实验中采用双叔丁基氨基硅烷(BTBAS)和臭氧(O3)作为反应前驱体,在熔石英光学元件表面进行了SiO2薄膜的原子层沉积工艺研究,以不同沉积温度条件制备了一系列膜样品.首先对原子层...     

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。     

制备工艺对HfO2薄膜抗激光损伤能力的影响

采用反应蒸镀法镀制了单层HfO2薄膜,观察了薄膜表面主要的微结构缺陷,研究了基片清洗工艺对薄膜损伤阈值的影响。测量了薄膜沉积前后表面粗糙度变化。结果表明：沉积工艺可以改变粗糙度,并对薄膜抗激光损伤能力有较大的影响。     

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。     

化学法制备的HfO2薄膜的激光损伤阈值研究

采用化学法制备了HfO2介质膜,研究了热处理、紫外辐照以及Al2O3复合对HfO2介质膜激光损伤阈值的影响。采用红外光谱（FTIR）和X射线衍射仪对薄膜进行了表征,并用输出波长为1.064 μm、脉宽为10 ns的电光调Q激光系统测试薄膜的激光损伤阈值。实验结果表明：采用150 ℃左右的温度对薄膜进行热处理可以提高薄膜的激光损伤阈值,所获得的薄膜的激光损伤阈值高达42.32 J/cm2,比热处理前的激光损伤阈值提高了82%;无机材料Al2O3的适量添加能够提高薄膜的激光损伤阈值,其中HfO2与Al2O3的最佳质量配比约为95∶5;另外,对薄膜进行适当的紫外辐照也可改善HfO2 薄膜以及HfO2-Al2O3复合薄膜的抗激光损伤性能。紫外辐照对提高HfO2-Al2O3复合薄膜的激光损伤阈值效果尤为显著,辐照40 min后的激光损伤阈值达到44.33 J/cm2,比紫外辐照前的激光损伤阈值提高了90%。     

HfO_2/SiO_2高反射膜的缺陷及其激光损伤

用原子力、Normaski和扫描电子显微镜等分析仪器 ,对高损伤阈值薄膜常采用的 Hf O2 /Si O2 薄膜进行了表面显微图象研究 ,分析了薄膜常见的表面缺陷 ,如节瘤 ,孔洞和划痕等。薄膜表面缺陷的激光损伤实验表明 ,不同缺陷的抗激光损伤能力大不相同 ,节瘤缺陷最低 ,约为 1 5 J/ cm2 ,薄膜的损伤阈值主要由其决定 ,孔洞的激光损伤能力与节瘤相比较高 ,约为节瘤的 2～ 3倍。节瘤缺陷在低能量密度的激光损伤所形成的孔洞 ,与镀制过程中形成的孔洞形貌相似 ,激光再损伤能力也相似。低能量密度的激光把节瘤缺陷变为孔洞缺陷是激光预处理提高薄膜损伤阈值的原因之一     

缺陷对HfO2薄膜的激光弱吸收与损伤阈值的影响

激光弱吸收是导致光学薄膜损伤的重要原因。在(5~43)mPa的氧分压下制备并测试了一组HfO2薄膜。实验发现,当氧分压小于20mPa时,薄膜弱吸收越大,损伤阈值越低;当氧分压大于20mPa时,薄膜的损伤阈值与弱吸收并不一一对应,具有较高弱吸收的薄膜可能同时具有较高的损伤阈值。建立了缺陷模型,采用有限元法模拟了缺陷对弱吸收测量和损伤阈值测量的影响,分析了缺陷尺寸、密度、吸收系数对弱吸收和损伤阈值的影响。研究结果显示,吸收系数高于薄膜1 000倍的缺陷可以降低薄膜的损伤阈值1 000倍,却并不影响薄膜的弱吸收。缺陷对HfO2薄膜的激光弱吸收与损伤阈值测试有完全不同的影响,是导致某些薄膜弱吸收与损伤阈值背离的原因。     

Influence of different oxidants on the band alignment of HfO2 films deposited by atomic layer deposition

Based on X-ray photoelectron spectroscopy （XPS）, influences of different oxidants on band alignment of HfO2 films deposited by atomic layer deposition （ALD） are investigated in this paper. The measured valence band offset （VBO） value for H2O-based HfO2 increases from 3.17 eV to 3.32 eV after annealing, whereas the VBO value for O3-based HfO2 decreases from 3.57 eV to 3.46 eV. The research results indicate that the silicate layer changes in different ways for H2O-based and O3-based HfO2 films after the annealing process, which plays a key role in generating the internal electric field formed by the dipoles. The variations of the dipoles at the interface between the HfO2 and SiO2 after annealing may lewd the VBO values of H2O-based and O3-based HfO2 to vary in different ways, which fits with the variation of fiat band （VFB） voltage.     

Roughness simulation for thin films prepared by atomic layer deposition

The kinetic lattice Monte Carlo method for film growth simulation without taking crystallization into account was applied to study the roughness of the HfO₂ film grown by atomic layer deposition at 100–500°C from HfCl₄ and H₂O. The calculations were performed using a simplified kinetic mechanism of the growth of HfO₂ films obtained by reducing the detailed kinetic mechanism developed earlier. Ab initio quantum-chemical calculations were performed to determine the kinetic parameters of diffusion processes on the surface of hafnium oxide that could influence film roughness. Because of the special features of atomic layer deposition, the rate of film growth and film roughness were finite even if surface relaxation was ignored. It was found that, irrespective of the temperature, the diffusion of hydrogen and adsorbed HfCl₄ complexes did not change the profile of the growing film and only insignificantly increased the mean rate of growth. The results obtained were also qualitatively applicable to zirconium dioxide at fairly low (≤100°C) temperatures in the absence of crystallization.     

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     

Preparation of tantalum oxide thin films by photo-assisted atomic layer deposition

Tantalum oxide thin films were prepared by photo-assisted atomic layer deposition (Photo-ALD) in the substrate temperature range of 170–400 °C using Ta(OC₂H₅)₅ and H₂O as precursors. The constant growth rates of 0.42 and 0.47 Å per cycle were achieved for the films grown by normal ALD and Photo-ALD, respectively. The increased growth rate in Photo-ALD is probably due to the reactive surface by photon energy and faster surface reaction. In Photo-ALD, however, the constant growth rate started at lower temperature of 30 °C and one cycle time shortened up to 5.7 s than that of normal ALD. The films grown by normal ALD and Photo-ALD were amorphous and very smooth (0.21–0.35 nm) as examined by X-ray diffractometer and atomic force microscopy, respectively. Also, the refractive index was found to be 2.12–2.16 at the substrate temperature of 190–300 °C, similar to that of the film grown by normal ALD. However, the remarkably low leakage current density of 0.6×10⁻⁶ A/cm² to 1×10⁻⁶ A/cm² at applied field of 1 MV/cm is several order of magnitude smaller than that of normal ALD, probably due to the presence of reactive atom species.     

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.     

Laser deposited YBaCuO thin films

YBa₂Cu₃O_7-x thin films were deposited by laser ablation using KrF excimer laser. In deposition on polycrystalline ZrO₂/(1–102) sapphire substrates influence of deposition conditions on film properties were studied. Zero resistance temperatureT _z of 83 K of epitaxially grown YBaCuO films on poly-ZrO₂/sapphire substrates was reached. Epitaxially grown yttria stabilized zirconia (YSZ) buffer layers were deposited by laser ablation on (1–102) sapphire substrates. On YSZ/sapphire, SrTiO₃ and NdGaO₃ substrates, temperatures T_z between 89–90 K were measured. Results of X-ray diffraction and SEM are also presented.We would like to express our thanks to L. Cibulka, L. and L. Rouek, and J. Stránský for their efficient help during the solution of technological problems connected with the construction of experimental apparatus.     

Properties including step coverage of TiN thin films prepared by atomic layer deposition

The physical properties including the step coverage of the TiN films deposited by atomic layer deposition (ALD) technique, using TiCl₄ and NH₃ as the precursors have been investigated. The deposition rate of the TiN film is constant and moderately high (0.6 Å per cycle) under an optimum deposition condition. The film resistivity is appreciably low (200 μΩ cm). The XRD analysis results indicate polycrystalline nature of the TiN films with a (1 1 1) preferred orientation. The XPS and AES analysis results establish that the Cl impurity concentration in the TiN films is lower than 1 at.% and the ratio of Ti and N by atomic concentration in the TiN films is nearly equal to 1:1 AFM analysis reveals that the RMS surface roughness is low. Also it is found by SEM observation that the step coverage of the TiN films with trenches (the aspect ratio being 10:1) is excellent. One hundred percent conformality is observed for both the side/bottom and the side/top sections.     

Low-temperature plasma enhanced atomic layer deposition of large area HfS_2 nanocrystal thin films

Hafnium disulfide(HfS2) is a promising two-dimensional material for scaling electronic devices due to its higher carrier mobility, in which the combination of two-dimensional materials with traditional semiconductors in the framework of CMOS-compatible technology is necessary. We reported on the deposition of HfS2 nanocrystals by remote plasma enhanced atomic layer deposition at low temperature using Hf(N(CH3)(C2H5))4 and H2S as the reaction precursors. Selflimiting reaction behavior was observed at the deposition temperatures ranging from 150℃ to 350℃, and the film thickness increased linearly with the growth cycles. The uniform HfS2 nanocrystal thin films were obtained with the size of nanocrystal grain up to 27 nm. It was demonstrated that higher deposition temperature could enlarge the grain size and improve the HfS2 crystallinity, while causing crystallization of the mixed HfO2 above 450℃. These results suggested that atomic layer deposition is a low-temperature route to synthesize high quality HfS2 nanocrystals for electronic device or electrochemical applications.     

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.