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     

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)     

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.     

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.     

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.     

Properties of AlN grown by plasma enhanced atomic layer deposition

The influence of growth parameters on the properties of AlN films fabricated by plasma-enhanced atomic layer deposition using trimethylaluminum and ammonia precursors was investigated. The atomic concentrations, refractive index, mass density, crystallinity and surface roughness were studied from the films grown in the temperature range of 100-300 °C with plasma discharge times between 2.5 and 30 s. The AlN films were shown to be hydrogen rich having H concentrations in the range of 13-27 at.% with inverse dependence on the growth temperature. The carbon and oxygen concentrations in the films were less than 2.6% and 0.2%, respectively. The refractive index and mass density of the films correlated with the hydrogen concentration so that higher concentrations (lower growth temperatures) resulted in smaller refractive index and mass density. The film grown at 300 °C was found to be crystalline whereas lower growth temperature produced amorphous films.     

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)。     

Ternary semiconductor compounds CuInS2 (CIS) thin films synthesized by electrochemical atomic layer deposition (EC-ALD)

In this paper the formation and characterization of the I-III-VI₂ semiconductor compound CuInS₂ (CIS) on gold substrate at room temperature by electrochemical atomic layer deposition (EC-ALD) method are reported. Optimum deposition potentials for each element are determined using cyclic voltammetry (CV) technique and Amperometric I-t method is used to prepare the semiconductor compound. These thin films were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FE-SEM) and Fourier transform infrared spectroscopy (FT-IR). XRD results indicate that the CIS thin films have a (1 1 2) preferred orientation. The XPS analyses of the films reveal that Cu, In and S are present in an atomic ratio of approximately 1:1:2. And their semiconductor band gaps are found to be 1.50 eV by FT-IR.     

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.     

Plasma enhanced atomic layer deposition of gallium oxide on crystalline silicon: demonstration of surface passivation and negative interfacial charge

Herein we report on the passivation of crystalline silicon by gallium oxide (Ga₂O₃) using oxygen plasma as the oxidizing reactant in an atomic layer deposition (ALD) process. Excess carrier lifetimes of 2.1 ms have been measured on 1.75 Ω cm p‐type silicon, from which a surface recombination current density J₀ of 7 fA cm^–2 is extracted. From high frequency capacitance‐voltage (HF CV) measurements it is shown that, as in the case of Al₂O₃, the presence of a high negative charge density Q_tot/q of up to –6.2 × 10¹² cm^–2 is one factor contributing to the passivation of silicon by Ga₂O₃. Defect densities at midgap on the order of ～5 × 10¹¹ eV^–1 cm^–2 are extracted from the HF CV data on samples annealed at 300 °C for 30 minutes in a H₂/Ar ambient, representing an order of magnitude reduction in the defect density compared to pre‐anneal data. Passivation of a boron‐diffused p⁺ surface (96 Ω/□) is also demonstrated, resulting in a J₀ of 52 fA cm^–2. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Influences of annealing on structural and compositional properties of Al_2O_3 thin films grown on 4H–SiC by atomic layer deposition

Annealing effects on structural and compositional performances of Al_2O_3 thin films on 4H–Si C substrates are studied comprehensively. The Al_2O_3 films are grown by atomic layer deposition through using trimethylaluminum and H_2 O as precursors at 300?C, and annealed at various temperatures in ambient N_2 for 1 min. The Al_2O_3 film transits from amorphous phase to crystalline phase as annealing temperature increases from 750?C to 768?C. The refractive index increases with annealing temperature rising, which indicates that densification occurs during annealing. The densification and grain formation of the film upon annealing are due to crystallization which is relative with second-nearest-neighbor coordination variation according to the x-ray photoelectron spectroscopy(XPS). Although the binding energies of Al 2p and O 1s increase together during crystallization, separations between Al 2p and O 1s are identical between as-deposited and annealed sample, which suggests that the nearest-neighbour coordination is similar.     

Influence of annealing temperature on passivation performance of thermal atomic layer deposition Al_2O_3 films

Chemical and field-effect passivation of atomic layer deposition （ALD） Al2O3 films are investigated, mainly by corona charging measurement. The interface structure and material properties are characterized by transmission electron microscopy （TEM） and X-ray photoelectron spectroscopy （XPS）, respectively. Passivation performance is improved remarkably by annealing at temperatures of 450 ℃ and 500 ℃, while the improvement is quite weak at 600 ℃, which can be attributed to the poor quality of chemical passivation. An increase of fixed negative charge density in the films during annealing can be explained by the Al2O3/Si interface structural change. The Al–OH groups play an important role in chemical passivation, and the Al–OH concentration in an as-deposited film subsequently determines the passivation quality of that film when it is annealed, to a certain degree.     

Controlled growth of rutile TiO2 by atomic layer deposition on oxidized ruthenium

Crystalline rutile TiO₂ films were grown by atomic layer deposition on oxidized Ru electrodes using a titanium methoxide as the metal precursor and O₃ as the oxidant. A protective layer of ～0.3 nm TiO₂ grown with H₂O as the oxidant was first deposited in order to avoid etching of the Ru bottom electrode by the O₃ used for the growth of the TiO₂ (bulk) layer. Electrical evaluation of the capacitor stacks with TiO₂ as dielectric, RuO₂/Ru and Pt as the bottom and top electrodes respectively, resulted in superior characteristics of the rutile phase as compared to the anatase. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Atomic layer deposition of TiO2 and Al‐doped TiO2 films on Ir substrates for ultralow leakage currents

TiO₂ and Al‐doped TiO₂ (ATO) films were grown on Ir substrates by atomic layer deposition using O₃ as the oxygen source. With increasing O₃ feeding time, the crystalline structure of the TiO₂ films was transformed from anatase to rutile. Above an O₃ feeding time of 35 s, the films crystallized as only rutile due to the formation of IrO₂ layer at the interface. The TiO₂ and ATO films showed higher dielectric constants of 78 and 51, respectively. The films on Ir showed superior leakage properties compared to the films on Ru due to the high work‐function of Ir. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

TiO2/Al2O3薄膜的原子层沉积和光学性能分析

采用原子层沉积技术在熔石英和BK7玻璃基片上镀制了TiO2/Al2O3薄膜,沉积温度分别为110℃和280℃。利用X射线粉末衍射仪对膜层微观结构进行了分析研究,并在激光损伤平台上进行了抗激光损伤阈值测量。采用Nomarski微分干涉差显微镜和原子力显微镜对激光损伤后的形貌进行了观察分析。结果表明,采用原子层沉积技术镀制的TiO2/Al2O3增透膜的厚度均匀性较好,Φ50 mm样品的膜层厚度均匀性优于99%;光谱增透效果显著,在1 064 nm处的透过率〉99.8%;在熔石英和BK7基片上,TiO2/Al2O3薄膜在110℃时的激光损伤阈值分别为（6.73±0.47）J/cm2和（6.5±0.46）J/cm2,明显高于在280℃时的损伤阈值。     

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.     

Characterization and application in XRF of HfO_2-coated glass monocapillary based on atomic layer deposition

Coating a glass monocapillary x-ray optics with high-density film is a promising way to improve transmission characteristics. For a long time, it has been a challenge to coat a high-density film in the inside of monocapillary with an extremely high length-to-diameter ratio. In this work, Hf O2 film is deposited on the inner wall of a tapered glass monocapillary with length 9.9 cm, entrance diameter 596.4 μm, and exit diameter 402.3 μm by atomic layer deposition. The coated and uncoated monocapillaries are studied by the transmission process of x-rays with energy from 5 ke V to 100 ke V and the x-ray fluorescence(XRF) spectra of a Mo sample are detected. Improved transmission characteristics have been obtained for the Hf O_2-coated monocapillary. The energy upper limit of focused x-rays increases from 18.1 ke V to 33.0 ke V and the ‘penetration halo' is suppressed to some extent. The XRF spectrum presents two stronger peaks at ～ 17.4 ke V and～ 19.6 ke V which are considered as the characteristic x-rays of Mo K_α and Mo K_β. These results reveal that more higher energy x-rays from the W x-ray tube are totally reflected on the inner wall of the Hf O_2-coated glass monocapillary due to the increase of total reflection critical angle. This work is significant for more applications of monocapillary in higher energy x-ray field.     

ZnS thin films grown by atomic layer deposition on GaAs and HgCdTe substrates at very low temperature

ZnS films grown on GaAs and HgCdTe substrates by atomic layer deposition (ALD) under very low temperature were investigated in this work. ZnS films were grown under several temperatures lower than 140 °C. The properties of the films were investigated with high-resolution X-ray diffraction (HRXRD), scanning electron microscope (SEM), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). The results showed the ZnS films were polycrystalline. The growth rate monotonically decreased with temperature, as well as the root mean square (r.m.s) roughness measured by AFM. XPS measurement revealed the films were stoichiometric in Zn and S.     

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.