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.     

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.     

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.     

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。     

热原子层沉积氧化铝对硅的钝化性能及热稳定性

原子层沉积氧化铝已经成为应用于钝化发射极和背面点接触（PERC）型晶硅太阳能电池优异的钝化材料．对于基于丝网印刷技术的太阳能电池,钝化材料的钝化效果及其热稳定性是非常重要的．本文在太阳能级硅片上用热原子层沉积设备制备了20nm和30nm的氧化铝,少子寿命测试结果显示初始沉积的氧化铝薄膜具有一定的钝化效果,在退火后可达到100μs以上,相当于硅表面复合速度小于100cm／s．经过制备传统晶硅太阳能电池的烧结炉后,少子寿命能够保持在烧结前的一半以上,可应用于工业PERC型电池的制备．通过电子显微镜观察到了较厚的氧化铝薄膜有气泡,解释了30nm氧化铝比20nm氧化铝钝化性能和稳定性更差的异常表现．     

Structural properties of the titanium dioxide thin films grown by atomic layer deposition at various numbers of reaction cycles

A dependence of structural properties of TiO₂ films grown on both Si- and Ti-substrates by atomic layer deposition (ALD) at the temperature range of 250-300 °C from titanium ethoxide and water on the number of reaction cycles N was investigated using Fourier-transform infrared (FTIR) spectroscopy and X-Ray diffraction (XRD). TiO₂ films grown on both Si- and Ti-substrates revealed amorphous structure at low values of N < 400. However, an increase of N up to values 400-3600 resulted in the growth of polycrystalline TiO₂ with structure of anatase on both types of substrates and according to XRD-measurements the sizes of crystallites rose with the increase of N. The maximum anatase crystallite size for TiO₂ grown on Ti-substrate was found to be on ∼35% lower in comparing with that for TiO₂ grown on Si-substrate. A use of titanium methoxide as a Ti precursor with the ligand size smaller than in case of titanium ethoxide allowed to observe an influence of the ligand size on both the growth per cycle and structural properties of TiO₂. The average growth per cycle of TiO₂ deposited from titanium methoxide and water (0.052 ± 0.01 nm/cycle) was essentially higher than that for TiO₂ grown from titanium ethoxide and water (0.043 ± 0.01 nm/cycle). Ligands of smaller sizes were found to promote the higher crystallinity of TiO₂ in comparison with the case of using the titanium precursor with ligands of bigger sizes.     

气相沉积技术在原子制造领域的发展与应用

随着未来信息器件朝着更小尺寸、更低功耗和更高性能方向的发展,构建器件的材料尺寸将进一步缩小.传统的"自上而下"技术在信息器件发展到纳米量级时遇到瓶颈,而气相沉积技术由于其能在原子尺度构筑纳米结构引起极大关注,被认为是最有潜力突破现有制造极限进而在原子尺度构造、搭建物质形态的"自下而上"方法.本文重点讨论适用于低维材料的...     

Layer-by-layer deposition of Ti-4,4′-oxydianiline hybrid thin films

Features of the two thin-film techniques, atomic layer deposition (ALD) and molecular layer deposition (MLD), are combined to build up a stable novel inorganic-organic hybrid material of the (-Ti-N-C₆H₄-O-C₆H₄-N-)_n type, deposited from successive pulses of TiCl₄ and 4,4′-oxydianiline precursors. Depositions in the temperature range of 160-230 °C resulted in unstable films, while the films obtained in the temperature range of 250-490 °C were found stable in atmospheric air. The growth rate increased with increasing temperature, from 0.3 Å per cycle at 160 °C to 1.1 Å per cycle at 490 °C.     

First nucleation steps during deposition of SiO2 thin films by plasma enhanced chemical vapour deposition

The initial nucleation stages during deposition of SiO₂ by remote plasma enhanced chemical vapour deposition (PECVD) have been monitored by XPS inelastic peak shape analysis. Experiments have been carried out on two substrates, a flat ZrO₂ thin film and a silicon wafer with a native silicon oxide layer on its surface. For the two substrates it is found that PECVD SiO₂ grows in the form of islands. When the SiO₂ particles reach heights close to 10 nm they coalesce and cover completely the substrate surface. The particle formation mechanism has been confirmed by TEM observation of the particles grown on silicon substrates. The kinetic Monte Carlo simulation of the nucleation and growth of the SiO₂ particles has shown that formation of islands is favoured under PECVD conditions because the plasma species may reach the substrate surface according to off-perpendicular directions. The average energy of these species is the main parameter used to describe their angular distribution function, while the reactivity of the surface is another key parameter used in the simulations.     

Effect of crystalline structure of TiO2 substrates on initial growth of atomic layer deposited Ru thin films

Ru thin films were grown on polymorphic TiO₂ thin film substrates at 230 and 250 °C by atomic layer deposition using 2,4-(dimethylpentadienyl)(ethylcyclopentadienyl)Ru and an O₂ gas. While the Ru films grown on amorphous and rutile TiO₂ substrates showed a relatively long incubation cycle number of approximately 350 and 100 at 230 and 250 °C, respectively, the Ru films grown on anatase TiO₂ substrates exhibited a significantly shorter incubation delay which was attributed to the catalytic activity of anatase TiO₂. This difference in the incubation cycle affected the surface morphology of the Ru films on different TiO₂ substrates.     

Structural study of TiO2 thin films by micro-Raman spectroscopy

The Raman spectroscopy method was used for structural characterization of TiO₂ thin films prepared by atomic layer deposition (ALD) and pulsed laser deposition (PLD) on fused silica and single-crystal silicon and sapphire substrates. Using ALD, anatase thin films were grown on silica and silicon substrates at temperatures 125–425 °C. At higher deposition temperatures, mixed anatase and rutile phases grew on these substrates. Post-growth annealing resulted in anatase-to-rutile phase transitions at 750 °C in the case of pure anatase films. The films that contained chlorine residues and were amorphous in their as-grown stage transformed into anatase phase at 400 °C and retained this phase even after annealing at 900 °C. On single crystal sapphire substrates, phase-pure rutile films were obtained by ALD at 425 °C and higher temperatures without additional annealing. Thin films that predominantly contained brookite phase were grown by PLD on silica substrates using rutile as a starting material.     

Transparent conductive ZnO:Al films grown by atomic layer deposition for Si-wire-based solar cells

Structural, electrical, and optical properties of atomic layer-controlled Al-doped ZnO (ZnO:Al) films grown by atomic layer deposition (ALD) on glass substrates were characterized at various growth temperatures for use as transparent electrodes. The Al atomic content in ZnO:Al films increased due to the reduced ZnO film growth rate with increasing temperature. The preferred orientation of ZnO:Al films was changed, and the optimum condition for best crystallinity was identified by varying the growth temperature. Furthermore, the carrier concentration of free electron was increased by substituting the Zn sites with Al atoms in the crystal, resulting from monolayer growth based on alternate self-limiting surface chemical reactions. The electrical resistivity of ZnO:Al film grown by ALD at 225 °C reached the lowest value of 8.45 × 10⁻⁴ Ω cm, with a carrier mobility of 9.00 cm² V⁻¹ s⁻¹ and optical transmittance of ∼93%. This result demonstrates that ZnO:Al films grown by ALD possess excellent potential for applications in electronic devices and displays as transparent electrodes and surface passivation layers.     

Electrical properties of La2O3 thin films grown on TiN/Si substrates via atomic layer deposition

The electrical as well as the structural properties of La₂O₃ thin films on TiN substrates were investigated. Amorphous stoichiometric La₂O₃ thin films were grown at 300 °C via atomic layer deposition technique by using lanthanum 2,2,6,6-tetramethyl-3,5-heptanedione [La(TMHD)₃] and H₂O as precursors. Post-annealing of the grown film induced dramatic changes in structural and the electrical properties. Crystalline phases of the La₂O₃ film emerged with the increase of the post-annealing temperature. Metal-insulator-metal (MIM) capacitor was fabricated to measure the electrical properties of the grown film. The dielectric constant of the La₂O₃ thin films increased with annealing temperature to reach the value of 17.3 at 500 °C. The leakage current density of the film post-annealed at 400 °C was estimated to be 2.78 × 10⁻¹⁰ and 2.1 × 10⁻⁸ A/cm² at ±1 V, respectively.     

Protective silicon coating for nanodiamonds using atomic layer deposition

Ultrathin silicon coating was deposited on nanodiamonds using atomic layer deposition (ALD) from gaseous monosilane (SiH₄). The coating was performed by sequential reaction of SiH₄ saturated adsorption and in situ decomposition. X-ray diffraction (XRD) and transmission electron microscopy (TEM) were utilized to investigate the structural and morphological properties of the coating. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) were used to compare the thermal stability of nanodiamonds before and after silicon coating. The results confirmed that the deposited cubic phase silicon coating was even and continuous. The protective silicon coating could effectively improve the oxidation resistance of nanodiamonds in air flow, which facilitates the applications of nanodiamonds that are commonly hampered by their poor thermal stability.     

Nanotribological behavior of ZnO films prepared by atomic layer deposition

We used atomic layer deposition to form ZnO thin-film coatings on Si substrates and then evaluate the effect of pile-up using the nanoscratch technique under a ramped mode. The wear volume decreased with increasing annealing temperature from room temperature to 400 °C for a given load. Elastic-to-plastic deformation occurred during sliding scratch processing between the groove and film for loading penetration of 30 nm. The onset of non-elastic behavior and greater contact pressure were evident for loading penetration of 150 nm; thus, full plastic deformation occurred as a result of a substrate effect. We suspect that elastic–plastic failure events were related to edge bulging between the groove and film, with elastic–plastic deformation attributable to adhesion discontinuities and/or cohesion failure of the ZnO films.     

Effects of precursors on nucleation in atomic layer deposition of HfO2

Atomic layer deposition of hafnium dioxide (HfO₂) on silicon substrates was studied. It was revealed that due to low adsorption probability of HfCl₄ on silicon substrates at higher temperatures (450–600 °C) the growth was non-uniform and markedly hindered in the initial stage of the HfCl₄–H₂O process. In the HfI₄–H₂O and HfI₄–O₂ processes, uniform growth with acceptable rate was obtained from the beginning of deposition. As a result, the HfI₄–H₂O and HfI₄–O₂ processes allowed deposition of smoother, more homogeneous and denser films than the HfCl₄–H₂O process did. The crystal structure developed, however, faster at the beginning of the HfCl₄–H₂O process.     

Influence of ignition condition on the growth of silicon thin films using plasma enhanced chemical vapour deposition

The influences of the plasma ignition condition in plasma enhanced chemical vapour deposition (PECVD) on the interfaces and the microstructures of hydrogenated microcrystalline Si (μc-Si:H) thin films are investigated.The plasma ignition condition is modified by varying the ratio of SiH 4 to H 2 (R H).For plasma ignited with a constant gas ratio,the time-resolved optical emission spectroscopy presents a low value of the emission intensity ratio of Hα to SiH (I Hα /I SiH) at the initial stage,which leads to a thick amorphous incubation layer.For the ignition condition with a profiling R H,the higher I Hα /I SiH values are realized.By optimizing the R H modulation,a uniform crystallinity along the growth direction and a denser μc-Si:H film can be obtained.However,an excessively high I Hα /I SiH may damage the interface properties,which is indicated by capacitance-voltage (C-V) measurements.Well controlling the ignition condition is critically important for the applications of Si thin films.