In-situ synchrotron X-ray scattering study of thin film growth by atomic layer deposition

We report an atomic layer deposition chamber for in-situ synchrotron X-ray scattering study of thin film growth. The chamber was designed for combined synchrotron X-ray reflectivity and two-dimensional grazing-incidence X-ray diffraction measurement to do a in-situ monitoring of ALD growth. We demonstrate ruthenium thermal ALD growth for the performance of the chamber. 10, 20, 30, 50, 70, 100, 150 and 250-cycled states are measured by X-ray scattering methods during ALD growth process. Growth rate is calculated from thickness values and the surface roughness of each state is estimated by X-ray reflectivity analysis. The crystal structure of initial growth state is observed by Grazing-incidence X-ray diffraction. These results indicate that in-situ X-ray scattering method is a promising analysis technique to investigate the initial physical morphology of ALD films.     

原子层沉积氧化铝包覆层增强五氧化二钒多孔薄膜电化学循环稳定性

最近,包覆氧化物进行表面修饰的方法已成功应用于改善锂离子电池阴极材料的容量稳定性。本文中,我们通过V2O5溶胶结合提拉法制备了V2O5多孔薄膜,并利用原子层沉积法对其包覆Al2O3原子层。V2O5多孔薄膜的电化学性质受包覆层厚度的影响,我们研究了不同薄膜厚度下的修饰效果。结果显示,原子层沉积法包覆不同厚度Al2O3原子层对锂离子电池的循环稳定性都有所改善,经10个ALD包覆循环的样品表现出最好的修饰效果。在此基础上,我们讨论探索了包覆Al2O3对容量及稳定性增强的机理。     

Growth and characterization of epitaxial anatase TiO2(001) on SrTiO3-buffered Si(001) using atomic layer deposition

Epitaxial anatase titanium dioxide (TiO₂) films have been grown by atomic layer deposition (ALD) on Si(001) substrates using a strontium titanate (STO) buffer layer grown by molecular beam epitaxy (MBE) to serve as a surface template. The growth of TiO₂ was achieved using titanium isopropoxide and water as the co-reactants at a substrate temperature of 225-250 °C. To preserve the quality of the MBE-grown STO, the samples were transferred in-situ from the MBE chamber to the ALD chamber. After ALD growth, the samples were annealed in-situ at 600 °C in vacuum (10^− 7 Pa) for 1-2 h. Reflection high-energy electron diffraction was performed during the MBE growth of STO on Si(001), as well as after deposition of TiO₂ by ALD. The ALD films were shown to be highly ordered with the substrate. At least four unit cells of STO must be present to create a stable template on the Si(001) substrate for epitaxial anatase TiO₂ growth. X-ray diffraction revealed that the TiO₂ films were anatase with only the (004) reflection present at 2θ = 38.2°, indicating that the c-axis is slightly reduced from that of anatase powder (2θ = 37.9°). Anatase TiO₂ films up to 100 nm thick have been grown that remain highly ordered in the (001) direction on STO-buffered Si(001) substrates.     

Charge-trapping characteristics of Al2O3/Cu/Al2O3 nanolaminate structures prepared through atomic layer deposition

The nanolaminate Al2O3/Cu/Al2O3 structures were constructed on p-type Si (001) substrates using atomic layer deposition (ALD) process with the aim to fabricating nonvolatile charge-trap memories. Low temperature Cu thin layers were deposited through plasma-enhanced atomic layre depositon of Cu aminoalkoxide (Cu(dmamb)2) combined with hydrogen plasma and Al2O3 layers were prepared by thermal atomic layer deposition of trimethylaluminum (TMA) combined with H2O. Nonvolatile features were confirmed using capacitance-voltage (C-V) measurements. The copper film functions as a charge-trapping layer and the Al2O3 thin layers were employed as tunneling and control oxide layers. Line shapes and binding energies of Cu metal and the thin layer of 6 nm Cu in nanolaminate structures were observed in the X-ray photoelectron spectroscopy (XPS) and high resolution transmission electron microscopy (TEM) image. The V(FB) shift width of the Al2O3 (28 nm)/Cu (6 nm)/Al2O3 (4.2 nm)/Si laminate structure is found to be 4.75 V in voltage sweeping between -10 and +10 V, leading to the trap density of 1.68 x 10(18) cm(-3).     

Bi2Te3热电薄膜的电化学原子层外延制备

采用电化学原子层外延法(ECALE)在Au电极上成功地制备了Bi2Te3化合物热电薄膜.通过循环伏安扫描研究Te和Bi在Au衬底上的电化学特性,使用自动沉积系统交替欠电位沉积Te、Bi原子层200个循环获得沉积物.XRD、EDX和FESEM测试结果表明循环沉积200层后得到的沉积物Bi和Te的化学计量比为2:3,且是Bi2Te3薄膜化合物,而非单质Bi和Te的简单混合;薄膜均匀、致密、平整且可重复性好,以(015)为最优取向外延生长的.     

Al2O3 and TiO2 atomic layer deposition on copper for water corrosion resistance

Al(2)O(3) and TiO(2) atomic layer deposition (ALD) were employed to develop an ultrathin barrier film on copper to prevent water corrosion. The strategy was to utilize Al(2)O(3) ALD as a pinhole-free barrier and to protect the Al(2)O(3) ALD using TiO(2) ALD. An initial set of experiments was performed at 177 °C to establish that Al(2)O(3) ALD could nucleate on copper and produce a high-quality Al(2)O(3) film. In situ quartz crystal microbalance (QCM) measurements verified that Al(2)O(3) ALD nucleated and grew efficiently on copper-plated quartz crystals at 177 °C using trimethylaluminum (TMA) and water as the reactants. An electroplating technique also established that the Al(2)O(3) ALD films had a low defect density. A second set of experiments was performed for ALD at 120 °C to study the ability of ALD films to prevent copper corrosion. These experiments revealed that an Al(2)O(3) ALD film alone was insufficient to prevent copper corrosion because of the dissolution of the Al(2)O(3) film in water. Subsequently, TiO(2) ALD was explored on copper at 120 °C using TiCl(4) and water as the reactants. The resulting TiO(2) films also did not prevent the water corrosion of copper. Fortunately, Al(2)O(3) films with a TiO(2) capping layer were much more resilient to dissolution in water and prevented the water corrosion of copper. Optical microscopy images revealed that TiO(2) capping layers as thin as 200 ? on Al(2)O(3) adhesion layers could prevent copper corrosion in water at 90 °C for ~80 days. In contrast, the copper corroded almost immediately in water at 90 °C for Al(2)O(3) and ZnO films by themselves on copper. Ellipsometer measurements revealed that Al(2)O(3) films with a thickness of ~200 ? and ZnO films with a thickness of ~250 ? dissolved in water at 90 °C in ~10 days. In contrast, the ellipsometer measurements confirmed that the TiO(2) capping layers with thicknesses of ~200 ? on the Al(2)O(3) adhesion layers protected the copper for ~80 days in water at 90 °C. The TiO(2) ALD coatings were also hydrophilic and facilitated H(2)O wetting to copper wire mesh substrates.     

Characterization of Al2O3 thin films fabricated through atomic layer deposition on polymeric substrates

This paper reports on the fabrication of good quality Al₂O₃ thin films on flexible substrates including polyethylene naphthalate (PEN), polyethylene terephthalate (PET) and Polyamide at different temperatures down to 50 °C under very short water purging steps of 10 s. Al₂O₃ films with appreciable growth rates having good morphological, chemical, electrical and optical characteristics have been produced. Growth rates of 1.16, 1.14 and 1.15 Å/cycle have been observed at 50 °C for PET, PEN and polyamide substrates respectively. The surface morphology has been improved with the increase in deposition temperature. Low average arithmetic roughness of 0.88 and 0.78 nm have been recorded for the Al₂O₃ films deposited at 150 °C on PEN and polyamide respectively. The XPS analysis confirmed the fabrication of Al₂O₃ films without any carbon contamination and Al 2p, Al 2s and O 1s peaks were appeared at binding energies of 74, 119 and 531 eV, respectively. Excellent insulating properties were observed for the Al₂O₃ films and optical transmittance of more than 85 % was recorded in the visible region. The experimental results suggest that polymeric materials are excellent candidates to be used as substrates in the fabrication of Al₂O₃ thin films through atomic layer deposition.     

(111)-Oriented Pb(Zr0.52Ti0.48)O3 thin film on Pt(111)/Si substrate using CoFe2O4 nano-seed layer by pulsed laser deposition

Perovskite Pb(Zr_0.52Ti_0.48)O₃ (PZT) thin film with perfect (111)-orientation was achieved on CoFe₂O₄ seeded-Pt(111)/Ti/SiO₂/Si substrate by pulsed laser deposition technique using target with limited excess Pb. Pyrochlore phase formation was suppressed on Pt by CoFe₂O₄ nano-seed layer (~7 nm), and perovskite PZT was achieved at temperature as low as 550 °C. CoFe₂O₄ seed layer that has perfect (111)-orientation acts as a promoter for perfectly (111)-orientated growth of PZT. PZT film grown at 600 °C has higher degree of crystalline orientation, lower surface roughness, and compacted microstructure in comparison to the film grown at 550 °C. The PZT film has a nano-size grain-feature structure with grain size of about 40–60 nm. Perovskite formation was also confirmed by ferroelectric measurement. The ferroelectric properties of PZT film grown at 600 °C is higher than that grown at 550 °C which could be attributed to the enhancement of the crystalline orientation, crystallinity, and microstructure of the film.     

Comparative study of the luminescence of Al2O3:Ti and Al2O3 crystals under VUV synchrotron radiation excitation

The comparative study of the luminescent properties of Al₂O₃:Ti crystal in comparison with those for undoped Al₂O₃ crystal counterpart is performed under synchrotron radiation excitation with an energy of 3.7–25 eV. Apart from the main emission band peaked at 725 nm related to the ²E → ²T₂ radiative transitions of Ti³⁺ ions, the luminescence of excitons localized around Ti ions in the band peaked at 290 nm and the luminescence of F⁺–Ti and F–Ti centers in the bands peaked at 325 and 434 nm are also found in the emission spectra of Al₂O₃:Ti crystal. We show also that the luminescence of Ti³⁺ ions in Al₂O₃:Ti crystal can be effectively excited by the luminescence of excitons localized around Ti dopant as well as by the luminescence of F–Ti centers.     

Characteristics of nanocomposite ZrO2/Al2O3 films deposited by plasma-enhanced atomic layer deposition

Nanocomposite ZrO2/Al2O3 (ZAO) films were deposited on Si by plasma-enhanced atomic layer deposition and the film characteristics including interfacial oxide formation, dielectric constant (k), and electrical breakdown strength were investigated without post-annealing process. In both the mixed and nano-laminated ZAO films, the thickness of the interfacial oxide layer (T(IL)) was considerably reduced compared to ZrO2 and Al2O3 films. The T(IL) was 0.8 nm in nano-composite films prepared at a mixing ratio (ZrO2:Al2O3) of 1:1. The breakdown strength and the leakage current level were greatly improved by adding Al2O3 as little as 7.9% compared to that of ZrO2 and were enhanced more with increasing content of Al2O3. The k of ZrO2 and mixed ZAO (Al2O3 7.9%) films were 20.0 and 16.5, respectively. These results indicate that the addition of Al2O3 to ZrO2 greatly improves the electrical properties with less cost of k compared to the addition of SiO2.     

Temperature-dependent evolution of the wetting layer thickness during Ge deposition on Si(001)

The evolution of the wetting layer (WL) thickness during Ge deposition on Si(001) is analyzed with the help of a rate-equation approach. The combined role of thickness, island volume and shape-dependent chemical potentials is considered. Several experimental observations, such as WL thinning following the pyramid-to-dome transformation, are captured by the model, as directly demonstrated by a close comparison with photoluminescence measurements (PL) on samples grown at three different temperatures. The limitations of the model in describing late stages of growth are critically addressed.     

Laser damage properties of TiO2/Al2O3 thin films grown by atomic layer deposition

Research on thin film deposited by atomic layer deposition (ALD) for laser damage resistance is rare. In this paper, it has been used to deposit TiO(2)/Al(2)O(3) films at 110 °C and 280 °C on fused silica and BK7 substrates. Microstructure of the thin films was investigated by x-ray diffraction. The laser-induced damage threshold (LIDT) of samples was measured by a damage test system. Damage morphology was studied under a Nomarski differential interference contrast microscope and further checked under an atomic force microscope. Multilayers deposited at different temperatures were compared. The results show that the films deposited by ALD had better uniformity and transmission; in this paper, the uniformity is better than 99% over 100 mm Φ samples, and the transmission is more than 99.8% at 1064 nm. Deposition temperature affects the deposition rate and the thin film microstructure and further influences the LIDT of the thin films. As to the TiO(2)/Al(2)O(3) films, the LIDTs were 6.73±0.47 J/cm(2) and 6.5±0.46 J/cm(2) at 110 °C on fused silica and BK7 substrates, respectively. The LIDTs at 11 °C are notably better than 280 °C.     

Large area nanorings fabricated using an atomic layer deposition Al(2)O(3) spacer for magnetic random access memory application

We have designed a novel atomic layer deposition (ALD) Al(2)O(3) spacer mask technique for fabricating large area high density nanoscale magnetic rings by photolithography for magnetic random access memory applications. A simple mask design and a low temperature ALD process were utilized to simplify the process. Dry etching of Al(2)O(3) and cobalt was investigated for optimizing the nanostructure dimension control. A ring array with density and dimensions below the limits for photolithography tools has been achieved. The magnetic behavior of the ring array was characterized using a SQUID (superconducting quantum interference device). The switching distribution and effects of interaction among ring arrays were studied by correlating simulation with experimental results.     

Effects of NH3 plasma pre-treatment of Ta substrate on atomic layer deposition of Cu thin film

Cu has replaced Al as an interconnection material in ultra-large integrated circuits, reducing resistance capacitance delay and yielding higher electro-migration reliability. However, as the feature size decreases, it becomes more difficult to produce reliable Cu wiring. In this work, the Plasma Enhanced Atomic Layer Deposition (PEALD) of Cu seed layers deposited on Ta substrates (both with and without NH3 plasma pretreatment) was investigated. The Cu seed layers deposited on NH3 plasma-pretreated Ta substrates were found to have favorable properties compared to films deposited without plasma pretreatment because of an increase in the surface energy and of the Ta substrate, which resulted in improved surface wetting.     

氨化Si基Ga2O3/In制备GaN薄膜

研究了Ga2O3/In 膜反应自组装制备GaN薄膜,再将Ga2O3/In膜在高纯氨气气氛中氨化反应得到GaN薄膜,用X射线衍射(XRD),傅里叶红外吸收(FTIR),扫描电镜(SEM),原子力显微镜(AFM),透射电镜(TEM)对样品进行结构,形貌的分析.测试结果表明:用此方法得到了六方纤锌矿结构的GaN多晶膜,且900℃时成膜的质量最好.     

Surface treatment for high-quality Al2O3 and HfO2 layers deposited on HF-dipped surface by atomic layer deposition

Al₂O₃ and HfO₂ thin layers were deposited on either 0.7-nm chemical SiO₂ surface layers, HF-dipped Si surfaces or on HF-dipped Si surfaces with an innovative Cl₂ surface treatment. This chemical treatment leads to the formation of one mono-layer of –OH groups on the silicon surface without any SiO _x growth. Thicknesses, composition, and structure of the high-k layers as well as the nature of their interfaces with silicon were studied using spectrometric ellipsometry, attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS). While deposition on a HF-dipped Si surface led to a nucleation retardation and to a 3-dimensional growth mode, high-quality, uniform Al₂O₃ layers were obtained on a Cl₂-treated Si surface. XPS and ATR analyses showed a very small SiO _x regrowth, less than 0.26 nm during deposition.     

Characterization of air-exposure/activation cycles of porous Ti-Zr-V getter film using synchrotron radiation photoemission spectroscopy

Highly porous TiZrV films on (100) Si wafers were used to study the oxidation state of a film surface after three gas-adsorption/activation cycles using synchrotron radiation photoemission spectroscopy (SRPES). The oxidation state and composition of porous TiZrV film are highly affected by the present conditions of air-exposure/activation cycles. In the porous TiZrV films after activation treatment, the C content on the surface of the films gradually increased with increasing air-exposure/activation cycles. In the porous TiZrV film after air-exposure treatment, the O content on the surface of the films decreased with increasing of air-exposure/activation cycles. The concentration of Zr on the film surface increased with increasing of air-exposure/activation cycles. These results are caused by the formation of metal carbides on the film surface.     

Electron energy-loss spectroscopy investigation of Y2O3 films on Si (001) substrate

Electron energy -loss spectroscopy has been used to investigate the interface between a Y₂O₃ film and the silicon substrate. The chemical composition of the interface layer is revealed to be nearly pure amorphous SiO₂. Yttrium silicates are found at the Y₂O₃/SiO₂ interface region. The formation of the interfacial yttrium silicates has been interpreted by the direct chemical reaction between the deposited Y₂O₃ film and the SiO₂ interface layer. The Si L₂₃ and O K edges of yttrium silicates (Y₂SiO₅ and Y₂Si₂O₇) have been calculated by the first-principle full multiple - scattering method. The theoretical results are consistent with the experimental spectra, which confirms the formation of yttrium silicates.     

Growth of textured LiNbO3 thin film on Si (111) substrate by pulsed laser deposition

Highly c-axis oriented LiNbO₃ thin films have been deposited on Si (111) substrates by pulsed laser deposition. A stoichiometric sintered LiNbO₃ is used as the target. The c-axis orientation and stoichiometry of LiNbO₃ films are strongly influenced by substrate temperature and oxygen pressure. The substrate temperature 600 °C and oxygen pressure 20–30 Pa are found to be optimized parameters for the growth of textured film. The results showed that the size and the density of droplets decreased with increasing substrate temperature, and droplets would disappear when substrate temperature is increased above 600 °C. The surface microstructures of LiNbO₃ films under optimized conditions are fine, uniform and dense. The AFM images ensured that the as-grown films are good enough to be integrated with the semiconductor devices.