前驱体和退火温度对Nd2O3薄膜组分影响的定量研究

采用Nd(thd)₃和O₃作为反应前驱体, 利用先进的原子层淀积方法在P型硅(100)衬底上制备了超薄Nd₂O₃介质膜, 并在N₂气氛下进行了退火处理. 采用X射线光电子能谱仪对薄膜样品组分进行分析. 研究结果表明, 淀积过程中将前驱体温度从175 ℃提高到185 ℃后, 薄膜的质量得到提高, O/Nd 原子比达到1.82, 更接近理想的化学计量比, 介电常数也从6.85升高到10.32.     

Characterization and electrical properties of high-<Emphasis Type="Italic">k</Emphasis> GdScO<Subscript>3</Subscript> thin films grown by atomic layer deposition

Gadolinium scandium oxide (Gd-scandate, GdScO₃) thin films were grown by atomic layer deposition (ALD) from β-diketonate precursors M(thd)₃ (M=Gd, Sc; thd=2,2,6,6-tetramethyl-3,5-heptanedionato) and ozone. The deposition parameters were optimized to produce films with the stoichiometric 1:1 metal ratio and a series of samples with nominal thicknesses of 5, 10, 15, and 20 nm were prepared. At 300 °C the metal precursor pulsing ratio Gd:Sc=5:6 yielded amorphous stoichiometric films and a growth rate of 0.21 Å/cycle. The films stayed amorphous up to 900 °C. The surface was probed with an AFM and the rms roughness was found to be 0.3 nm for the 5–20 nm thick films. The electrical properties of the as-deposited films proved to be very promising, with a dielectric constant of ～22 and leakage current density of 340 μA/cm², measured at -2 V.     

Effects of deposition temperature and hydrogen flow rate on the properties of the Al-doped ZnO thin films and amorphous silicon thin-film solar cells

A compound of 98 mol% ZnO and 1 mol% Al₂O₃ (AZO, Al:Zn = 98:2) was sintered at 1350 °C as a target and the AZO thin films were deposited on glass using a radio frequency magnetron sputtering system. The effects of deposition temperature (from room temperature to ～300 °C) on the optical transmission spectrum of the AZO thin films were studied. The Burstein–Moss shift was observed and used to prove that defects in the AZO thin films decreased with increasing deposition temperature. The variations in the optical band gap (E _g) values of the AZO thin films were evaluated from plots of (αhv)²=c(hν?E _g), revealing that the measured E _g values increased with increasing deposition temperature. The effects of the H₂ flow rate during deposition (0 %～11.76 %, deposition temperature of 200 °C) on the crystallization, morphology, resistivity, carrier concentration, carrier mobility, and optical transmission spectrum of the AZO thin films were measured. The chemical structures of the Ar-deposited and 2 % H₂-flow rate-deposited AZO thin films (both were deposited at 200 °C) were investigated by XPS to clarify the mechanism of improvement in resistivity. The prepared AZO thin films were also used as transparent electrodes to fabricate amorphous silicon thin-film solar cells, and their properties were also measured.     

Photoactivity passivation of TiO<Subscript>2</Subscript> nanoparticles using molecular layer deposited (MLD) polymer films

Pigment-grade anatase TiO₂ particles (160 nm) were passivated using ultra-thin insulating films deposited by molecular layer deposition (MLD). Trimethylaluminum (TMA) and ethylene glycol (E.G) were used as aluminum alkoxide (alucone) precursors in the temperature range of 100–160 °C. The growth rate varied from 0.5 nm/cycle at 100 °C to 0.35 nm/cycle at 160 °C. Methylene blue oxidation tests indicated that the photoactivity of pigment-grade TiO₂ particles was quenched after 20 cycles of alucone MLD film, which was comparable to 70 cycles of Al₂O₃ film deposited by atomic layer deposition (ALD). Alucone films would decompose in the presence of water at room temperature and would form a more stable composite containing aluminum, which decreased the passivation effect on the photoactivity of TiO₂ particles.     

Effective surface passivation of crystalline silicon using ultrathin Al2O3 films and Al2O3/SiNx stacks

We measure surface recombination velocities (SRVs) below 10 cm/s on p‐type crystalline silicon wafers passivated by atomic–layer–deposited (ALD) aluminium oxide (Al₂O₃) films of thickness ≥10 nm. For films thinner than 10 nm the SRV increases with decreasing Al₂O₃ thickness. For ultrathin Al₂O₃ layers of 3.6 nm we still attain a SRV < 22 cm/s on 1.5 Ω cm p‐Si and an exceptionally low SRV of 1.8 cm/s on high‐resistivity (200 Ω cm) p‐Si. Ultrathin Al₂O₃ films are particularly relevant for the implementation into solar cells, as the deposition rate of the ALD process is extremely low compared to the frequently used plasma‐enhanced chemical vapour deposition of silicon nitride (SiN_x). Our experiments on silicon wafers passivated with stacks composed of ultrathin Al₂O₃ and SiN_x show that a substantially improved thermal stability during high‐temperature firing at 830 °C is obtained for the Al₂O₃/SiN_x stacks compared to the single‐layer Al₂O₃ passivation. Al₂O₃/SiN_x stacks are hence ideally suited for the implementation into industrial‐type silicon solar cells where the metal contacts are made by screen‐printing and high‐temperature firing of metal pastes. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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.     

Reaction mechanism studies for platinum nanoparticle growth by atomic layer deposition

Mass spectrometry is used to study the reaction mechanism of platinum (Pt) atomic layer deposition (ALD) on large quantities of high surface area silica gel particles in a fluidized bed reactor. (Methylcyclopentadienyl)trimethylplatinum [(MeCp)PtMe₃] and oxygen are used as precursors. Studies are conducted at a substrate temperature of 320 °C. The self-limiting behavior of ALD appears to be disrupted with overexposure of Pt precursor. The amount of the deposited Pt and the size of the Pt nanoparticles increase with an increasing overdose time of Pt precursor. This can be explained by the thermal decomposition of Pt precursor at the reaction temperature of 320 °C and the in situ sintering of Pt nanoparticles forming larger particles. This finding is significant and its understanding is essential for better control of Pt deposition to achieve desirable morphological and structural properties for different application requirements.     

Enhancement of photoluminescence intensity from Si nanodots using Al2O3 surface passivation layer grown by atomic layer deposition

Temperature-dependent photoluminescence (PL) from Si nanodots with Al₂O₃ surface passivation layers was studied. The Si nanodots were grown by low pressure chemical vapor deposition and the Al₂O₃ thin films were prepared by atomic layer deposition (ALD), respectively. The BOE (Buffer-Oxide-Etch) treatment resulted in the damaged surface of Si nanodots and thus caused dramatic reduction in the PL intensity. Significant enhancement of the PL intensity from Si nanodots after the deposition of Al₂O₃ thin films was observed over a wide temperature range, indicating the remarkable surface passivation effect to suppress the non-radiative recombination at the surface of Si nanodots. The results demonstrated that the Al₂O₃ surface passivation layers grown by ALD are effectually applicable to nanostructured silicon devices.     

Monitoring structural defects and crystallinity of carbon nanotubes in thin films

We report the influence of catalyst formulation and reaction temperature on the formation of carbon nanotube (CNT) thin films by the chemical vapour deposition (CVD) method. Thin films of CNTs were grown on Fe-Mo/Al₂O₃-coated silicon wafer by thermal decomposition of methane at different temperatures ranging from 800 to 1000°C. The electron microscopic investigations, SEM as well as HRTEM, of the as-grown CNT thin films revealed the growth of uniform multi-walled CNTs in abundance. The intensity ratio of D-band to G-band and FWHM of G-band through Raman measurements clearly indicated the dependency of structural defects and crystallinity of CNTs in thin films on the catalyst formulation and CVD growth temperature. The results suggest that thin films of multi-walled CNTs with negligible amount of defects in the nanotube structure and very high crystallinity can be obtained by thermal CVD process at 925°C.     

High mobility In2O3:H transparent conductive oxides prepared by atomic layer deposition and solid phase crystallization

The preparation of high‐quality In₂O₃:H, as transparent conductive oxide (TCO), is demonstrated at low temperatures. Amorphous In₂O₃:H films were deposited by atomic layer deposition at 100 °C, after which they underwent solid phase crystallization by a short anneal at 200 °C. TEM analysis has shown that this approach can yield films with a lateral grain size of a few hundred nm, resulting in electron mobility values as high as 138 cm²/V s at a device‐relevant carrier density of 1.8 × 10²⁰ cm^–3. Due to the extremely high electron mobility, the crystallized films simultaneously exhibit a very low resistivity (0.27 mΩ cm) and a negligible free carrier absorption. In conjunction with the low temperature processing, this renders these films ideal candidates for front TCO layers in for example silicon heterojunction solar cells and other sensitive optoelectronic applications. (© 2014 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Fabrication of coaxial nanowire heterostructures: SiO x nanowires with conformal TiO2 coatings

Silica nanowires, grown via the active oxidation of a silicon substrate, have been coated with TiO₂ using two coating methods: solution-based deposition of Ti-alkoxides and atomic layer deposition. Analysis of as-deposited and annealed films shows that it is possible to produce stable conformal coatings of either the anatase or rutile phases of TiO₂ on nanowires with diameters greater than 100 nm when annealed between 500–600°C and 800–900°C, respectively, with annealing at higher temperatures (1050°C) producing coatings with a highly facetted rutile morphology. The efficacy of the process is shown to depend on nanowire diameter, with nanowires having diameters less than about 100 nm fusing together during solution-based coating and decomposing during TiO₂ atomic layer deposition. The use of a suitable buffer layer is shown to be an effective means of minimizing nanowire decomposition. Finally, annealing coated nanowires under active oxidation conditions (1100°C) is shown to be an effective technique for depositing additional conformal SiO _x coatings, thereby providing a means of fabricating multi-layered coaxial nanostructures.     

Low‐temperature atomic layer deposition of MoOx for silicon heterojunction solar cells

The preparation of high‐quality molybdenum oxide (MoO_x) is demonstrated by plasma‐enhanced atomic layer deposition (ALD) at substrate temperatures down to 50 °C. The films are amorphous, slightly substoichiometric with respect to MoO₃, and free of other elements apart from hydrogen (&11 at%). The films have a high transparency in the visible region and their compatibility with a‐Si:H passivation schemes is demonstrated. It is discussed that these aspects, in conjunction with the low processing temperature and the ability to deposit very thin conformal films, make this ALD process promising for the future application of MoO_x in hole‐selective contacts for silicon heterojunction solar cells. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Effect of the Si excess on the structure and the optical properties of Nd-doped Si-rich silicon oxide

Nd-doped Si-rich silicon oxide thin films were produced by radio frequency magnetron co-sputtering of three confocal cathodes: Si, SiO₂, and Nd₂O₃, in pure argon plasma at 500 °C. The microstructure and optical properties of the films were investigated versus silicon excess and post-deposition annealing treatment by means of ellipsometry and Fourier transform infrared spectrometry as well as by the photoluminescence method. A notable emission from Nd³⁺ ions was obtained for the as-deposited sample, while the films annealed at 900 °C showed the highest peak intensity. The maximum emission was observed for the films with 4.7 at% of Si excess.     

Surface reactions of TiCl4 and Al(CH3)3 on GaAs(100) during the first half-cycle of atomic layer deposition

GaAs(100) was exposed to pulses of trimethylaluminum (TMA, Al(CH₃)₃) and titanium tetrachloride (TiCl₄) to mimic the first half-cycle of atomic layer deposition (ALD). Both precursors removed the 9.0 ± 1.6 Å-thick mixed oxide consisting primarily of As₂O₃ with a small Ga₂O component that was left on the surface after aqueous HF treatment and vacuum annealing. In its place, TMA deposited an Al₂O₃ layer, but TiCl₄ exposure left Cl atoms adsorbed to an elemental As layer. This suggests that oxygen was removed by the formation of a volatile oxychloride species. A small TiO₂ coverage of approximately 0.04 monolayer remained on the surface for deposition temperatures of 89 °C to 135 °C, but no TiO₂ was present from 170 °C to 230 °C. The adsorbed Cl layer chemically passivated the surface at these temperatures and blocked TiO₂ deposition even after 50 full ALD cycles of TiCl₄ and water vapor. The Cl and As layers desorbed simultaneously at higher temperature producing peaks in the temperature programmed desorption spectrum in the range 237–297 °C. This allowed TiO₂ deposition at 300 °C in single TiCl₄ pulse experiments. On the native oxide-covered surface where there was a higher proportional Ga oxide composition, TiCl₄ exposure deposited TiO₂.     

Crystallization behaviour of ALD-Ta2O5 thin films: the application of in-situ TEM

The microstructure of Ta₂O₅ thin films, deposited onto Si substrates by atomic layer deposition (ALD), was investigated, using in situ transmission electron microscopy (TEM). As-deposited amorphous films crystallize as the orthorhombic phase L-Ta₂O₅ upon heating at 750°C. Two dominant crystallographic orientations are found, one with (0?0?1) and (1?11?0) planes perpendicular to the substrate, while the other has (0?0?1) planes parallel to the substrate. The grains consist of subgrains which are rotated a few degrees with respect to each other. The kinetics of the crystallization were studied by in-situ TEM heating experiments carried out at nominal temperatures of 790°C, 820°C and 850°C. They reveal that the growth and crystallization activation energies are about 4.2?eV and 6.3?eV, respectively. Tilted subgrains keep forming during growth until they come in contact with neighbouring grains. The crystallization behaviour can be approximated by the Kolmogorov–Johnson–Mehl–Avrami (KJMA or Avrami) equation, giving mode parameters of 2.5, 1.9, and 1.7 at 790°C, 820°C and 850°C, respectively. A small value of mode parameters is attributed to decreasing growth and nucleation rates with time.     

Challenges regarding thin film deposition of garnet electrolytes for all-solid-state lithium batteries with high energy density

In this work, we studied the deposition of garnet electrolyte thin films in order to realize an all-solid-state battery with high energy density. Therefore, in a first step we investigated the stability of the garnet Li₅La₃Ta₂O₁₂ with the spinel LiCoMnO₄ in order to determine the temperature window for a successful thin film deposition on high-voltage spinels. A mixture of both materials showed a thermal stability up to 600 °C, so that all-solid-state batteries could be realized when the electrolyte is applied at a low deposition temperature. The second part of the work was the thin film deposition of Li₅La₃Ta₂O₁₂ by a sputter deposition process. When a stoichiometric Li₅La₃Ta₂O₁₂ sputter target was used, the surface of the target showed a depletion of lithium after several depositions, which leads to decreasing Li content in the thin films. In order to compensate the lithium loss we enriched the target with LiOH?H₂O. Depositions carried out with the lithium rich target showed the garnet structure on glass substrates after deposition at 500 °C. The garnet structure was observed on Au-coated EN 1.4767 substrates already at a substrate temperature of 400 °C, which is 300 K lower than comparable depositions of Li₇La₃Zr₂O₁₂. These results show that the combination of thin garnet-structured electrolytes and high-voltage spinels is possible.     

Ultrathin surface coatings to enhance cycling stability of LiMn2O4 cathode in lithium-ion batteries

Spinel LiMn₂O₄ suffers from severe dissolution when used as a cathode material in rechargeable Li-ion batteries. To enhance the cycling stability of LiMn₂O₄, we use the atomic layer deposition (ALD) method to deposit ultrathin and highly conformal Al₂O₃ coatings (as thin as 0.6–1.2 nm) onto LiMn₂O₄ cathodes with precise thickness control at atomic scale. Both bare and ALD-coated cathodes are cycled at a specific current of 300 mA g^?1 (2.5 C) in a potential range of 3.4–4.5 V (vs. Li/Li⁺). All ALD-coated cathodes exhibit significantly improved cycleability compared to bare cathodes. Particularly, the cathode coated with six Al₂O₃ ALD layers (0.9 nm thick) shows the best cycling performance, delivering an initial capacity of 101.5 mA h?g^?1 and a final capacity of 96.5 mA h?g^?1 after 100 cycles, while bare cathode delivers an initial capacity of 100.6 mA h?g^?1 and a final capacity of only 78.6 mA h?g^?1. Such enhanced electrochemical performances of ALD-coated cathodes are ascribed to the high-quality ALD oxide coatings that are highly conformal, dense, and complete, and thus protect active material from severe dissolution into electrolytes. Besides, cycling performances of coated cathodes can be easily optimized by accurately tuning coating thickness via varying ALD growth cycles.     

The effect of iridium precursor on oxide-supported iridium catalysts prepared by atomic layer deposition

Alumina, silica and beta zeolite supported iridium catalysts were prepared by atomic layer deposition (ALD) from two different metal precursors, Ir(acac)₃ and Ir(thd)(COD). The use of Ir(thd)(COD) in ALD is reported for the first time. The aim was to investigate the effect of the precursor on catalyst surface species, chemical state and characteristics.Controllable ALD reaction was successful with both iridium precursors on alumina and with Ir(acac)₃ on β zeolite. On these catalysts, iridium particle sizes were very small (1-3 nm). Instead, some thermal decomposition of both precursors was observed during deposition on silica. At conditions, where no or very little decomposition of the precursors took place, the differences in the chemical state and characteristics of the as-prepared Ir/support samples were negligible, In ALD, Ir(acac)₃ is slightly more stable at high deposition temperatures (>200 °C) while Ir(thd)(COD) enables the utilization of larger temperature range since it vaporizes at lower temperature compared to Ir(acac)₃. The results thus indicate that Ir(thd)(COD) is a suitable new precursor for ALD.     

High-rate reactive magnetron sputtering of zirconia films for laser optics applications

ZrO₂ exhibits low optical absorption in the near-UV range and is one of the highest laser-induced damage threshold (LIDT) materials; it is, therefore, very attractive for laser optics applications. This paper reports explorations of reactive sputtering technology for deposition of ZrO₂ films with low extinction coefficient k values in the UV spectrum region at low substrate temperature. A high deposition rate (64 % of the pure metal rate) process is obtained by employing active feedback reactive gas control which creates a stable and repeatable deposition processes in the transition region. Substrate heating at 200 °C was found to have no significant effect on the optical ZrO₂ film properties. The addition of nitrogen to a closed-loop controlled process was found to have mostly negative effects in terms of deposition rate and optical properties. Open-loop O₂ gas-regulated ZrO₂ film deposition is slow and requires elevated (200 °C) substrate temperature or post-deposition annealing to reduce absorption losses. Refractive indices of the films were distributed in the range n = 2.05–2.20 at 1,000 nm and extinction coefficients were in the range k = 0.6 × 10^?4 and 4.8 × 10^?3 at 350 nm. X-ray diffraction analysis showed crystalline ZrO₂ films consisted of monoclinic + tetragonal phases when produced in Ar/O₂ atmosphere and monoclinic + rhombohedral or a single rhombohedral phase when produced in Ar/O₂ + N₂. Optical and physical properties of the ZrO₂ layers produced in this study are suitable for high-power laser applications in the near-UV range.     

Active metal brazing of Al2O3 to Kovar® (Fe–29Ni–17Co wt.%) using Copper ABA® (Cu–3.0Si–2.3Ti–2.0Al wt.%)

The application of an active braze alloy (ABA) known as Copper ABA® (Cu–3.0Si–2.3Ti–2.0Al wt.%) to join Al₂O₃ to Kovar® (Fe–29Ni–17Co wt.%) has been investigated. This ABA was selected to increase the operating temperature of the joint beyond the capabilities of typically used ABAs such as Ag–Cu–Ti-based alloys. Silica present as a secondary phase in the Al₂O₃ at a level of ~5 wt.% enabled the ceramic component to bond to the ABA chemically by forming a layer of Si₃Ti₅ at the ABA/Al₂O₃ interface. Appropriate brazing conditions to preserve a near-continuous Si₃Ti₅ layer on the Al₂O₃ and a continuous Fe₃Si layer on the Kovar® were found to be a brazing time of ≤15 min at 1025 °C or ≤2 min at 1050 °C. These conditions produced joints that did not break on handling and could be prepared easily for microscopy. Brazing for longer periods of time, up to 45 min, at these temperatures broke down the Si₃Ti₅ layer on the Al₂O₃, while brazing at ≥1075 °C for 2–45 min broke down the Fe₃Si layer on the Kovar® significantly. Further complications of brazing at ≥1075 °C included leakage of the ABA out of the joint and the formation of a new brittle silicide, Ni₁₆Si₇Ti₆, at the ABA/Al₂O₃ interface. This investigation demonstrates that it is not straightforward to join Al₂O₃ to Kovar® using Copper ABA®, partly because the ranges of suitable values for the brazing temperature and time are quite limited. Other approaches to increase the operating temperature of the joint are discussed.