Quantum cascade laser-based measurement of metal alkylamide density during atomic layer deposition

An in situ gas-phase diagnostic for the metal alkylamide compound tetrakis(ethylmethylamido) hafnium (TEMAH), Hf[N(C(2)H(5))(CH(3))](4), was demonstrated. This diagnostic is based on direct absorption measurement of TEMAH vapor using an external cavity quantum cascade laser emitting at 979 cm(-1), coinciding with the most intense TEMAH absorption in the mid-infrared spectral region, and employing 50 kHz amplitude modulation with synchronous detection. Measurements were performed in a single-pass configuration in a research-grade atomic layer deposition (ALD) chamber. To examine the detection limit of this technique for use as a TEMAH delivery monitor, this technique was demonstrated in the absence of any other deposition reactants or products, and to examine the selectivity of this technique in the presence of deposition products that potentially interfere with detection of TEMAH vapor, it was demonstrated during ALD of hafnium oxide using TEMAH and water. This technique successfully detected TEMAH at molecular densities present during simulated industrial ALD conditions. During hafnium oxide ALD using TEMAH and water, absorbance from gas-phase reaction products did not interfere with TEMAH measurements while absorption by reaction products deposited on the optical windows did interfere, although interfering absorption by deposited reaction products corresponded to only ≈4% of the total derived TEMAH density. With short measurement times and appropriate signal averaging, estimated TEMAH minimum detectable densities as low as ≈2 × 10(12) molecules/cm(3) could be obtained. While this technique was demonstrated specifically for TEMAH delivery and hafnium oxide ALD using TEMAH and water, it should be readily applicable to other metal alkylamide compounds and associated metal oxide and nitride deposition chemistries, assuming similar metal alkylamide molar absorptivity and molecular density in the measurement chamber.     

In situ deposition of metal coatings

Ceramic powder particles were metal coated by in situ deposition from decomposable compounds. The ceramic powder and a decomposable metal compound were mixed by tumbling and then heat treated in argon or in hydrogen to deposit the metal. Cermets with continuous metal matrices were obtained by hot pressing metal-coated powders or by in situ decomposition to form the metal during hot pressing. Tungsten-coated Eu₂O₃ powders were obtained by thermal decomposition of W(CO)₆ or by hydrogen reduction of WO₃. Europia-tantalum cermets were made by decomposition of tantalum hydride during hot pressing. Particles of Eu₂O₃ were coated with rhenium by decomposition of ReCl₃ or ReO_x and with molybdenum from the oxide. Cobalt and platinum coatings were deposited on ZrO₂-Y₂O₃ particles by decomposition of the chlorides. The uniformity of metal deposition depends on the mixing and on the particle size of the decomposable compound. The concurrent chemical reaction appears to enhance distribution of the metal by surface diffusion during the heat treatment that results in deposition. The extent of adherence or chemical bonding can be varied through the rate of deposition.     

Rayleigh-instability-induced metal nanoparticle chains encapsulated in nanotubes produced by atomic layer deposition

Cu nanoparticle chains encapsulated in Al2O3 nanotubes were successfully generated in a controlled manner by reduction of CuO nanowires embedded in Al2O3 at a sufficiently high temperature. The Al2O3 coating was deposited by atomic layer deposition (ALD). The particles mainly show a rodlike shape and are regularly distributed. The particle diameters and chain lengths corresponding to the inner diameters and lengths of the tubes, respectively, are controlled by the size of the CuO nanowire templates. Rayleigh instability, assisted by the uniform volume shrinkage created by the reduction of oxide to metal, is proposed to induce the formation of the nanochains. This method may potentially be extended to the synthesis of nanochains of other metals by reducing corresponding oxide nanowires embedded in ALD shells.     

Highly porous metal oxide networks of interconnected nanotubes by atomic layer deposition

Mesoporous metal oxide networks composed of interconnected nanotubes with ultrathin tube walls down to 3 nm and high porosity up to 90% were fabricated by atomic layer deposition (ALD) of alumina or titania onto templates of swelling-induced porous block copolymers. The nanotube networks possessed dual sets of interconnected pores separated by the tube wall whose thickness could be finely tuned by altering ALD cycles. Because of the excellent pore interconnectivity and high porosity, the alumina nanotube networks showed superior humidity-sensing performances.     

Spontaneous formation of vertical magnetic-metal-nanorod arrays during plasma-enhanced atomic layer deposition

A novel fabrication method of Co and Ni metal nanorods (NRs) without catalyst or template, based on the spontaneous formation of NRs during plasma-enhanced atomic layer deposition (PE-ALD) is developed. Pure Co and Ni NRs 9-10 nm in diameter are synthesized on SiO(2) and Si substrates by using metal-organic precursors and an NH(3) plasma mixed with a suitable amount of SiH(4) as a reactant. The lengths of the NRs are controlled on the nanometer scale by changing the number of PE-ALD growth cycles. Superconducting quantum interference device magnetometer measurements confirm the magnetic anisotropy of Co NRs caused by shape anisotropy.     

In situ electrical property measurements of metal/(plasma polysiloxane)/metal structures

The in situ dielectric response of plasma-polymerized hexamethyldisiloxane was measured. Evidence for evolution of the dielectric response as a function of time and environmental conditions was reported. A strong correlation between the electron spin resonance signal and dielectric losses was shown. Under vacuum, the dielectric losses could arise from active radicals acting as trapping-detrapping centres whereas contamination of the film by the atmosphere gives rise to a high level of dielectric losses owing to the formation of polar bonds involving the reaction of radicals with oxygen atoms.     

In situ thickness control during plasma deposition of hydrogenated amorphous silicon films by time-resolved microwave conductivity measurements

Transient photoconductivity measurements have been performed in situ during plasma-enhanced chemical vapor deposition of amorphous hydrogenated silicon by a contactless method that uses the change of the microwave reflection after laser pulse illumination. Through the use of the interference pattern of the amplitude of the transients of microwave reflection during the layer growth, the actual thickness of the amorphous film can be determined. In the case of crystalline silicon substrates, the change in the light absorption in the substrate modified by the growth of the amorphous layer is measured directly. An example of the optimization of antireflective layers on crystalline silicon substrates is shown. A good agreement is found between the experimental data and calculations of optical reflection and transmission on the multilayer structures.     

In situ observation of electrochemical Ostwald ripening during sodium deposition

Sodium(Na)metal batteries(SMBs)using Na anode are potential"beyond lithium"electrochemical technology for future energy storage applications.However,uncontrolla...     

GaPO4 sensors for gravimetric monitoring during atomic layer deposition at high temperatures

The quartz crystal microbalance is extremely useful for in situ monitoring of thin-film growth by atomic layer deposition (ALD) in a viscous flow environment. Unfortunately, conventional AT-quartz sensors are limited to growth temperatures below approximately 300 degrees C. Gallium orthophosphate (GaPO4) is an alternative piezoelectric material offering much greater high-temperature frequency stability than AT-quartz (SiO2). Our measurements reveal that the temperature coefficient for Y-11 degrees GaPO4 decreases linearly with temperature reaching 3 Hz/ degrees C at 450 degrees C. In contrast, the temperature coefficient for the SiO2 sensor increases as the cube of the sensor temperature to 650 Hz/ degrees C at 390 degrees C. To examine the effect of temperature fluctuations on the sensor frequency, we exposed the SiO2 and GaPO4 sensors to helium pulses at 400 degrees C. The resulting frequency change measured for the SiO2 sensor was approximately 40 times greater than that of the GaPO4 sensor. Next, we performed Al2O3 ALD using alternating tri-methylaluminum/water exposures at 400 degrees C and monitored the growth using the SiO2 and GaPO4 sensors. The GaPO4 sensor yielded well-defined pulse shapes in agreement with predictions, while the SiO2 pulses were severely distorted. Measurements during TiO2 ALD using alternating titanium tetrachloride/water exposures at 450 degrees C with the GaPO4 sensor also showed well-defined ALD mass steps.     

原子层淀积制备金属氧化物薄膜研究进展

原子层淀积(ALD)技术作为一种先进的薄膜制备方法近年来越来越得到重视,它能精确地控制薄膜的厚度和组分,实现原子层级的生长,生长的薄膜具有很好的均匀性和保形性,因而在微电子和光电子等领域有广泛的应用前景。本文综述了ALD技术的基本原理,及其在金属氧化物薄膜制备上的研究进展。     

Making inert polypropylene fibers chemically responsive by combining atomic layer deposition and vapor phase chemical grafting

Uniformly grafting organic reactive molecular species, e.g. -NH?, onto substrates that have three-dimensional complex structures and are chemically inert is challenging. The vapor phase chemical grafting of organic molecules enabled by low temperature metal oxide atomic layer deposition (ALD) is presented as a general and promising solution to functionalize inert matrices with complex morphology, such as nonwoven polypropylene mats, through the controllable self-limited molecular assembly mechanism in a combined ALD and vapor phase chemical grafting process.     

Ultrathin oxide films by atomic layer deposition on graphene

In this paper, a method is presented to create and characterize mechanically robust, free-standing, ultrathin, oxide films with controlled, nanometer-scale thickness using atomic layer deposition (ALD) on graphene. Aluminum oxide films were deposited onto suspended graphene membranes using ALD. Subsequent etching of the graphene left pure aluminum oxide films only a few atoms in thickness. A pressurized blister test was used to determine that these ultrathin films have a Young's modulus of 154 ± 13 GPa. This Young's modulus is comparable to much thicker alumina ALD films. This behavior indicates that these ultrathin two-dimensional films have excellent mechanical integrity. The films are also impermeable to standard gases suggesting they are pinhole-free. These continuous ultrathin films are expected to enable new applications in fields such as thin film coatings, membranes, and flexible electronics.     

Thin film atomic layer deposition equipment for semiconductor processing

Atomic layer deposition (ALD) of ultrathin high-K dielectric films has recently penetrated research and development lines of several major memory and logic manufacturers due to the promise of unprecedented control of thickness, uniformity, quality and material properties. LYNX-ALD technology from Genus, currently at beta phase, was designed around the anticipation that future ultrathin materials are likely to be binary, ternary or quaternary alloys or nanolaminate composites. A unique chemical delivery system enables synergy between traditional, production-proven low pressure chemical vapor deposition (LPCVD) technology and atomic layer deposition (ALD) controlled by sequential surface reactions. Source chemicals from gas, liquid or solid precursors are delivered to impinge on reactive surfaces where self-limiting surface reactions yield film growth with layer-by-layer control. Surfaces are made reactive by the self-limiting reactions, by surface species manipulation, or both. The substrate is exposed to one reactant at a time to suppress possible chemical vapor deposition (CVD) contribution to the film. Precisely controlled composite materials with multiple-component dielectric and metal–nitride films can be deposited by ALD techniques. The research community has demonstrated these capabilities during the past decade. Accordingly, ALD equipment for semiconductor processing is unanimously in high demand. However, mainstream device manufacturers still criticize ALD to be non-viable for Semiconductor device processing. This article presents a broad set of data proving feasibility of ALD technology for semiconductor device processing.     

Low temperature atomic layer deposition of titania thin films

This paper presents a comprehensive study of atomic layer deposition of TiO₂ films on silicon and polycarbonate substrates using TiCl₄ and H₂O as precursors at temperatures in the range 80-120 °C. An in-situ quartz crystal microbalance was used to monitor different processing conditions and the resultant films were characterised ex-situ using a suite of surface analytical tools. In addition, the contact angle and wettability of as-deposited and UV irradiated films were assessed. The latter was found to reduce the contact angle from ≥ 80° to < 10°. Finally, the effect of surface pre-treatment on film toughness and adhesion was investigated and the results show a significant improvement for the pre-treated films.     

Spatial atomic layer deposition of zinc oxide thin films

Zinc oxide thin films have been deposited at high growth rates (up to ~1 nm/s) by spatial atomic layer deposition technique at atmospheric pressure. Water has been used as oxidant for diethylzinc (DEZ) at deposition temperatures between 75 and 250 °C. The electrical, structural (crystallinity and morphology), and optical properties of the films have been analyzed by using Hall, four-point probe, X-ray diffraction, scanning electron microscopy, spectrophotometry, and photoluminescence, respectively. All the films have c-axis (100) preferential orientation, good crystalline quality and high transparency (～ 85%) in the visible range. By varying the DEZ partial pressure, the electrical properties of ZnO can be controlled, ranging from heavily n-type conductive (with 4 mOhm.cm resistivity for 250 nm thickness) to insulating. Combining the high deposition rates with a precise control of functional properties (i.e., conductivity and transparency) of the films, the industrially scalable spatial ALD technique can become a disruptive manufacturing method for the ZnO-based industry.     

Monocrystalline zinc oxide films grown by atomic layer deposition

In the present work we report on the monocrystalline growth of (00.1) ZnO films on GaN template by the Atomic Layer Deposition technique. The ZnO films were obtained at temperature of 300 °C using dietylzinc (DEZn) as a zinc precursor and deionized water as an oxygen precursor. High resolution X-ray diffraction analysis proves that ZnO layers are monocrystalline with rocking curve FWHM of the 00.2 peak equals to 0.07°. Low temperature photoluminescence shows a sharp and bright excitonic line with FWHM of 13 meV.     

Selective atomic layer deposition of metal oxide thin films on patterned self-assembled monolayers formed by microcontact printing

We demonstrate a selective atomic layer deposition of TiO2, ZrO2, and ZnO thin films on patterned alkylsiloxane self-assembled monolayers. Microcontact printing was done to prepare patterned monolayers of the alkylsiloxane on Si substrates. The patterned monolayers define and direct the selective deposition of the metal oxide thin films using atomic layer deposition. The selective atomic layer deposition is based on the fact that the metal oxide thin films are selectively deposited only on the regions exposing the silanol groups of the Si substrates because the regions covered with the alkylsiloxane monolayers do not have any functional group to react with precursors.     

Understanding 'clean-up' of III-V native oxides during atomic layer deposition using bulk first principles models

The use of III-V materials as the channel in future transistor devices is dependent on removing the deleterious native oxides from their surface before deposition of a gate dielectric. Trimethylaluminium has been found to achieve in situ 'clean-up' of the oxides of GaAs and InGaAs before atomic layer deposition (ALD) of alumina. Here we propose six reaction mechanisms for 'clean-up,' featuring exchange of ligands between surface atoms, reduction of arsenic oxide by methyl groups and desorption of various products. We use first principles Density Functional Theory (DFT) to determine which mechanistic path is thermodynamically favoured based on models of the bulk oxides and gas-phase products. We therefore predict that 'clean-up' of arsenic oxides mostly produces As4 gas. Most C is predicted to form C2H6 but with some C2H4, CH4 and H2O. An alternative pathway is non-redox ligand exchange, which allows non-reducible oxides to be cleaned-up.     

Energy deposition in boundary gas layer during initiation of nanosecond sliding surface discharge

The process of rapid gas heating in the region of distributed pulsed sliding surface gas discharge (plasma sheet) of nanosecond duration has been studied. The fraction of electric energy converted into heat during the passage of discharge current has been estimated from a detailed analysis of the dynamics of shock wave fields arising upon the initiation of discharge. Experiments are performed in quiescent gases (air, nitrogen, helium) and in supersonic airflows behind a plane shock wave in a shock tube at gas densities within 0.04–0.45 kg/m³ and flow velocities up to 1600 m/s.     

In situ and ex situ stress measurements of YF3 single layer optical coatings deposited by electron beam evaporator

Yttrium fluoride (YF₃) is a material with good potential as a single-layer anti-reflection (AR) coating deposited onto glass substrates. YF₃ is a possible candidate to replace more studied fluorides such as MgF₂ or ThF₄ the latter being radioactive. For thin-film photovoltaic solar cells, depositing such layers could be a cost-effective way of improving the transmission of light to the p–n junction. However, long-term stability of these AR coatings is an important issue to be considered. This paper is concerned with the residual stress of YF₃ single layers deposited onto glass substrates, being a potential failure mechanism. The measured stress values are correlated to the structure of the layers, using ex situ characterization techniques, such as X-ray diffraction (XRD) and atomic force microscopy (AFM), in an attempt to explain the observed changes. Three substrate temperatures were investigated during deposition, namely 25, 115, and 210 °C. Intrinsic stress of up to 197 MPa has been observed in amorphous YF₃ single layers deposited by electron beam evaporation, at ambient temperature. At a substrate temperature of 210 °C, the intrinsic stress decreased to 67 MPa in the YF₃ layer, developing an orthorhombic structure. Adsorptive stress is an important issue encountered in YF₃ layers, directly related to a low packing density. The in situ stress measurements were carried out using a novel optical approach with a laser-fiber system, briefly introduced here. The residual stress values measured with this novel optical system were compared to two ex situ stress measurement techniques. The optical performance of the YF₃ single layers was also assessed using a spectrometer ex situ and in situ by the interferometry capability of the novel in situ monitoring device.