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At least 703 records · Page 39

Electrical behavior of atomic layer deposited high quality SiO{sub 2} gate dielectric

Comprehensive and systematic electrical studies were performed on fabrication of high quality SiO{sub 2} thin films MOS capacitor using the robust, novel, and simple atomic layer deposition (ALD) technique using highly reactive ozone and tris (dimethylamino) silane (TDMAS) precursors. Ideal capacitance–voltage curve exhibits a very small frequency dispersion and hysteresis behavior of the SiO{sub 2} MOS capacitor grown at 1 s TDMAS pulse, suggesting excellent interfacial quality and purity of the film as probed using x-ray photoelectron studies. The flat-band voltage of the device shifted from negative toward positive voltage axis with increase of TDMAS pulses from 0.2 to 2 s. Based on an equivalent oxide thickness point of view, all SiO{sub 2} films have gate leakage current density of (5.18 × 10{sup −8} A/cm{sup 2}) as well as high dielectric break down fields of more than (∼10 MV/cm), which is better and comparable to that of thermally grown SiO{sub 2} at temperatures above 800 °C. These appealing electrical properties of ALD grown SiO{sub 2} thin films enable its potential applications such as high-quality gate insulators for thin film MOS transistors, as well as insulators for sensor and nanostructures on nonsilicon substrates.

36 MATERIALS SCIENCE↗

Infrared study on room-temperature atomic layer deposition of HfO{sub 2} using tetrakis(ethylmethylamino)hafnium and remote plasma-excited oxidizing agents

Room-temperature atomic layer deposition (ALD) of HfO{sub 2} was examined using tetrakis (ethylmethylamino)hafnium (TEMAH) and remote plasma-excited water and oxygen. A growth rate of 0.26 nm/cycle at room temperature was achieved, and the TEMAH adsorption and its oxidization on HfO{sub 2} were investigated by multiple internal reflection infrared absorption spectroscopy. It was observed that saturated adsorption of TEMAH occurs at exposures of ∼1 × 10{sup 5} L (1 L = 1 × 10{sup −6} Torr s) at room temperature, and the use of remote plasma-excited water and oxygen vapor is effective in oxidizing the TEMAH molecules on the HfO{sub 2} surface, to produce OH sites. The infrared study suggested that Hf–OH plays a role as an adsorption site for TEMAH. The reaction mechanism of room temperature HfO{sub 2} ALD is discussed in this paper.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impact of surface morphology of Si substrate on performance of Si/ZnO heterojunction devices grown by atomic layer deposition technique

In this paper, the authors have investigated the structural, optical, and electrical characteristics of silicon nanowire (SiNW)/zinc oxide (ZnO) core–shell nanostructure heterojunctions and compared their characteristics with Si/ZnO planar heterojunctions to investigate the effect of surface morphology of Si substrate in the characteristics of Si/ZnO heterojunction devices. In this work, ZnO thin film was conformally deposited on both p-type 〈100〉 planar Si substrate and substrate with vertically aligned SiNW arrays by atomic layer deposition (ALD) method. The x-ray diffraction spectra show that the crystalline structures of Si/ZnO heterojunctions are having (101) preferred orientation, whereas vertically oriented SiNW/ZnO core–shell heterojunctions are having (002)-oriented wurtzite crystalline structures. The photoluminescence (PL) spectra of Si/ZnO heterojunctions show a very sharp single peak at 377 nm, corresponding to the bandgap of ZnO material with no other defect peaks in visible region; hence, these devices can have applications only in UV region. On the other hand, SiNW/ZnO heterojunctions are having band-edge peak at 378 nm along with a broad emission band, spreading almost throughout the entire visible region with a peak around 550 nm. Therefore, ALD-grown SiNW/ZnO heterojunctions can emit green and red light simultaneously. Reflectivity measurement of the heterojunctions further confirms the enhancement of visible region peak in the PL spectra of SiNW/ZnO heterojunctions, as the surface of the SiNW/ZnO heterojunctions exhibits extremely low reflectance (<3%) in the visible wavelength region compared to Si/ZnO heterojunctions (>20%). The current–voltage characteristics of both Si/ZnO and SiNW/ZnO heterojunctions are measured with large area ohmic contacts on top and bottom of the structure to compare the electrical characteristics of the devices. Due to large surface to-volume ratio of SiNW/ZnO core–shell heterojunction devices, the output current rating is about 130 times larger compared to their planar version at 2 V forward bias voltage. This higher output current rating can be exploited for fabricating high-performance nanoelectronic and optoelectronic devices in near future.

42 ENGINEERING↗

Integration of molecular-layer-deposited aluminum alkoxide interlayers into inorganic nanolaminate barriers for encapsulation of organic electronics with improved stress resistance

Diffusion barrier stacks for the encapsulation of organic electronics made from inorganic nanolaminates of Al{sub 2}O{sub 3} and TiO{sub 2} with aluminum alkoxide interlayers have been deposited by atomic layer deposition (ALD) and molecular layer deposition (MLD). As a part of the MLD process development, the deposition of aluminum alkoxide with low a density of about 1.7 g/cm{sup 3} was verified. The ALD/MLD diffusion barrier stack is meant to be deposited either on a polymer film, creating a flexible barrier substrate, or on top of a device on glass, creating a thin-film encapsulation. In order to measure the water vapor transmission rate (WVTR) through the barrier, the device is replaced by a calcium layer acting as a water sensor in an electrical calcium test. For the barrier stack applied as thin-film encapsulation on glass substrates, high resolution scanning electron microscopy investigations indicate that the inorganic nanolaminates without MLD interlayers are brittle as they crack easily upon the stress induced by the corroding calcium below. The introduction of up to three MLD interlayers of 12 nm each into the 48 nm barrier film laminate successfully mitigates stress issues and prevents the barrier from cracking. Using the three MLD interlayer configurations on glass, WVTRs of as low as 10{sup −5} g/m{sup 2}/d are measured at 38 °C and 32% relative humidity. On polymer barrier substrates, the calcium is evaporated onto the barrier stack and encapsulated with a cavity glass. In this configuration, the corroding calcium has space for expansion and gas release without affecting the underlying barrier film. In consequence, a WVTR of about 3 × 10{sup −3} g/m{sup 2}/d is measured for all samples independently of the number of MLD interlayers. In conclusion, a stabilization and preservation of the ALD barrier film against mechanical stress is achieved by the introduction of MLD interlayers into the inorganic nanolaminate.

36 MATERIALS SCIENCE↗

Infrared and thermoelectric power generation in thin atomic layer deposited Nb-doped TiO{sub 2} films

Infrared radiation is used to radiatively transfer heat to a nanometric power generator (NPG) device with a thermoelectric Nb-doped TiO{sub 2} film deposited by atomic layer deposition (ALD) as the active element, onto a borosilicate glass substrate. The linear rise of the produced voltage with respect to the temperature difference between the “hot” and “cold” junctions, typical of the Seebeck effect, is missing. The discovery of the violation of the Seebeck effect in NPG devices combined with the ability of ALD to tune thermoelectric thin film properties could be exploited to increase the efficiency of these devices for energy harvesting purposes.

36 MATERIALS SCIENCE↗

Characterization of Ru thin films from a novel CVD/atomic layer deposition precursor “Rudense” for capping layer of Cu interconnects

The authors have succeeded in development of a novel Ru precursor, Ru(EtCp)(η{sup 5}-CH{sub 2}C(Me)CHC(Me)O) [Rudense], for CVD and atomic layer deposition (ALD) processes under nonoxidative condition. Rudense has sufficient vapor pressure and good thermal stability (decomposition temperature = ca. 230 °C). Ru thin films were grown on Pt, Ru, Si, and SiO{sub 2} substrates using Rudense and NH{sub 3} as Ru precursor and reactant, respectively. Rudense gave the conformal, low-impurity (<10{sup 21} atoms/cc), and low-resistivity (16 μΩ cm) Ru thin films. Moreover, Rudense showed substrate selectivity; therefore, Rudense will be a candidate for area-selective CVD and ALD precursor for Ru capping layers of Cu interconnects.

36 MATERIALS SCIENCE↗

Characterization of ZnO film grown on polycarbonate by atomic layer deposition at low temperature

ZnO is an attractive material for use in various technological products such as phosphors, gas sensors, and transparent conductors. Recently, aluminum-doped zinc oxide has received attention as a potential replacement for indium tin oxide, which is one of the transparent conductive oxides used in flat panel displays, organic light-emitting diodes, and organic solar cells. In this study, the characteristics of ZnO films deposited on polycarbonate (PC) substrates by atomic layer deposition (ALD) are investigated for various process temperatures. The growth mechanism of these films was investigated at low process temperatures using x-ray diffraction (XRD) and x-ray photoelectron spectroscopy (XPS). XRD and XPS were used to determine the preferred orientation and chemical composition of the films, respectively. Furthermore, the difference of the deposition mechanisms on an amorphous organic material, i.e., PC substrate and an inorganic material such as silicon was discussed from the viewpoint of the diffusion and deposition of precursors. The structure of the films was also investigated by chemical analysis in order to determine the effect of growth temperature on the films deposited by ALD.

36 MATERIALS SCIENCE↗

Improved film quality of plasma enhanced atomic layer deposition SiO{sub 2} using plasma treatment cycle

Chemical, physical, and electrical characteristics of high quality silicon dioxide (SiO{sub 2}) films grown using low temperature plasma enhanced atomic layer deposition (PE-ALD) have been investigated as a buffer layer for three dimensional vertical NAND flash memory devices. The comparative angle resolved x-ray photoelectron spectroscopy studies show the plasma treatment cycle causes to shift the core level binding energy (chemical shifts) in the SiO{sub 2} film. The wet etch rates with respect to plasma treatment cycle times were varied due to curing of the SiO{sub 2} network defects by Ar{sup +} ions and oxygen radicals. It is assumed that the angle between the bonds linking SiO{sub 4} tetrahedra is a critical point understanding the variation in wet etch rate of SiO{sub 2}. The features of wet etch rate of low temperature high quality SiO{sub 2} demonstrated lower than high temperature low-pressure chemical vapor deposition (LP-CVD) SiO{sub 2} values. In addition, the better step-coverage compared to that of the LP-CVD SiO{sub 2} film was achieved from the deep trench structure having the 20:1 aspect ratio. PE-ALD SiO{sub 2} with plasma treatment cycle showed excellent I–V properties with higher breakdown voltage compared to LP-CVD SiO{sub 2} and similar to the thermal SiO{sub 2} carrier transport plot.

36 MATERIALS SCIENCE↗

Influence of PEDOT:PSS on the effectiveness of barrier layers prepared by atomic layer deposition in organic light emitting diodes

Organic light emitting diodes (OLEDs) are well suited for energy saving lighting applications, especially when thinking about highly flexible and large area devices. In order to avoid the degradation of the organic components by water and oxygen, OLEDs need to be encapsulated, e.g., by a thin sheet of glass. As the device is then no longer flexible, alternative coatings are required. Atomic layer deposition (ALD) is a very promising approach in this respect. The authors studied OLEDs that were encapsulated by 100 nm Al{sub 2}O{sub 3} deposited by ALD. The authors show that this coating effectively protects the active surface area of the OLEDs from humidity. However, secondary degradation processes still occur at sharp edges of the OLED stack where the extremely thin encapsulation layer does not provide perfect coverage. Particularly, the swelling of poly(3,4-ethylenedioxythiophene) mixed with poly(styrenesulfonate), which is a popular choice for the planarization of the bottom electrode and at the same time acts as a hole injection layer, affects the effectiveness of the encapsulation layer.

36 MATERIALS SCIENCE↗

Continuous production of nanostructured particles using spatial atomic layer deposition

In this paper, the authors demonstrate a novel spatial atomic layer deposition (ALD) process based on pneumatic transport of nanoparticle agglomerates. Nanoclusters of platinum (Pt) of ∼1 nm diameter are deposited onto titania (TiO{sub 2}) P25 nanoparticles resulting to a continuous production of an active photocatalyst (0.12–0.31 wt. % of Pt) at a rate of about 1 g min{sup −1}. Tuning the precursor injection velocity (10–40 m s{sup −1}) enhances the contact between the precursor and the pneumatically transported support flows. Decreasing the chemisorption temperature (from 250 to 100 °C) results in more uniform distribution of the Pt nanoclusters as it decreases the reaction rate as compared to the rate of diffusion into the nanoparticle agglomerates. Utilizing this photocatalyst in the oxidation reaction of Acid Blue 9 showed a factor of five increase of the photocatalytic activity compared to the native P25 nanoparticles. The use of spatial particle ALD can be further expanded to deposition of nanoclusters on porous, micron-sized particles and to the production of core–shell nanoparticles enabling the robust and scalable manufacturing of nanostructured powders for catalysis and other applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Atomic layer deposition of tin oxide and zinc tin oxide using tetraethyltin and ozone

Silicon or glass substrates exposed to sequential pulses of tetraethyltin (TET) and ozone (O{sub 3}) were coated with thin films of SnO{sub 2}. Self-limiting deposition was found using 8 s pulse times, and a uniform thickness per cycle (TPC) of 0.2 nm/cycle was observed in a small, yet reproducible, temperature window from 290 to 320 °C. The as-deposited, stoichiometric SnO{sub 2} films were amorphous and transparent above 400 nm. Interspersing pulses of diethylzinc and O{sub 3} among the TET:O{sub 3} pulses resulted in deposition of zinc tin oxide films, where the fraction of tin, defined as [at. % Sn/(at. % Sn + at. % Zn)], was controlled by the ratio of TET pulses, specifically n{sub TET}:(n{sub TET} + n{sub DEZ}) where n{sub TET} and n{sub DEZ} are the number of precursor/O{sub 3} subcycles within each atomic layer deposition (ALD) supercycle. Based on film thickness and composition measurements, the TET pulse time required to reach saturation in the TPC of SnO{sub 2} on ZnO surfaces was increased to >30 s. Under these conditions, film stoichiometry as a function of the TET pulse ratio was consistent with the model devised by Elliott and Nilsen. The as-deposited zinc tin oxide (ZTO) films were amorphous and remained so even after annealing at 450 °C in air for 1 h. The optical bandgap of the transparent ZTO films increased as the tin concentration increased. Hall measurements established that the n-type ZTO carrier concentration was 3 × 10{sup 17} and 4 × 10{sup 18} cm{sup −3} for fractional tin concentrations of 0.28 and 0.63, respectively. The carrier mobility decreased as the concentration of tin increased. A broken gap pn junction was fabricated using ALD-deposited ZTO and a sputtered layer of cuprous oxide. The junction demonstrated ohmic behavior and low resistance consistent with similar junctions prepared using sputter-deposited ZTO.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Surface compositions of atomic layer deposited Zn{sub 1−x}Mg{sub x}O thin films studied using Auger electron spectroscopy

In this paper, the authors present Auger electron spectroscopy (AES) studies of Zn{sub 1−x}Mg{sub x}O (ZMO) films grown via interrupted atomic-layer deposition (ALD) techniques. The ZMO films were fabricated by alternating ALD deposition of ZnO and MgO layers up to 1000 cycles. Zn{sub 1−x}Mg{sub x}O films with progressively decreasing Mg/Zn ratios (Mg/Zn = 1/1, 1/2, 1/3, 1/4, 1/5, 1/6, 1/9, and 2/8, 3/12, 4/16, and 5/20) were fabricated for this study. The AES results exhibit an abrupt drop of Mg composition on the ZMO surface when the Mg/Zn < 1/3. Additionally, the surface composition ratios of O to Mg, O to Zn, and Mg to Zn were estimated with known Auger sensitivity factors. The results indicate that Mg ions diffuse into the bulk, forming Zn{sub 1−x}Mg{sub x}O alloys.

42 ENGINEERING↗

Dynamic order reduction of thin-film deposition kinetics models: A reaction factorization approach

A set of numerical tools for the analysis and dynamic dimension reduction of chemical vapor and atomic layer deposition (ALD) surface reaction models is developed in this work. The approach is based on a two-step process where in the first, the chemical species surface balance dynamic equations are factored to effectively decouple the (nonlinear) reaction rates, a process that eliminates redundant dynamic modes and that identifies conserved quantities. If successful, the second phase is implemented to factor out redundant dynamic modes when species relatively minor in concentration are omitted; if unsuccessful, the technique points to potential model structural problems. An alumina ALD process is used for an example consisting of 19 reactions and 23 surface and gas-phase species. Using the approach developed, the model is reduced by nineteen modes to a four-dimensional dynamic system without any knowledge of the reaction rate values. Results are interpreted in the context of potential model validation studies.

42 ENGINEERING↗

Low-temperature atomic layer deposition of copper(II) oxide thin films

Copper(II) oxide thin films were grown by atomic layer deposition (ALD) using bis-(dimethylamino-2-propoxide)copper [Cu(dmap){sub 2}] and ozone in a temperature window of 80–140 °C. A thorough characterization of the films was performed using x-ray diffraction, x-ray reflectivity, UV‐Vis spectrophotometry, atomic force microscopy, field emission scanning electron microscopy, x-ray photoelectron spectroscopy, and time-of-flight elastic recoil detection analysis techniques. The process was found to produce polycrystalline copper(II) oxide films with a growth rate of 0.2–0.3 Å per cycle. Impurity content in the films was relatively small for a low temperature ALD process.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Gas permeation barriers deposited by atmospheric pressure plasma enhanced atomic layer deposition

This paper reports on aluminum oxide (Al{sub 2}O{sub 3}) thin film gas permeation barriers fabricated by atmospheric pressure atomic layer deposition (APPALD) using trimethylaluminum and an Ar/O{sub 2} plasma at moderate temperatures of 80 °C in a flow reactor. The authors demonstrate the ALD growth characteristics of Al{sub 2}O{sub 3} films on silicon and indium tin oxide coated polyethylene terephthalate. The properties of the APPALD-grown layers (refractive index, density, etc.) are compared to that deposited by conventional thermal ALD at low pressures. The films films deposited at atmospheric pressure show water vapor transmission rates as low as 5 × 10{sup −5} gm{sup −2}d{sup −1}.

36 MATERIALS SCIENCE↗

Atomic layer deposition of environmentally benign SnTiO{sub x} as a potential ferroelectric material

Inspired by the need to discover environmentally friendly, lead-free ferroelectric materials, here the authors report the atomic layer deposition of tin titanate (SnTiO{sub x}) aiming to obtain the theoretically predicted perovskite structure that possesses ferroelectricity. In order to establish the growth conditions and probe the film structure and ferroelectric behavior, the authors grew SnTiO{sub x} films on the commonly used Si(100) substrate. Thin films of SnTiO{sub x} have been successfully grown at a deposition temperature of 200 °C, with a Sn/Ti atomic layer deposition (ALD) cycle ratio of 2:3 and postdeposition heat treatments under different conditions. X-ray photoelectron spectroscopy revealed excellent composition tunability of ALD. X-ray diffraction spectra suggested anatase phase for all films annealed at 650 and 350 °C, with peak positions shifted toward lower 2-theta angles indicating enlarged unit cell volume. The film annealed in O{sub 2} at 350 °C exhibited piezoresponse amplitude and phase hysteresis loops, indicative of the existence of switchable polarization.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Plasma-enhanced atomic layer deposition of titanium oxynitrides films: A comparative spectroscopic and electrical study

The process parameters' impact of the plasma-enhanced atomic layer deposition (PE-ALD) method on the oxygen to nitrogen (O/N) ratio in titanium oxynitride (TiO{sub x}N{sub y}) films was studied. Titanium(IV)isopropoxide in combination with NH{sub 3} plasma and tetrakis(dimethylamino)titanium by applying N{sub 2} plasma processes were investigated. Samples were characterized by the in situ spectroscopic ellipsometry, x-ray photoelectron spectroscopy, and electrical characterization (current–voltage: I-V and capacitance–voltage: C-V) methods. The O/N ratio in the TiO{sub x}N{sub y} films is found to be very sensitive for their electric properties such as conductivity, dielectric breakdown, and permittivity. Our results indicate that these PE-ALD film properties can be tuned, via the O/N ratio, by the selection of the process parameters and precursor/coreactant combination.

36 MATERIALS SCIENCE↗