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At least 361 records · Page 20
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Photo-stability and time-resolved photoluminescence study of colloidal CdSe/ZnS quantum dots passivated in Al{sub 2}O{sub 3} using atomic layer deposition

We report photo-stability enhancement of colloidal CdSe/ZnS quantum dots (QDs) passivated in Al{sub 2}O{sub 3} thin film using the atomic layer deposition (ALD) technique. 62% of the original peak photoluminescence (PL) intensity remained after ALD. The photo-oxidation and photo-induced fluorescence enhancement effects of both the unpassivated and passivated QDs were studied under various conditions, including different excitation sources, power densities, and environment. The unpassivated QDs showed rapid PL degradation under high excitation due to strong photo-oxidation in air while the PL intensity of Al{sub 2}O{sub 3} passivated QDs was found to remain stable. Furthermore, recombination dynamics of the unpassivated and passivated QDs were investigated by time-resolved measurements. The average lifetime of the unpassivated QDs decreases with laser irradiation time due to photo-oxidation. Photo-oxidation creates surface defects which reduces the QD emission intensity and enhances the non-radiative recombination rate. From the comparison of PL decay profiles of the unpassivated and passivated QDs, photo-oxidation-induced surface defects unexpectedly also reduce the radiative recombination rate. The ALD passivation of Al{sub 2}O{sub 3} protects QDs from photo-oxidation and therefore avoids the reduction of radiative recombination rate. Our experimental results demonstrated that passivation of colloidal QDs by ALD is a promising method to well encapsulate QDs to prevent gas permeation and to enhance photo-stability, including the PL intensity and carrier lifetime in air. This is essential for the applications of colloidal QDs in light-emitting devices.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2020

Chemical approaches to artificial photosynthesis: A molecular, dye-sensitized photoanode for O 2 production prepared by layer-by-layer self-assembly

We describe here the preparation of a family of photoanodes for water oxidation that incorporate an electron acceptor–chromophore–catalyst in single molecular assemblies on nano-indium tin oxide (nanoITO) electrodes on fluorine-doped tin oxide (FTO). The assemblies were prepared by using a layer-by-layer, Atomic Layer Deposition (ALD), self-assembly approach. In the procedure, addition of an electron acceptor viologen derivative followed by a Ru II (bpy) chromophore and a pyridyl derivative of the water oxidation catalyst [Ru(bda) (L) 2 ] (bda = 2,2'-bipyridine-6,6'-dicarboxylate) 2 , were linked by ALD by addition of the bridge precursors TiO 2 , ZrO 2 , and Al 2 O 3 as the bridging groups giving the assemblies, FTO|nanoITO|–MV 2+ –ALD MO 2 –RuP2 2+ –ALD M'O 2 –WOC. In a series of devices, the most efficient gave water oxidation with an incident photon to current efficiency of 2.2% at 440 nm. Transient nanosecond absorption measurements on the assemblies demonstrated that the slow step in the intra-assembly electron transfer is the electron transfer from the chromophore through the viologen bridge to the nanoITO electrode.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Correlation between ferroelectricity and ferroelectric orthorhombic phase of Hf x Zr 1-x O 2 thin films using synchrotron x-ray analysis

The change in the interplanar spacing ( d -spacing) including the ferroelectric orthorhombic (O) phase in the low-temperature fabricated Hf x Zr 1-x O 2 (HZO) films was studied using synchrotron grazing-incidence wide-angle x-ray scattering analysis. The 10-nm-thick HZO films were fabricated by thermal and plasma-enhanced atomic layer deposition (TH- and PE-ALD) methods using H 2 O gas and O 2 plasma as oxidants, respectively, and a post-metallization annealing (PMA) was performed at 300–400 °C. The d -spacing of the mixture of (111)-, (101)-, and (111)-planes of O, tetragonal (T), and cubic (C) phases, respectively, for the TH- and PE-ALD HZO films increased up to 2.99 Å with an increase in PMA temperature, while the d -spacing estimated by conventional x-ray diffraction was 2.92 Å regardless of the PMA temperature. The remanent polarization (2 P r = P r + - P r - ) of the HZO films increased as the PMA temperature increased. It is clear that the 2 P r value satisfied a linear relationship as a function of the d -spacing of O(111)/T(101)/C(111) phases. Furthermore, the wake-up effect was found to depend on the ferroelectric O phase formation. The wake-up effect was significantly reduced in both the TH- and PE-ALD HZO films after the PMA at 400 °C due to the increase in the ferroelectric O phase formation. The leakage current density ( J )–electric field properties of the PE-ALD HZO film with the lowest d -spacing were divided into three steps, such as low, middle, and large J values, in the wake-up (10 3 cycles), pristine (10 0 cycle), and fatigue (10 7 cycles) states, respectively. Therefore, an analysis of the ferroelectric O phase is very important for understanding the ferroelectricity including endurance.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Nucleation and growth process of atomic layer deposition platinum nanoparticles on strontium titanate nanocuboids

Uniform, well-dispersed platinum nanoparticles were grown on SrTiO 3 nanocuboids via atomic layer deposition (ALD) using (methylcyclopentadienyl)trimethylplatinum (MeCpPt(Me)3) and water. For the first half-cycle of the deposition particles formed through two sequential processes: initial nucleation and growth. The final particle size after a single complete ALD cycle was dependent on the reaction temperature which alters the net Pt deposition per cycle. Additional cycles resulted in further growth of previously formed particles. However, the increase in size per cycle during additional ALD cycles, beyond the first, was significantly lower as less Pt was deposited due to carbonaceous material that partially covers the surface and prevents further MeCpPt(Me) 3 adsorption and reaction. The increase in particle size was also temperature dependent due to changes in the net Pt deposition. Pt nanoparticles increased in size by 59% and 76% after 15 ALD cycles for reaction temperatures of 200 °C and 300 °C, respectively. There was minimal change in the number of particles per unit area as a function of reaction time, indicating that there was minimal Ostwald ripening or secondary nucleation for the reaction conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Ultra-thin ZrO 2 overcoating on CuO-ZnO-Al 2 O 3 catalyst by atomic layer deposition for improved catalytic performance of CO 2 hydrogenation to dimethyl ether

Abstract An ultra-thin overcoating of zirconium oxide (ZrO 2 ) film on CuO-ZnO-Al 2 O 3 (CZA) catalysts by atomic layer deposition (ALD) was proved to enhance the catalytic performance of CZA/HZSM-5 (H form of Zeolite Socony Mobil-5) bifunctional catalysts for hydrogenation of CO 2 to dimethyl ether (DME). Under optimal reaction conditions (i.e. 240 °C and 2.8 MPa), the yield of product DME increased from 17.22% for the bare CZA/HZSM-5 catalysts, to 18.40% for the CZA catalyst after 5 cycles of ZrO 2 ALD with HZSM-5 catalyst. All the catalysts modified by ZrO 2 ALD displayed significantly improved catalytic stability of hydrogenation of CO 2 to DME reaction, compared to that of CZA/HZSM-5 bifunctional catalysts. The loss of DME yield in 100 h of reaction was greatly mitigated from 6.20% (loss of absolute value) to 3.01% for the CZA catalyst with 20 cycles of ZrO 2 ALD overcoating. Characterizations including hydrogen temperature programmed reduction, x-ray powder diffraction, and x-ray photoelectron spectroscopy revealed that there was strong interaction between Cu active centers and ZrO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Low temperature atomic layer deposition of PbO 2 for electrochemical applications

A low temperature atomic layer deposition (ALD) process for PbO 2 was developed using bis(1-dimethylamino-2-methyl-2-propanolate)lead(II), Pb(DMAMP) 2 , and O 3 as the reactants, with a high growth rate of 2.6 Å/cycle. PbO 2 readily reduces under low oxygen partial pressures at moderate temperatures making it challenging to deposit ALD PbO 2 from Pb 2+ precursors. However, thin films deposited with this process showed small crystalline grains of α-PbO 2 and β-PbO 2 , without signs of reduced PbO x phases. The ALD PbO 2 thin films show the high electrical conductivity characteristic of bulk PbO 2 . In situ measurements of ALD PbO 2 film conductivity during growth suggest a reaction mechanism by which sub-surface oxygen mobility contributes to the growth of resistive PbO or PbO x during the Pb(DMAMP) 2 surface reaction step, which is only fully oxidized from Pb 2+ to Pb 4+ during the O 3 reaction step. These films were electrochemically reduced to PbSO 4 in H 2 SO 4 and then reoxidized to PbO 2 , demonstrating their suitability for use as an electrode material for fundamental battery research and other electrochemical applications.

atomic layer deposition↗
DOE OSTI2025

Development of an atomic layer deposition system for deposition of alumina as a hydrogen permeation barrier

Tritium permeation into and through materials poses a critical challenge for the development of nuclear fusion reactors. Minimizing tritium permeation is essential for the safe and efficient use of available fuel supplies. In this work, we present the design, construction, and validation of custom atomic layer deposition (ALD) and deuterium permeation measurement systems aimed at developing thin-film hydrogen permeation barriers. Using the ALD system, we deposited conformal $\mathrm{Al}_{2}\mathrm{O}_{3}$ films on copper foil substrates and characterized their growth behavior, morphology, and composition. ALD growth rates of ∼1.1 Å/cycle were achieved for temperatures between 100 ∘ C and 210 ∘ C. Permeation measurements on bare and alumina coated copper foils revealed a significant reduction in deuterium flux with the addition of a ∼10 nm $\mathrm{Al}_{2}\mathrm{O}_{3}$ layer. While bare copper followed diffusion-limited transport consistent with Sievert’s law, the alumina-coated samples exhibited surface-limited, pore-mediated transport with linear pressure dependence. Arrhenius analysis showed distinct differences in activation energy for the two transport regimes, and permeation reduction factors exceeding an order of magnitude were observed. These results demonstrate the potential of ALD-grown $\mathrm{Al}_{2}\mathrm{O}_{3}$ films as effective hydrogen isotope barriers and provide a foundation for future studies on film optimization and integration into fusion-relevant components.

atomic layer deposition↗
DOE OSTI2020

In situ x-ray studies of the incipient ZnO atomic layer deposition on In 0.53 Ga 0.47 As

We describe in detail how ZnO films grow on In 0.53 Ga 0.47 As substrates by atomic layer deposition (ALD), employing a suite of in situ synchrotron x-ray techniques. Combining results from different measurements allows the distinguishment of three different growth behaviors: an initial, slow linear growth, often referred to as a growth delay (regime I), followed by a nonlinear growth (regime II), and finally, a steady, linear growth (regime III), the last of which is the self-limited growth behavior characteristic of ALD. By the end of regime I, the In 0.53 Ga 0.47 As surface is covered with an ultrathin, poorly ordered Zn oxide layer. The transition from regime I to II is clearly evidenced by the appearance in the x-ray absorption spectra of characteristic features of the wurtzite structure, as well as the nucleation and growth of ZnO grains (three-dimensional) on top of the poorly ordered Zn oxide layer. Regime II ends when the growth per cycle reaches a constant level. We show that the water pressure during growth has an impact on the duration of the growth delay (regime I), unlike the substrate temperature. In the regime of steady growth, we observe that the rate of deposition obtained for all temperatures inside the ALD window is 0.17 nm cy(-1). The deposition temperature has clear effects on the film texture and initial crystallization behavior, as well as the final crystallinity and thicknesses of the layers adjacent to the In 0.53 Ga 0.47 As substrate. Based on the experimental results and earlier ab initio calculations and Monte Carlo simulations of ZnO ALD on ZnO, we suggest reaction mechanisms consistent with our findings, and we present a model of growth starting from the very earliest stages of deposition to the steady growth regime.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Growth behavior and properties of atomic layer deposited tin oxide on silicon from novel tin(II)acetylacetonate precursor and ozone

In this work, a novel liquid tin(II) precursor, tin(II)acetylacetonate [Sn(acac){sub 2}], was used to deposit tin oxide films on Si(100) substrate, using a custom-built hot wall atomic layer deposition (ALD) reactor. Three different oxidizers, water, oxygen, and ozone, were tried. Resulting growth rates were studied as a function of precursor dosage, oxidizer dosage, reactor temperature, and number of ALD cycles. The film growth rate was found to be 0.1 ± 0.01 nm/cycle within the wide ALD temperature window of 175–300 °C using ozone; no film growth was observed with water or oxygen. Characterization methods were used to study the composition, interface quality, crystallinity, microstructure, refractive index, surface morphology, and resistivity of the resulting films. X-ray photoelectron spectra showed the formation of a clean SnO{sub x}–Si interface. The resistivity of the SnO{sub x} films was calculated to be 0.3 Ω cm. Results of this work demonstrate the possibility of introducing Sn(acac){sub 2} as tin precursor to deposit conducting ALD SnO{sub x} thin films on a silicon surface, with clean interface and no formation of undesired SiO{sub 2} or other interfacial reaction products, for transparent conducting oxide applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Self-forming Al oxide barrier for nanoscale Cu interconnects created by hybrid atomic layer deposition of Cu–Al alloy

The authors synthesized a Cu–Al alloy by employing alternating atomic layer deposition (ALD) surface reactions using Cu and Al precursors, respectively. By alternating between these two ALD surface chemistries, the authors fabricated ALD Cu–Al alloy. Cu was deposited using bis(1-dimethylamino-2-methyl-2-butoxy) copper as a precursor and H{sub 2} plasma, while Al was deposited using trimethylaluminum as the precursor and H{sub 2} plasma. The Al atomic percent in the Cu–Al alloy films varied from 0 to 15.6 at. %. Transmission electron microscopy revealed that a uniform Al-based interlayer self-formed at the interface after annealing. To evaluate the barrier properties of the Al-based interlayer and adhesion between the Cu–Al alloy film and SiO{sub 2} dielectric, thermal stability and peel-off adhesion tests were performed, respectively. The Al-based interlayer showed similar thermal stability and adhesion to the reference Mn-based interlayer. Our results indicate that Cu–Al alloys formed by alternating ALD are suitable seed layer materials for Cu interconnects.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Reactor concepts for atomic layer deposition on agitated particles: A review

The number of possible applications for nanoparticles has strongly increased in the last decade. For many applications, nanoparticles with different surface and bulk properties are necessary. A popular surface modification technique is coating the particle surface with a nanometer thick layer. Atomic layer deposition (ALD) is known as a reliable method for depositing ultrathin and conformal coatings. In this article, agitation or fluidization of the particles is necessary for performing ALD on (nano)particles. The principles of gas fluidization of particles will be outlined, and a classification of the gas fluidization behavior of particles based on their size and density will be given. Following different reactor concepts that have been designed to conformally coat (nano)particles with ALD will be described, and a concise overview will be presented of the work that has been performed with each of them ending with a concept reactor for performing spatial ALD on fluidized particles.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Development of atomic layer deposition-activated microchannel plates for single particle detection at cryogenic temperatures

Atomic layer deposition (ALD) technology is used to nanoengineer functional films inside the pores of microchannel plate (MCP) electron multipliers, enabling a novel MCP manufacturing technology that substantially improves performance and opens novel applications. The authors have developed custom tools and recipes for the growth of conformal films, with optimized conductance and secondary electron emission inside very long channels (∼6–20 μm diameter and >600 μm length, with tens of millions of channels per single MCP) by ALD. The unique ability to tune the characteristics of these ALD films enables their optimization to applications where time-resolved single particle imaging can be performed in extreme conditions, such as high counting rates at cryogenic temperatures. Adhesion of the conductive and emissive nanofilms to the 20 μm pore MCP glass substrates and their mechanical stability over a very wide range of temperatures (10–700 K) were confirmed experimentally. Resistance of ALD MCPs was reproducible during multiple cool-down cycles with no film degradation observed. Optimizing resistance of novel MCPs for operation at cryogenic temperature should enable high count rate event detection at temperatures below 20 K.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Scalable control program for multiprecursor flow-type atomic layer deposition system

The authors report the development and implementation of a scalable control program to control flow type atomic layer deposition (ALD) reactor with multiple precursor delivery lines. The program logic is written and tested in LABVIEW environment to control ALD reactor with four precursor delivery lines to deposit up to four layers of different materials in cyclic manner. The programming logic is conceived such that to facilitate scale up for depositing more layers with multiple precursors and scale down for using single layer with any one precursor in the ALD reactor. The program takes precursor and oxidizer exposure and purging times as input and controls the sequential opening and closing of the valves to facilitate the complex ALD process in cyclic manner. The program could be used to deposit materials from any single line or in tandem with other lines in any combination and in any sequence.

42 ENGINEERING↗
DOE OSTI2015

Initial growth, refractive index, and crystallinity of thermal and plasma-enhanced atomic layer deposition AlN films

The authors have studied and compared the initial growth and properties of AlN films deposited on Si(111) by thermal and plasma-enhanced atomic layer deposition (ALD) using trimethylaluminum and either ammonia or a N{sub 2}-H{sub 2} mixture as precursors. In-situ spectroscopic ellipsometry was employed to monitor the growth and measure the refractive index of the films during the deposition. The authors found that an incubation stage only occurred for thermal ALD. The linear growth for plasma-enhanced ALD (PEALD) started instantly from the beginning due to the higher nuclei density provided by the presence of plasma. The authors observed the evolution of the refractive index of AlN during the growth, which showed a rapid increase up to a thickness of about 30 nm followed by a saturation. Below this thickness, higher refractive index values were obtained for AlN films grown by PEALD, whereas above that the refractive index was slightly higher for thermal ALD films. X-ray diffraction characterization showed a wurtzite crystalline structure with a (101{sup ¯}0) preferential orientation obtained for all the layers with a slightly better crystallinity for films grown by PEALD.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Microscopic silicon-based lateral high-aspect-ratio structures for thin film conformality analysis

Film conformality is one of the major drivers for the interest in atomic layer deposition (ALD) processes. This work presents new silicon-based microscopic lateral high-aspect-ratio (LHAR) test structures for the analysis of the conformality of thin films deposited by ALD and by other chemical vapor deposition means. The microscopic LHAR structures consist of a lateral cavity inside silicon with a roof supported by pillars. The cavity length (e.g., 20–5000 μm) and cavity height (e.g., 200–1000 nm) can be varied, giving aspect ratios of, e.g., 20:1 to 25 000:1. Film conformality can be analyzed with the microscopic LHAR by several means, as demonstrated for the ALD Al{sub 2}O{sub 3} and TiO{sub 2} processes from Me{sub 3}Al/H{sub 2}O and TiCl{sub 4}/H{sub 2}O. The microscopic LHAR test structures introduced in this work expose a new parameter space for thin film conformality investigations expected to prove useful in the development, tuning and modeling of ALD and other chemical vapor deposition processes.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Atomic layer deposition of aluminum sulfide thin films using trimethylaluminum and hydrogen sulfide

Sequential exposures of trimethylaluminum and hydrogen sulfide are used to deposit aluminum sulfide thin films by atomic layer deposition (ALD) in the temperature ranging from 100 to 200 °C. Growth rate of 1.3 Å per ALD cycle is achieved by in-situ quartz crystal microbalance measurements. It is found that the growth rate per ALD cycle is highly dependent on the purging time between the two precursors. Increased purge time results in higher growth rate. Surface limited chemistry during each ALD half cycle is studied by in-situ Fourier transformed infrared vibration spectroscopy. Time of flight secondary ion-mass spectroscopy measurement is used to confirm elemental composition of the deposited films.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Role of atomic layer deposited aluminum oxide as oxidation barrier for silicon based materials

In this paper, the authors study the protective effect against oxidation of a thin layer of atomic layer deposited (ALD) aluminum oxide (Al{sub 2}O{sub 3}). Nitrogen doped silicon carbide (poly-SiC:N) based microheaters coated with ALD Al{sub 2}O{sub 3} are used as test structure to investigate the barrier effect of the alumina layers to oxygen and water vapor at very high temperature (up to 1000 °C). Different device sets have been fabricated changing the doping levels, to evaluate possible interaction between the dopants and the alumina layer. The as-deposited alumina layer morphology has been evaluated by means of AFM analysis and compared to an annealed sample (8 h at 1000 °C) to estimate the change in the grain structure and the film density. The coated microheaters are subjected to very long oxidation time in dry and wet environment (up to 8 h at 900 and 1000 °C). By evaluating the electrical resistance variation between uncoated reference devices and the ALD coated devices, the oxide growth on the SiC is estimated. The results show that the ALD alumina coating completely prevents the oxidation of the SiC up to 900 °C in wet environment, while an oxide thickness reduction of 50% is observed at 1000 °C compared to uncoated devices.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Atomic layer deposition grown MO{sub x} thin films for solar water splitting: Prospects and challenges

The magnitude of energy challenge not only calls for efficient devices but also for abundant, inexpensive, and stable photoactive materials that can enable efficient light harvesting, charge separation and collection, as well as chemical transformations. Photoelectrochemical systems based on semiconductor materials have the possibility to transform solar energy directly into chemical energy the so-called “solar hydrogen.” The current challenge lies in the harvesting of a larger fraction of electromagnetic spectrum by enhancing the absorbance of electrode materials. In this context, atomically precise thin films of metal oxide semiconductors and their multilayered junctions are promising candidates to integrate high surface areas with well-defined electrode–substrate interface. Given its self-limited growth mechanism, the atomic layer deposition (ALD) technique offers a wide range of capabilities to deposit and modify materials at the nanoscale. In addition, it opens new frontiers for developing precursor chemistry that is inevitable to design new processes. Herein, the authors review the properties and potential of metal oxide thin films deposited by ALD for their application in photoelectrochemical water splitting application. The first part of the review covers the basics of ALD processes followed by a brief discussion on the electrochemistry of water splitting reaction. The second part focuses on different MO{sub x} films deposited by atomic layer deposition for water splitting applications; in this section, The authors discuss the most explored MO{sub x} semiconductors, namely, Fe{sub 2}O{sub 3}, TiO{sub 2}, WO{sub 3}, and ZnO, as active materials and refer to their application as protective coatings, conductive scaffolds, or in heterojunctions. The third part deals with the current challenges and future prospects of ALD processed MO{sub x} thin films for water splitting reactions.

36 MATERIALS SCIENCE↗