Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “ALD”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 451 records · Page 25

Three-Dimensional Solid-State Lithium-Ion Batteries Fabricated by Conformal Vapor-Phase Chemistry

Three-dimensional thin-film solid-state batteries (3D TSSB) were proposed by Long et al. in 2004 as a structure-based approach to simultaneously increase energy and power densities. Here, we report experimental realization of fully conformal 3D TSSBs, demonstrating the simultaneous power-and-energy benefits of 3D structuring. All active battery components—electrodes, solid electrolyte, and current collectors—were deposited by atomic layer deposition (ALD) onto standard CMOS processable silicon wafers microfabricated to form arrays of deep pores with aspect ratios up to approximately 10. The cells utilize an electrochemically prelithiated LiV 2 O 5 cathode, a very thin (40–100 nm) Li 2 PO 2 N solid electrolyte, and a SnNx anode. The fabrication process occurs entirely at or below 250 °C, promising compatibility with a variety of substrates as well as integrated circuits. The multilayer battery structure enabled all-ALD solid-state cells to deliver 37 μAh/cm 2 ·μm (normalized to cathode thickness) with only 0.02% per-cycle capacity loss. Conformal fabrication of full cells over 3D substrates increased the areal discharge capacity by an order of magnitude while simulteneously improving power performance, a trend consistent with a finite element model. Furthermore, this work shows that the exceptional conformality of ALD, combined with conventional semiconductor fabrication methods, provides an avenue for the successful realization of long-sought 3D TSSBs which provide power performance scaling in regimes inaccessible to planar form factor cells.

25 ENERGY STORAGE↗

Plasma-Enhanced Atomic Layer Deposition Synthesis of Nanolayered Molybdenum Diselenide (MoSe 2 ) Thin Films for Nanoelectronics

Nanolayered molybdenum diselenide (MoSe 2 ) thin films were synthesized by plasma-enhanced atomic layer deposition (PE-ALD) using molybdenum pentachloride (MoCl 5 ) and diethyldiselenide (C 4 H 10 Se 2 ) precursors. Scanning and transmission electron microscopy revealed horizontally stacked nanolayers near the substrate and vertically oriented nanosheets at the surface of the film. X-ray diffraction confirmed the (002), (100), and (110) reflections of crystalline MoSe 2 , while X-ray photoelectron spectroscopy showed relative atomic concentrations of 33.5% Mo and 66.5% Se, consistent with stoichiometric MoSe 2 . Raman spectra exhibited characteristic E 1g , A 1g , and E$^1_{2g}$ vibrational modes. Field-effect transistors incorporating PE-ALD-grown MoSe 2 as the channel material displayed p-type behavior, demonstrating the potential of nanolayered MoSe 2 for nanoelectronic applications. This work demonstrates the feasibility of low-temperature, stoichiometric growth of nanolayered MoSe 2 by PE-ALD and its direct integration into transistor architectures.

36 MATERIALS SCIENCE↗

Atomic Layer Deposition of L-Alanine Polypeptide

L-Alanine polypeptide thin films were synthesized via atomic layer deposition (ALD). Rather, instead of using an amino acid monomer as the precursor, an L-alanine amino acid derivatized with a protecting group was used to prevent self-polymerization, increase the vapor pressure, and allow linear cycle-by-cycle growth emblematic of ALD. Moreover, the successful deposition of a conformal polypeptide film has been confirmed by FTIR, TEM, and Mass Spectrometry, and the ALD process has been extended to polyvaline.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Substantial lifetime enhancement for Si-based photoanodes enabled by amorphous TiO2 coating with improved stoichiometry

Abstract Amorphous titanium dioxide (TiO 2 ) film coating by atomic layer deposition (ALD) is a promising strategy to extend the photoelectrode lifetime to meet the industrial standard for solar fuel generation. To realize this promise, the essential structure-property relationship that dictates the protection lifetime needs to be uncovered. In this work, we reveal that in addition to the imbedded crystalline phase, the presence of residual chlorine (Cl) ligands is detrimental to the silicon (Si) photoanode lifetime. We further demonstrate that post-ALD in-situ water treatment can effectively decouple the ALD reaction completeness from crystallization. The as-processed TiO 2 film has a much lower residual Cl concentration and thus an improved film stoichiometry, while its uniform amorphous phase is well preserved. As a result, the protected Si photoanode exhibits a substantially improved lifetime to ~600 h at a photocurrent density of more than 30 mA/cm 2 . This study demonstrates a significant advancement toward sustainable hydrogen generation.

36 MATERIALS SCIENCE↗

Controlled Phase and Tunable Magnetism in Ordered Iron Oxide Nanotube Arrays Prepared by Atomic Layer Deposition

Highly-ordered and conformal iron oxide nanotube arrays on an atomic scale are successfully prepared by atomic layer deposition (ALD) with controlled oxidization states and tunable magnetic properties between superparamagnetism and ferrimagnetism. Non-magnetic α-Fe 2 O 3 and superparamagnetic Fe 2 O 3 with a blocking temperature of 120 K are in-situ obtained by finely controlling the oxidation reaction. Both of them exhibit a very small grain size of only several nanometers due to the nature of atom-by-atom growth of the ALD technique. Post-annealing α-Fe 2 O 3 in a reducing atmosphere leads to the formation of the spinel Fe 3 O 4 phase which displays a distinct ferrimagnetic anisotropy and the Verwey metal-insulator transition that usually takes place only in single crystal magnetite or thick epitaxial films at low temperatures. Finally, the ALD deposition of iron oxide with well-controlled phase and tunable magnetism demonstrated in this work provides a promising opportunity for the fabrication of 3D nano-devices to be used in catalysis, spintronics, microelectronics, data storages and bio-applications.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

The initial stages of ZnO atomic layer deposition on atomically flat In 0.53 Ga 0.47 As substrates

InGaAs is one of the III–V active semiconductors used in modern high-electron-mobility transistors or high-speed electronics. ZnO is a good candidate material to be inserted as a tunneling insulator layer at the metal–semiconductor junction. A key consideration in many modern devices is the atomic structure of the hetero-interface, which often ultimately governs the electronic or chemical process of interest. Here, a complementary suite of in situ synchrotron X-ray techniques (fluorescence, reflectivity and absorption) as well as modeling is used to investigate both structural and chemical evolution during the initial growth of ZnO by atomic layer deposition (ALD) on In 0.53 Ga 0.47 As substrates. Prior to steady-state growth behavior, we discover a transient regime characterized by two stages. First, substrate-inhibited ZnO growth takes place on InGaAs terraces. This leads eventually to the formation of a 1 nm-thick, two-dimensional (2D) amorphous layer. Second, the growth behavior and its modeling suggest the occurrence of dense island formation, with an aspect ratio and surface roughness that depends sensitively on the growth condition. Lastly, ZnO ALD on In 0.53 Ga 0.47 As is characterized by 2D steady-state growth with a linear growth rate of 0.21 nm cy -1 , as expected for layer-by-layer ZnO ALD.

36 MATERIALS SCIENCE↗

Mechanisms of alumina growth via atomic layer deposition on nickel oxide and metallic nickel surfaces

We aim at elucidating the mechanism of the trimethyl aluminum (TMA) decomposition on oxidized nickel (NiO) and metallic nickel (Ni) facets in the absence of a source of hydroxyl groups. This TMA decomposition mechanism constitutes the earliest stage of growth of Al 2 O 3 coatings with the atomic layer decomposition (ALD) method, which stabilizes nickel catalysts in energy-intensive processes such as the dry reforming of methane. Our first-principles calculations suggest thermodynamic favorability for the TMA decomposition on metallic nickel compared to oxidized nickel. Moreover, the decomposition of TMA on metallic nickel showed almost no differences in terms of energy barriers between flat and stepped surfaces. Regarding the impact of the CH 3 radicals formed after TMA decomposition, we calculated stronger adsorption on metallic nickel facets than on oxidized nickel, and these adsorption energies are comparable to the adsorption energies calculated in earlier works on Al 2 O 3 ALD growth on palladium surfaces. These results lead us to believe in the growth of porous Al 2 O 3 coatings triggered by CH 3 contamination rather than due to preferential TMA decomposition on stepped and/or defective facets. The CH 3 radicals are likely to be thermally stable at temperatures used during Al 2 O 3 ALD processes, partially passivating the surface towards further TMA decomposition.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ultrathin alumina passivation for improved photoelectrochemical water oxidation catalysis of tin oxide sensitized by a phosphonate-functionalized perylene diimide first without, and then with, CoOy

Previously, a photoanode composed of nanostructured SnO 2 coated with the perylene diimide dye N,N'-bis(phosphonomethyl)-3,4,9,10-perylenediimide (PMPDI) plus photoelectrochemically deposited cobalt oxide (CoO y ) was shown to photoelectrochemically oxidize water at 31 ± 7% faradaic efficiency. A non-ideal part of that prior system is that the addition of the known CoO y water oxidation catalyst (WOC) resulted in a reduction of the total photocurrent rather than the anticipated increase, due to an increase in charge-carrier recombination. Herein, we show deposition of an ultrathin alumina overlayer applied by atomic layer deposition (ALD) on the SnO 2 /PMPDI photoanode can improve the photoactivity and catalytic activity of the system; the addition a ca. 1 nm-thick AlO x layer deposited on a 4000 nm (i.e., 4 micron) thick mesoporous anode system can and does have a positive, 2.5-fold improvement in the steady-state photocurrent with 29 ± 9% faradaic efficiency vs. the control anode without alumina passivation by reducing charge-carrier recombination. Moreover, ALD-deposited AlO x layer does help support the understanding of the “anti-catalysis” of co-depositing a CoO y WOC on the SnO 2 /PMPDI DS-PECs—specifically the picture of direct CoO y –SnO 2 contact-mediated recombination—but that AlO x layer was unable to improve the photocurrent in a net SnO 2 /PMPDI/AlO x (/CoO y ) system. We attribute the lack of a performance enhancement by CoOy WOC to incomplete coverage of each SnO 2 nanoparticle by the AlO x . Overall, we find the addition of an optimized ultrathin AlOx layer (0.6 nm thick; deposited at 85 °C) improves the SnO 2 /PMPDI/AlO x system's photoactivity by a factor of up to ca. 3-fold with reduced recombination. These results document that metal-oxide passivation by low-temperature ALD can be an effective strategy for improving the water oxidation performance of even nanostructured dye sensitized-photoelectrochemical cell.

36 MATERIALS SCIENCE↗

Synthesis of platinum nanoparticles on strontium titanate nanocuboids via surface organometallic grafting for the catalytic hydrogenolysis of plastic waste

Pt/SrTiO 3 (Pt/STO), prepared on small scale by atomic layer deposition (ALD), is a capable heterogeneous catalyst for the selective hydrogenolysis of polyolefins to hydrocarbon oils, providing a promising approach for upcycling plastic waste. However, because deposition by ALD is costly and resource-intensive, a new synthesis of Pt/STO is needed to effectively scale catalyst production and pursue the commercialization of upcycling processes. To that effect, this work details a scalable deposition method for Pt/STO made by surface organometallic chemistry (SOMC) techniques using Pt(II) acetylacetonate or and trimethyl(methylcyclopentadienyl)platinum. The STO support was calcined (550 °C), treated with ozone (200 °C), and finally steamed (200 °C) to afford a clean STO surface populated with only hydroxyl groups. Pt precursors were dissolved in toluene and deposited onto STO. After reduction at 300 °C, the STO support was decorated with 1.0–1.5 nm Pt nanoparticles. The size and loading of these nanoparticles were varied by employing a multi-cycle deposition and oxidation and/or reduction process designed to ALD techniques. In conclusion, these Pt/STO catalysts hydrogenolyzed isotactic polypropylene into liquid products (>95% yield) with average molecular weights of 200–300 Da (~25 carbon atoms) and narrow size distributions at 300 °C and 180 psi H 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Atomic layer deposition for surface area determination of solid oxide electrodes

Surface area measurements are important for characterizing porous solids, but commonly used methods such as Brunauer–Emmett–Teller (BET) gas adsorption and computed nanotomography are lacking for certain applications such as the development of solid oxide fuel cell electrodes, which often have absolute surface areas <1 m 2 and contain nanoscale features. Presented is a novel method for the surface area determination of samples with total measurable areas of 1–1000 cm 2 with a standard deviation ± 1 cm 2 , utilizing the atomic layer deposition (ALD) of Al 2 O 3 over microstructurally complex internal porosity. The volume of alumina is then quantified using plasma spectroscopy and converted to an area using the known ALD layer thickness. Under the modest ALD reactor soak times used (8.5 s), the precursor penetration depth is found to be ~50 μm, exceeding the requirement for uniformly coating SOFC functional layers. A model system, (La 0.8 Sr 0.2 ) 0.98 MnO 3–δ /Ce 0.9 Gd 0.1 O 1.95 (LSM/GDC) scaffolds of ~2.7 m 2 g –1 , was measured using the technique and compared against the BET method, and comparable results were obtained but with 1000 times less material needed. The technique is demonstrated for measurements in two example areas of active SOFC research: exsolved (Ni, Fe) nanoparticles on an Sr(Ti, Fe, Ni)O 3–δ electrode and PrO x catalyst nanoparticles infiltrated onto LSM/GDC scaffolds. Finally, the technique may be broadly useful wherever the accurate surface area determination of small absolute quantities of porous ceramic structures on the order of 0.1–50 m 2 g –1 is sought.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Radio frequency plasma power dependence of the moisture permeation barrier characteristics of Al{sub 2}O{sub 3} films deposited by remote plasma atomic layer deposition

In the present study, we investigated the gas and moisture permeation barrier properties of Al{sub 2}O{sub 3} films deposited on polyethersulfone films (PES) by capacitively coupled plasma (CCP) type Remote Plasma Atomic Layer Deposition (RPALD) at Radio Frequency (RF) plasma powers ranging from 100 W to 400 W in 100 W increments using Trimethylaluminum [TMA, Al(CH{sub 3}){sub 3}] as the Al source and O{sub 2} plasma as the reactant. To study the gas and moisture permeation barrier properties of 100-nm-thick Al{sub 2}O{sub 3} at various plasma powers, the Water Vapor Transmission Rate (WVTR) was measured using an electrical Ca degradation test. WVTR decreased as plasma power increased with WVTR values for 400 W and 100 W of 2.6 × 10{sup −4} gm{sup −2}day{sup −1} and 1.2 × 10{sup −3} gm{sup −2}day{sup −1}, respectively. The trends for life time, Al-O and O-H bond, density, and stoichiometry were similar to that of WVTR with improvement associated with increasing plasma power. Further, among plasma power ranging from 100 W to 400 W, the highest power of 400 W resulted in the best moisture permeation barrier properties. This result was attributed to differences in volume and amount of ion and radical fluxes, to join the ALD process, generated by O{sub 2} plasma as the plasma power changed during ALD process, which was determined using a plasma diagnosis technique called the Floating Harmonic Method (FHM). Plasma diagnosis by FHM revealed an increase in ion flux with increasing plasma power. With respect to the ALD process, our results indicated that higher plasma power generated increased ion and radical flux compared with lower plasma power. Thus, a higher plasma power provides the best gas and moisture permeation barrier properties.

36 MATERIALS SCIENCE↗

Low interface defect density of atomic layer deposition BeO with self-cleaning reaction for InGaAs metal oxide semiconductor field effect transistors

In this paper, we discuss atomic configuration of atomic layer deposition (ALD) beryllium oxide (BeO) using the quantum chemistry to understand the theoretical origin. BeO has shorter bond length, higher reaction enthalpy, and larger bandgap energy compared with those of ALD aluminum oxide. It is shown that the excellent material properties of ALD BeO can reduce interface defect density due to the self-cleaning reaction and this contributes to the improvement of device performance of InGaAs MOSFETs. The low interface defect density and low leakage current of InGaAs MOSFET were demonstrated using X-ray photoelectron spectroscopy and the corresponding electrical results.

36 MATERIALS SCIENCE↗

High-performance self-aligned inversion-channel In{sub 0.53}Ga{sub 0.47}As metal-oxide-semiconductor field-effect-transistors by in-situ atomic-layer-deposited HfO{sub 2}

Self-aligned inversion-channel In{sub 0.53}Ga{sub 0.47}As metal-oxide-semiconductor field-effect-transistors (MOSFETs) have been fabricated using the gate dielectrics of in-situ directly atomic-layer-deposited (ALD) HfO{sub 2} followed by ALD-Al{sub 2}O{sub 3}. There were no surface pretreatments and no interfacial passivation/barrier layers prior to the ALD. TiN/Al{sub 2}O{sub 3} (4 nm)/HfO{sub 2} (1 nm)/In{sub 0.53}Ga{sub 0.47}As/InP MOS capacitors exhibited well-behaved capacitance-voltage characteristics with true inversion behavior, low leakage current densities of ∼10{sup −8} A/cm{sup 2} at ±1 MV/cm, and thermodynamic stability at high temperatures. Al{sub 2}O{sub 3} (3 nm)/HfO{sub 2} (1 nm)/In{sub 0.53}Ga{sub 0.47}As MOSFETs of 1 μm gate length, with 700 °C–800 °C rapid thermal annealing in source/drain activation, have exhibited high extrinsic drain current (I{sub D}) of 1.5 mA/μm, transconductance (G{sub m}) of 0.84 mS/μm, I{sub ON}/I{sub OFF} of ∼10{sup 4}, low sub-threshold swing of 103 mV/decade, and field-effect electron mobility of 1100 cm{sup 2}/V · s. The devices have also achieved very high intrinsic I{sub D} and G{sub m} of 2 mA/μm and 1.2 mS/μm, respectively.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

High performance organic field-effect transistors with ultra-thin HfO{sub 2} gate insulator deposited directly onto the organic semiconductor

We have produced stable organic field-effect transistors (OFETs) with an ultra-thin HfO{sub 2} gate insulator deposited directly on top of rubrene single crystals by atomic layer deposition (ALD). We find that ALD is a gentle deposition process to grow thin films without damaging rubrene single crystals, as results these devices have a negligibly small threshold voltage and are very stable against gate-bias-stress, and the mobility exceeds 1 cm{sup 2}/V s. Moreover, the devices show very little degradation even when kept in air for more than 2 months. These results demonstrate thin HfO{sub 2} layers deposited by ALD to be well suited as high capacitance gate dielectrics in OFETs operating at small gate voltage. In addition, the dielectric layer acts as an effective passivation layer to protect the organic semiconductor.

36 MATERIALS SCIENCE↗

Property transformation of graphene with Al{sub 2}O{sub 3} films deposited directly by atomic layer deposition

Al{sub 2}O{sub 3} films are deposited directly onto graphene by H{sub 2}O-based atomic layer deposition (ALD), and the films are pinhole-free and continuously cover the graphene surface. The growth process of Al{sub 2}O{sub 3} films does not introduce any detective defects in graphene, suppresses the hysteresis effect and tunes the graphene doping to n-type. The self-cleaning of ALD growth process, together with the physically absorbed H{sub 2}O and oxygen-deficient ALD environment consumes OH{sup −} bonds, suppresses the p-doping of graphene, shifts Dirac point to negative gate bias and enhances the electron mobility.

36 MATERIALS SCIENCE↗

Surface smoothing effect of an amorphous thin film deposited by atomic layer deposition on a surface with nano-sized roughness

Previously, Lau (one of the authors) pointed out that the deposition of an amorphous thin film by atomic layer deposition (ALD) on a substrate with nano-sized roughness probably has a surface smoothing effect. In this letter, polycrystalline zinc oxide deposited by ALD onto a smooth substrate was used as a substrate with nano-sized roughness. Atomic force microscopy (AFM) and cross-sectional transmission electron microscopy (XTEM) were used to demonstrate that an amorphous aluminum oxide thin film deposited by ALD can reduce the surface roughness of a polycrystalline zinc oxide coated substrate.

36 MATERIALS SCIENCE↗

An atomic layer deposition chamber for in situ x-ray diffraction and scattering analysis

The crystal structure of thin films grown by atomic layer deposition (ALD) will determine important performance properties such as conductivity, breakdown voltage, and catalytic activity. We report the design of an atomic layer deposition chamber for in situ x-ray analysis that can be used to monitor changes to the crystal structural during ALD. The application of the chamber is demonstrated for Pt ALD on amorphous SiO{sub 2} and SrTiO{sub 3} (001) using synchrotron-based high resolution x-ray diffraction, grazing incidence x-ray diffraction, and grazing incidence small angle scattering.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

High-reliability passivation of hydrogen-terminated diamond surface by atomic layer deposition of Al{sub 2}O{sub 3}

Although the two-dimensional hole gas (2DHG) of a hydrogen-terminated diamond surface provides a unique p-type conducting layer for high-performance transistors, the conductivity is highly sensitive to its environment. Therefore, the surface must be passivated to preserve the 2DHG, especially at high temperature. We passivated the surface at high temperature (450 °C) without the loss of C-H surface bonds by atomic layer deposition (ALD) and investigated the thermal reliability of the Al{sub 2}O{sub 3} film. As a result, C-H bonds were preserved, and the hole accumulation effect appeared after the Al{sub 2}O{sub 3} deposition by ALD with H{sub 2}O as an oxidant. The sheet resistivity and hole density were almost constant between room temperature and 500 °C by the passivation with thick Al{sub 2}O{sub 3} film thicker than 38 nm deposited by ALD at 450 °C. After the annealing at 550 °C in air The sheet resistivity and hole density were preserved. These results indicate the possibility of high-temperature application of the C-H surface diamond device in air. In the case of lower deposition temperatures, the sheet resistivity increased after air annealing, suggesting an insufficient protection capability of these films. Given the result of sheet resistivity after annealing, the increase in the sheet resistivity of these samples was not greatly significant. However, bubble like patterns were observed in the Al{sub 2}O{sub 3} films formed from 200 to 400 °C by air annealing at 550 °C for 1 h. On the other hand, the patterns were no longer observed at 450 °C deposition. Thus, this 450 °C deposition is the sole solution to enabling power device application, which requires high reliability at high temperatures.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗