Plasma-enhanced Atomic Layer Deposition Growth Research Articles

Substrate temperature effects on PEALD HfAlO dielectric films for IGZO-TFT applications

Aluminum incorporated hafnium oxide (HfAlO) has garnered significant attention due to its high dielectric constant. The present study employs supercycle plasma-enhanced atomic layer deposition (PEALD) to prepare HfAlO films, switching between HfO2 and Al2O3 deposition. The effects of substate temperature on the HfAlO films are systematically investigated. The experimental results indicate that increased substrate temperatures favor Al2O3 growth on HfO2, but excessively high temperatures result in deviated PEALD growth and deteriorated film properties. The PEALD window can be reached at substrate temperatures of 300 to 350 °C. The Al content is substantially affected by the substrate temperature, despite a constant Al2O3 PEALD cycle ratio used. The film deposited at 350 °C exhibits the highest Al content, density, and (111) crystalline orientation ratio, leading to a high breakdown field of 6 MV/cm and a considerable dielectric constant of 27. The HfAlO films are applied to indium gallium zinc oxide transistor as the dielectric layer, and the 350 °C-deposited HfAlO leads to the best device performance with a remarkably high on/off current ratio of 3.5 × 109, low threshold voltage of −0.1 V, saturated mobility of 6.1 cm2 V−1 s−1, and a low subthreshold swing of 76 mV/dec.

Investigation into the growth mode of GaN thin films on 4H–SiC substrates via plasma-enhanced atomic layer deposition

GaN ultra-thin films are deposited on 4H–SiC substrates using plasma-enhanced atomic layer deposition (PEALD). Our investigation reveals a remarkably narrow temperature window (225–275 °C) for GaN PEALD growth, characterized by substrate hindered nucleation retardation. Within this temperature window, the growth process exhibits three distinct stages, which are demarcated by the 35th and 200th cycles, each displaying unique characteristic, especially in aspects growth rate, film strain, surface topography, and crystallization. Notably, the instantaneous growth rate, which is often overlooked, provided a better representation of the growth state compared with growth per cycle (GPC) and shows better consistency with film strain and surface roughness. Additionally, we observed a step filling effect during the early stages (10 cycles) of ALD growth, which reduces surface roughness to 0.12 nm form 0.20 nm of substrate SiC. X-ray photoelectron spectroscopy (XPS) analysis reveals the formation of N–Si and N–C bonds on the sample surface following 20 cycles of plasma bombardment. Further analysis using high-resolution X-ray diffraction (HRXRD) and high-resolution transmission electron microscopy (HRTEM) consistently confirms the presence of a hexagonal wurtzite crystalline structure in GaN films deposited under varying cycle counts.

Graphene-assisted low temperature growth of nearly single-crystalline GaN thin films via plasma-enhanced atomic layer deposition

Direct growth of gallium nitride (GaN) thin films is performed using plasma-enhanced atomic layer deposition (PEALD) at 300 °C on a sapphire with a graphene interlayer. The x-ray diffraction and spherical aberration corrected transmission microscope results confirm that the GaN thin films are nearly single-crystalline. Additionally, the interfacial properties and nucleation behaviors of the GaN thin films deposited on graphene are investigated in detail. Therefore, this study offers a perspective on PEALD growth of high-quality nanoscale GaN epilayers and broadens the choice for low-temperature fabrication of GaN based-devices.

Atomic layer deposition of AlGaN alloy and its application in quantum dot sensitized solar cells

The role of plasma-enhanced atomic layer deposition growth of AlGaN ternary alloys on <i>c</i>-planar sapphire substrates and the preparation of quantum dot-sensitized solar cells are explored in this work. The interface between the film and the substrate as well as the band gap of AlGaN ternary alloys during atomic layer deposition is dependent on Al component. At high Al fraction, there appears a good interface between the AlGaN alloy film and the substrate, however, the interface becomes rough when the Al fraction is reduced. The AlGaN alloy prepared by atomic layer deposition has a high band gap, which is related to the oxygen content within the film. Subsequently, CdSe/AlGaN/ZnS and CdSe/ZnS/AlGaN structured cells are prepared and analyzed for quantum dot solar cells from AlGaN films with an AlN/GaN cycle ratio of 1∶1. It is found that AlGaN can modify and passivate quantum dots and TiO<sub>2</sub>, which can wrap and protect the structure of TiO<sub>2</sub> and CdSe quantum dot, thus avoiding the recombination of photo-generated carriers. This modification effect is also reflected in the improvement of open-circuit voltage, short-circuit current, filling factor and photovoltaic conversion efficiency of quantum dot solar cells. These factors are discussed in this work, trying to modify carrier transport characteristics of AlGaN films prepared by atomic layer deposition.

Influence of plasma species on the early-stage growth kinetics of epitaxial InN grown by plasma-enhanced atomic layer deposition

Plasma-enhanced atomic layer deposition (PEALD) enables the epitaxial growth of ultrathin indium nitride (InN) films at significantly reduced process temperatures and with greater control of layer thickness compared to other growth methods. However, the reliance on plasma-surface interactions increases the complexity of the growth process. A detailed understanding of the relationship between the plasma properties and the growth kinetics is therefore required to guide the tuning of growth parameters. We present an in situ investigation of the early-stage PEALD growth kinetics of epitaxial InN within three different plasma regimes using grazing incidence small-angle x-ray scattering (GISAXS). The GISAXS data are supported by diagnostic studies of the plasma species generation in the inductively coupled plasma source as a function of the relative concentrations of the nitrogen/argon gas mixture used in the growth process. The growth mode is found to be correlated to the production of nitrogen species in the plasma, with high concentrations of the atomic N species promoting Volmer–Weber growth (i.e., island growth) and low concentrations promoting Stranski–Krastanov growth (i.e., layer-plus-island growth). The critical thickness for island formation, island center-to-center distance, and island radius are found to increase with ion flux. Furthermore, the island center-to-center distance and areal density are observed to change only during plasma exposure and to continue changing with exposure even after the methylindium adlayer is believed to have fully reacted with the plasma. Our results demonstrate the potential to control the growth kinetics during PEALD of epitaxial films by intentionally accessing specific regimes of plasma species generation.

Shedding light on the initial growth of ZnO during plasma-enhanced atomic layer deposition on vapor-deposited polymer thin films

Interest in atomic layer deposition (ALD) processes on polymer substrates is fueled by the increasing rise of organic electronics and polymer-based nanodevices. This study provides new insights into the initial growth and interface formation during plasma-enhanced ALD (PE-ALD) of ZnO on poly ethylene glycol dimethylacrylate (pEGDMA) and poly 2-hydroxyethyl methacrylate (pHEMA) thin films, both deposited by initiated chemical vapor deposition (iCVD). In-situ spectroscopic ellipsometry showed that PE-ALD growth on the investigated polymers is a result of two competing processes: plasma etching of the polymer substrate and ZnO nucleation and growth. During the first 10–15 ALD cycles, polymer etching was found to prevail until at a certain point (depending on plasma power and type of polymer) ZnO growth takes over and the regime of linear ALD growth is entered. On pHEMA, though more sensitive to etching, ZnO film formation starts early on, whereas on pEGDMA, subsurface nucleation and island growth appear to dominate the initial stage of deposition. Despite the initial etching, resulting ZnO films are smooth and of comparable structural quality to those grown on silicon. These findings contribute to a deeper understanding of PE-ALD growth on polymers providing knowledge essential for the successful development of new processes and applications.

Modelling the Atomic Layer Deposition of Cobalt and Ruthenium on NHx-Terminated Metal Surfaces

Atomic layer deposition (ALD) is widely used in microelectronics and semiconductor industry to deposit very thin films as part of device fabrication in nano- or subnano-dimensions. The key advantages of ALD are the conformality and precise thickness control at the atomic scale, which are difficult for physical or traditional chemical vapor deposition methods. Cobalt (Co) and Ruthenium (Ru) are used as a seed layers for metallization of interconnects. They are also potential materials for the electrode in dynamic random-access memory (DRAM) capacitors and metal-oxide-semiconductor field-effect transistors (MOSFETs). Plasma-enhanced ALD (PE-ALD) is used for low-temperature thin film growth by alternating exposures of metal precursors and plasma reactants. During the PE-ALD growth of metals, N-plasma, for example, NH3 or a mixture of N2 and H2, has been applied to avoid surface metal oxidation. The PE-ALD of Ru and Co has been experimentally investigated using metal precursors such as RuCp2, Ru(EtCp)2, CoCp2, and CoCp(CO)2. However, the reaction mechanism is not clear and theoretical studies on the reaction mechanism is entirely lacking.In this presentation, we study the PE-ALD growth of Co and Ru by first principle calculations. The (001) surface of both metals, with a hexagonal structure, is the most stable and the (100) surface with a zigzag structure is less stable but has high reactivity. These two surfaces allow the study of the influence of the surface facet. The surface saturation coverage was studied by considering individual adsorption and co-adsorption of NH and NH2 to terminate both surfaces. On the (001) surface, the zero K saturation coverage for NH is 1ML on Ru and 6/9ML on Co. For NH2, the saturation coverages are 6/9ML on Co and Ru surfaces. On the (100) surface, the saturation coverages are 2ML for NH on Ru and Co surfaces, 1.33 ML for NH2 on Ru, and 1ML for NH2 on Co surface. The higher saturation coverage on (100) surface is attributed to the unique trench structure, which provides more available surface sites than that of (001) surface. We also consider co-adsorption of NH and NH2 on (001) and (100) surfaces. The results are then analyzed with ab initio thermodynamics by calculating the Gibbs free energy. Both the ultra-high vacuum (UHV) condition and standard ALD operating condition are used to elucidate the effect of pressure and temperature on the termination of metal surfaces.The adsorption and reactions of metal precursors (CoCp2 and RuCp2) on NHx terminated metal surfaces were investigated with the inclusion of van der Waals corrections. Two possible adsorption structures, namely the precursor lying parallel and perpendicular to the NHx-terminated surfaces, were considered at zero K and ALD conditions. Possible reactions include: precursor adsorption, first hydrogen transfer, first Cp ligand dissociation, first Cp ligand desorption, second hydrogen transfer, and second Cp ligand desorption. The barrier for proton transfer was calculated using climbing image nudged elastic band (CI-NEB) method. Our results show that (100) surface has higher activity than (001) surface. In addition, the Cp ligand elimination of CoCp2 has lower barrier than RuCp2, regardless of surface facet. After the metal precursor pulse, the surface is terminated with MCp fragment or M atom depending on surface facet, where M is Ru or Co. The surface N atom and H atom can be eliminated during the following plasma step by forming NH3, N2 or H2. After a full cycle, the surface is an NHx-terminated metal surface and ready for the next cycle. This work will be important to reveal the mechanism and feasibility of atomic layer deposition of metals using N-plasma.

HfO2/SiO2 anti-reflection films for UV lasers via plasma-enhanced atomic layer deposition

The laser-induced damage threshold (LIDT) of HfO2/SiO2 anti-reflection (AR) films for ultraviolet (UV) lasers was improved via low-temperature plasma-enhanced atomic layer deposition (PEALD). Focused on the chemical composition, optical absorption, surface scattering, and laser-resistance, the impact of precursor exposure time on PEALD SiO2 film properties and growth temperature on PEALD SiO2 and HfO2 film properties were investigated respectively. When irradiated by UV laser, PEALD SiO2 film exhibits a higher LIDT than the PEALD HfO2 film, which is consistent with their less impurity content and lower absorption. A bilayer structure HfO2/SiO2 AR film for 355 nm laser was designed and experimentally demonstrated via PEALD growth at a temperature of 150 °C. The prepared PEALD AR film shows a reflectance <0.2% at 355 nm as designed and better laser-damage resistance with a LIDT of 24.4 J/cm2 (355 nm, 7.8 ns) than the conventional e-beam deposition method.

Modelling the Atomic Layer Deposition of Cobalt and Ruthenium on NHx-Terminated Metal Surfaces

Atomic layer deposition (ALD) is widely used in microelectronics and semiconductor industry to deposit thin films as part of device fabrication in nano- or subnano-dimensions. The key advantages of ALD are the conformality and precise thickness control at the atomic scale, which are difficult for physical or traditional chemical vapor deposition methods. Cobalt (Co) and Ruthenium (Ru) are used as seed layers for metallization of interconnects. They are also potential materials for the electrode in dynamic random-access memory (DRAM) capacitors and metal-oxide-semiconductor field-effect transistors (MOSFETs). Plasma-enhanced ALD (PE-ALD) is used for low-temperature thin film growth by alternating exposures of metal precursors and plasma reactants. During the PE-ALD growth of metals, N-plasma, for example, NH3 or a mixture of N2 and H2, has been applied to avoid surface metal oxidation. The PE-ALD of Ru and Co has been experimentally investigated using metal precursors such as RuCp2, Ru(EtCp)2, CoCp2, and CoCp(CO)2. However, the reaction mechanism is not clear and theoretical studies on the reaction mechanism is entirely lacking.In this presentation, we study the PE-ALD growth of Co and Ru by first principle calculations. The (001) surface of both metals, with a hexagonal structure, is the most stable and the (100) surface with a zigzag structure is less stable but has high reactivity. These two surfaces allow the study of the influence of the surface facet. The surface saturation coverage was studied by considering individual adsorption and co-adsorption of NH and NH2 to terminate both surfaces. On the (001) surface, the zero K saturation coverage for NH is 1ML on Ru and 6/9ML on Co. For NH2, the saturation coverages are 6/9ML on Co and Ru surfaces. On the (100) surface, the saturation coverages are 2ML for NH on Ru and Co surfaces, 1.33 ML for NH2 on Ru, and 1ML for NH2 on Co surface. The higher saturation coverage on (100) surface is attributed to the unique trench structure, which provides more available surface sites than that of (001) surface. We also consider co-adsorption of NH and NH2 on (001) and (100) surfaces. The results are then analyzed with ab initio thermodynamics by calculating the Gibbs free energy. Both the ultra-high vacuum (UHV) condition and standard ALD operating condition are used to elucidate the effect of pressure and temperature on the termination of metal surfaces.The adsorption and reactions of metal precursors (CoCp2 and RuCp2) on NHx terminated metal surfaces were investigated with the inclusion of van der Waals corrections. Two possible adsorption structures, namely the precursor lying parallel and perpendicular to the NHx-terminated surfaces, were considered at zero K and ALD operating conditions. Possible reactions include: precursor adsorption, first hydrogen transfer, first Cp ligand dissociation, first Cp ligand desorption, second hydrogen transfer, and second Cp ligand desorption. The barrier for proton transfer was calculated using climbing image nudged elastic band (CI-NEB) method. Our results show that (100) surface has higher activity than (001) surface. In addition, the Cp ligand elimination of CoCp2 has lower barrier than RuCp2, regardless of surface facet. After the metal precursor pulse, the surface is terminated with MCp fragment or M atom depending on surface facet, where M is Ru or Co. The surface N atom and H atom can be eliminated during the following plasma step by forming NH3, N2 or H2. After a full cycle, the surface is an NHx-terminated metal surface and ready for the next cycle. This work will be important to reveal the mechanism and feasibility of atomic layer deposition of metals using N-plasma.

Edge-Site Nanoengineering of WS2 by Low-Temperature Plasma-Enhanced Atomic Layer Deposition for Electrocatalytic Hydrogen Evolution.

Edge-enriched transition metal dichalcogenides, such as WS2, are promising electrocatalysts for sustainable production of H2 through the electrochemical hydrogen evolution reaction (HER). The reliable and controlled growth of such edge-enriched electrocatalysts at low temperatures has, however, remained elusive. In this work, we demonstrate how plasma-enhanced atomic layer deposition (PEALD) can be used as a new approach to nanoengineer and enhance the HER performance of WS2 by maximizing the density of reactive edge sites at a low temperature of 300 °C. By altering the plasma gas composition from H2S to H2 + H2S during PEALD, we could precisely control the morphology and composition and, consequently, the edge-site density as well as chemistry in our WS2 films. The precise control over edge-site density was verified by evaluating the number of exposed edge sites using electrochemical copper underpotential depositions. Subsequently, we demonstrate the HER performance of the edge-enriched WS2 electrocatalyst, and a clear correlation among plasma conditions, edge-site density, and the HER performance is obtained. Additionally, using density functional theory calculations we provide insights and explain how the addition of H2 to the H2S plasma impacts the PEALD growth behavior and, consequently, the material properties, when compared to only H2S plasma.

Tetraallyltin precursor for plasma enhanced atomic layer deposition of tin oxide: Growth study and material characterization

In this letter, the authors report on the application of tetraallyltin (TASn) as an Sn-precursor for plasma enhanced atomic layer deposition (PEALD) of tin oxide (SnO2) thin films. The selection procedure for the TASn precursor is discussed. Tin oxide PEALD growth is shown to be self-limiting with a constant growth-per-cycle of 0.046 ± 0.002 nm/cycle in the substrate temperature (Tsub) range of 50–150 °C. Optical constants, chemical bonding, and electronic properties of as-grown PEALD films were characterized to evaluate the quality of tin oxide film obtained with the TASn precursor. A 21.6 nm tin oxide film grown at Tsub = 50 °C exhibited an indirect optical bandgap (Eg) of 2.94 eV and appeared amorphous from the glancing incidence x-ray diffraction pattern. Binding energy difference ΔBE(O1s, Sn3d5/2) = 43.77 eV and valence band emission in x-ray photoelectron spectroscopy showed that these were near-stoichiometric SnO2 with the relative O:Sn atomic ratio of 1.98 (or SnO1.98). Moreover, room temperature electrical resistivity ρele = 13.1 ± 1.6 mΩ cm, with electron concentration Ne = (3.78 ± 0.79) × 1019 cm−3 and Hall mobility μe = 13.2 ± 2.0 cm2 V−1 s−1, showed that electrical characteristics of the as-grown tin oxide films with the TASn precursor are comparable to those grown using other standard Sn precursors.

Metallic indium segregation control of InN thin films grown on Si(1 0 0) by plasma-enhanced atomic layer deposition

Abstract InN thin films were grown on Si(1 0 0) substrates by plasma-enhanced atomic layer deposition (PEALD). In this work, It is found that the island growth of InN on Si(1 0 0) easily happens at the initial PEALD period. The PEALD parameters have been systematically investigated to optimize the size, density, coalescence and distribution uniformity of InN grains with good crystallinity and no metallic indium clustering. Especially, indium segregation of PEALD-grown InN has a direct dependence on the deposition temperature (T), the supply of trimethylindium (TMIn) precursor and nitrogen plasma (NP) source. Based on our proposed PEALD mechanism of InN, a polycrystalline hexagonal InN thin film in the thickness of 24.2 nm has been well deposited at the growth per cycle (GPC) of 0.8 A/cycle. And it shows a (0 0 2) preferential orientation and no any structural phase of metallic indium segregation. As a result, it may provide a useful guide for deeply understanding the PEALD growth mechanism of InN and In-rich nitrides, which further extends the promising applications in high-efficiency photovoltaics and high speed electronic devices.

Low-Temperature One-Step Growth of AlON Thin Films with Homogenous Nitrogen-Doping Profile by Plasma-Enhanced Atomic Layer Deposition.

The AlON film with homogeneous nitrogen-doping profile was grown by plasma-enhanced atomic layer deposition (PEALD) at low temperature. In this work, the precursors of the NH3 and the O2 were simultaneously introduced into the chamber during the PEALD growth at a relatively low temperature of 185 °C. It is found that the composition of the obtained film quickly changes from AlN to Al2O3 when a small amount of O2 is added. Thus, the NH3:O2 ratio should be maintained at a relatively high level (>85%) for realizing the AlON growth. Benefited from the growth method, the nitrogen can be doped evenly in the entire film. Moreover, the AlON films exhibit a lower surface roughness than the AlN as well as the Al2O3 ones. The Al 2p and N 1s X-ray photoelectron spectra show that the AlON film is composed of Al-N, Al-O, and N-Al-O bonds. Moreover, a three-layer construction of the AlON film is proposed through the Si 2p spectra analysis and reconfirmed by the transmission electron microscopy characterization. At last, the electrical and optical tests indicate that the AlON films prepared in this work can be employed as the gate dielectric in transistor application as well as the antireflection layer in photovoltaic application.

Al2O3 dielectric layers on H-terminated diamond: Controlling surface conductivity

This study investigates how the surface conductivity of H-terminated diamond can be preserved and stabilized by using a dielectric layer with an in situ post-deposition treatment. Thin layers of Al2O3 were grown by plasma enhanced atomic layer deposition (PEALD) on H-terminated undoped diamond (100) surfaces. The changes of the hole accumulation layer were monitored by correlating the binding energy of the diamond C 1s core level with electrical measurements. The initial PEALD of 1 nm Al2O3 resulted in an increase of the C 1s core level binding energy consistent with a reduction of the surface hole accumulation and a reduction of the surface conductivity. A hydrogen plasma step restored the C 1s binding energy to the value of the conductive surface, and the resistance of the diamond surface was found to be within the range for surface transfer doping. Further, the PEALD growth did not appear to degrade the surface conductive layer according to the position of the C 1s core level and electrical measurements. This work provides insight into the approaches to establish and control the two-dimensional hole-accumulation layer of the H-terminated diamond and improve the stability and performance of H-terminated diamond electronic devices.

Structural and electrical properties of ultrathin niobium nitride films grown by atomic layer deposition

We studied and optimised the properties of ultrathin superconducting niobium nitride films fabricated with a plasma-enhanced atomic layer deposition (PEALD) process. By adjusting process parameters, the chemical embedding of undesired oxygen into the films was minimised and a film structure consisting of mainly polycrystalline niobium nitride with a small fraction of amorphous niobium oxide and niobium oxo-nitrides were formed. For this composition a critical temperature of 13.8 K and critical current densities of 7 × 106 A cm–2 at 4.2 K were measured on 40 nm thick films. A fundamental correlation between these superconducting properties and the crystal lattice size of the cubic δ-niobium-nitride grains were found. Moreover, the film thickness variation between 40 and 2 nm exhibits a pronounced change of the electrical conductivity at room temperature and reveals a superconductor–insulator-transition in the vicinity of 3 nm film thickness at low temperatures. The thicker films with resistances up to 5 kΩ per square in the normal state turn to the superconducting one at low temperatures. The perfect thickness control and film homogeneity of the PEALD growth make such films extremely promising candidates for developing novel devices on the coherent quantum phase slip effect.

Low-Temperature Growth of Indium Oxide Thin Film by Plasma-Enhanced Atomic Layer Deposition Using Liquid Dimethyl(N-ethoxy-2,2-dimethylpropanamido)indium for High-Mobility Thin Film Transistor Application.

Low-temperature growth of In2O3 films was demonstrated at 70-250 °C by plasma-enhanced atomic layer deposition (PEALD) using a newly synthesized liquid indium precursor, dimethyl(N-ethoxy-2,2-dimethylcarboxylicpropanamide)indium (Me2In(EDPA)), and O2 plasma for application to high-mobility thin film transistors. Self-limiting In2O3 PEALD growth was observed with a saturated growth rate of approximately 0.053 nm/cycle in an ALD temperature window of 90-180 °C. As-deposited In2O3 films showed negligible residual impurity, film densities as high as 6.64-7.16 g/cm3, smooth surface morphology with a root-mean-square (RMS) roughness of approximately 0.2 nm, and semiconducting level carrier concentrations of 1017-1018 cm-3. Ultrathin In2O3 channel-based thin film transistors (TFTs) were fabricated in a coplanar bottom gate structure, and their electrical performances were evaluated. Because of the excellent quality of In2O3 films, superior electronic switching performances were achieved with high field effect mobilities of 28-30 and 16-19 cm2/V·s in the linear and saturation regimes, respectively. Furthermore, the fabricated TFTs showed excellent gate control characteristics in terms of subthreshold swing, hysteresis, and on/off current ratio. The low-temperature PEALD process for high-quality In2O3 films using the developed novel In precursor can be widely used in a variety of applications such as microelectronics, displays, energy devices, and sensors, especially at temperatures compatible with organic substrates.

Low temperature plasma enhanced atomic layer deposition of conducting zirconium nitride films using tetrakis (dimethylamido) zirconium and forming gas (5% H2 + 95% N2) plasma

Zirconium nitride (ZrN) has the lowest bulk electrical resistivity and high thermal stability among group IV and V transition metal nitrides, which makes it a promising material for ULSI applications such as a diffusion barrier for Cu interconnects, contact metal in III-V semiconductor devices, and in high density memory structures. Plasma enhanced atomic layer deposition (PEALD) of conducting ZrN thin films using Zr[N(CH3)2]4 and forming gas (5% H2 + 95% N2) plasma is reported in this article. The growth per cycle (GPC) for every deposition was determined from analysis of dynamic in-situ spectroscopic ellipsometry (d-iSE) measurements. An experimental design is proposed for faster determination of ALD growth saturation curves. At substrate temperature of 150 °C, a GPC of 0.10 nm/cycle was observed for self-limiting ZrN PEALD growth. The electrical resistivity of ZrN films deposited on SiO2 substrate was found to be 559.5 ± 18.5 μΩ cm with negligible change in resistivity even after ∼1000 h exposure to air. The metallic behavior of our ZrN films was evident from the free electron dispersion component in dielectric response, the broad band of photoelectron emission across Fermi level and the positive temperature coefficient for resistivity of 0.0088/ °C.

Atomic layer deposition of AlN for thin membranes using trimethylaluminum and H2/N2 plasma

Aluminum nitride (AlN) thin films with thicknesses from 20 to 100nm were deposited on silicon, amorphous silica, silicon nitride, and vitreous carbon by plasma enhanced atomic layer deposition (PE-ALD). Trimethylaluminum (TMA) and a H2/N2 plasma mixture were used as precursors. We investigated the influence of deposition temperature and plasma parameters on the growth characteristics and the film properties of AlN. Stable PE-ALD growth conditions were obtained from 150°C to the highest tested temperature of 300°C. The growth rate, refractive index, and thickness homogeneity on 4″ wafers were determined by spectroscopic ellipsometry. X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM) and Rutherford backscattering spectrometry (RBS) were carried out to analyze crystallinity and composition of the films. Furthermore, the thermal conductivity and the film stress were determined. The stress was sufficiently low to fabricate mechanically stable free-standing AlN membranes with lateral dimensions of up to 2.2×2.2mm2. The membranes were patterned with focused ion beam etching. Thus, these AlN membranes qualify as dielectric support material for a variety of potential applications.

Impact of Direct Plasma Densification on Resistivity and Conformality of PEALD Tantalum Nitride

A novel plasma enhanced atomic layer deposition (PEALD) process was demonstrated for tantalum nitride (TaN) based on the reduction of pentakis(dimethylamino)tantalum (PDMAT). High-power, direct plasma densification steps were incorporated into each PEALD growth cycle, resulting in ion bombardment of the TaN surface during growth. These densification steps enabled the deposition of low-resistivity, high-density TaN. Physical film densification by ion bombardment was confirmed from the observed thickness reduction of TaN deposited by PEALD with densification steps compared to PEALD without densification steps, for an equivalent number of PEALD cycles. In terms of PEALD TaN resistivity, ion-bombardment induced densification resulted in a reduction by an order of magnitude, from ~4000 μΩcm to ~400 μΩcm. In patterned trench structures, ion bombardment can achieve densification of PEALD TaN at the trench bottom while sidewall surfaces appear to show a less significant reduction in film thickness.

A rotary reactor for thermal and plasma-enhanced atomic layer deposition on powders and small objects

To conformally coat large amounts of particles using atomic layer deposition (ALD), agitation of the particles and efficient reactant usage are necessary. A rotary reactor was developed to enable both thermal and plasma-enhanced ALD growth on agitated particles. The effectiveness of the rotary reactor design was demonstrated by depositing Al2O3, TiO2 and AlN by thermal and plasma-enhanced ALD on ZnO nanopowder, stainless steel micron sized powder, titanium granules and glass beads. In-situ optical emission spectroscopy (OES) and mass spectroscopy (MS) measurements were performed to monitor saturation of the ALD half reactions, while ex-situ X-ray fluorescence (XRF), X-ray photo-electron spectroscopy (XPS), energy-dispersive X-ray spectroscopy (EDX) and transmission electron microscopy (TEM) were used to confirm the composition and conformality of the deposited films.