Plasma-enhanced Atomic Layer Deposition Research Articles

Attaining quantitatively fewer defects in close-packed InGaZnO synthesized using atomic layer deposition

Owing to their uniformity across large areas, low-temperature processability, and low off-current characteristics, oxide semiconductors demonstrate significant potential for integration into displays, memories, and logic devices. In the hyper scaling era, atomic layer deposition (ALD) is well suited for downsizing device fabrication, leveraging self-limiting chemical reactions to provide nanoscale control, and conformal coating on substrates with high aspect ratios. Hence, in this study, we fabricated highly oriented c-axis-aligned crystalline (CAAC) indium-gallium-zinc oxide (IGZO) thin films using plasma-enhanced ALD (PEALD), introducing an additional thermodynamic driving force for crystallization. A comparative study was conducted on the properties of CAAC-IGZO in correspondence to conventional sputter-based IGZO. In particular, photo-induced current transient spectroscopy (PICTS) is employed to map the electronic structure (density of states (DOS)) of the films, which quantitatively confirmed fewer defects in CAAC-IGZO. Fewer defects result in highly stable CAAC-IGZO transistors with positive bias stress threshold (PBTS) at 0.03 V and negative bias stress threshold (NBTS) at - 0.06 V. Thus, this research on thermally and electrically stable CAAC-IGZO synthesized at low temperatures through PEALD offers insights into the processing and material perspectives for the application of oxide semiconductors in 3D integration.

Atom-Scaled Hafnium Doping for Strengthening the Germanium Oxide Interfacial Layer of The Gate Stack of Germanium P-Type Metal-Oxide-Semiconductor Field Effect Transistor

Abstract We have developed a method that uses a half-cycle Hf precursor adsorption to subtly dope GeO2 IL of the Hf-based gate stack through in situ plasma-enhanced atomic layer deposition. This technique can effectively reduce GeO vaporization and improve the thermal stability of the GeO2 layer. Our results indicated that the accumulation capacitance (Cacc) undergoing higher temperatures showed no noticeable increase in the capacitance-voltage (CV) curves once Hf was delicately introduced into the GeO2 layer. According to the Ge 3d spectra of X-ray photoelectron spectroscopy, we found that the IL had a signal from extra Hf-O bonds; thus, we conclude GeO evaporation can be suppressed substantially by Hf incorporation. As a result, adding metal into GeOx IL to form HfGeOx achieved a remarkably low leakage current of 9 × 10-5 A/cm2 and the lowest interface trap density (Dit) of approximately 2 × 1011 eV−1 cm−2 at 500C of PMA. In addition, applying this gate stack structure to device fabrication significantly reduced the leakage current of the off-state and improved the effective peak hole mobility.

Field Emission from Carbon Nanotubes on Titanium Nitride-Coated Planar and 3D-Printed Substrates.

Carbon nanotubes (CNTs) are well known for their outstanding field emission (FE) performance, facilitated by their unique combination of electrical, mechanical, and thermal properties. However, if the substrate of choice is a poor conductor, the electron supply towards the CNTs can be limited, restricting the FE current. Furthermore, ineffective heat dissipation can lead to emitter-substrate bond degradation, shortening the field emitters' lifetime. Herein, temperature-stable titanium nitride (TiN) was deposited by plasma-enhanced atomic layer deposition (PEALD) on different substrate types prior to the CNT growth. A turn-on field reduction of up to 59% was found for the emitters that were generated on TiN-coated bulk substrates instead of on pristine ones. This observation was attributed exclusively to the TiN layer as no significant change in the emitter morphology could be identified. The fabrication route and, consequently, improved FE properties were transferred from bulk substrates to free-standing, electrically insulating nanomembranes. Moreover, 3D-printed, polymeric microstructures were overcoated by atomic layer deposition (ALD) employing its high conformality. The results of our approach by combining ALD with CNT growth could assist the future fabrication of highly efficient field emitters on 3D scaffold structures regardless of the substrate material.

Tunable EOT Scaling Down to 0. 55 nm for HfO2-Based Gate-Stacks on Ge Substrate by In Situ H2 Plasma Treatment

Abstract We propose a continuous fabrication method for HfO2-based gate stacks on a Ge bulk p-type metal–oxide–semiconductor capacitor (pMOSCAP) with HfGeOx interfacial layer by H2 plasma treatment through in situ plasma-enhanced atomic layer deposition. The electrical characteristics showed that the proper hydrogen plasma treatment could obtain an aggressively scaled equivalent oxide thickness of approximately 0.55 nm and a relatively low gate leakage current of 8 × 10-4 A/cm2 under PMA 500C.

Plasma enhanced atomic layer deposition of silicon nitride using magnetized very high frequency plasma

To obtain high-quality SiN x films applicable to an extensive range of processes, such as gate spacers in fin field-effect transistors (FinFETs), the self-aligned quadruple patterning process, etc, a study of plasma with higher plasma density and lower plasma damage is crucial in addition to study on novel precursors for SiN x plasma-enhanced atomic layer deposition (PEALD) processes. In this study, a novel magnetized PEALD process was developed for depositing high-quality SiN x films using di(isopropylamino)silane (DIPAS) and magnetized N2 plasma at a low substrate temperature of 200 °C. The properties of the deposited SiN x films were analyzed and compared with those obtained by the PEALD process using a non-magnetized N2 plasma source under the same conditions. The PEALD SiN x film, produced using an external magnetic field (ranging from 0 to 100 G) during the plasma exposure step, exhibited a higher growth rate (∼1 Å/cycle) due to the increased plasma density. Additionally, it showed lower surface roughness, higher film density, and enhanced wet etch resistance compared to films deposited using the PEALD process with non-magnetized plasmas. This improvement can be attributed to the higher ion flux and lower ion energy of the magnetized plasma. The electrical characteristics, such as interface trap density and breakdown voltage, were also enhanced when the magnetized plasma was used for the PEALD process. Furthermore, when SiN x films were deposited on high-aspect-ratio (30:1) trench patterns using the magnetized PEALD process, an improved step coverage of over 98% was achieved, in contrast to the conformality of SiN x deposited using non-magnetized plasma. This enhancement is possibly a result of deeper radical penetration enabled by the magnetized plasma.

Remote inductively coupled plasmas in Ar/N2 mixtures and implications for plasma enhanced ALD

Plasma enhanced atomic layer deposition (PEALD) is a cyclic atomic layer deposition (ALD) process that incorporates plasma-generated species into one of the cycle substeps. The addition of plasma is advantageous as it generally provides unique reactants and a substantially reduced growth temperature compared to thermal approaches. However, the inclusion of plasma, coupled with the increasing variety of plasma sources used in PEALD, can make these systems challenging to understand and control. This work focuses on the use of plasma diagnostics to examine the plasma characteristics of a remote inductively coupled plasma (ICP) source, a type of plasma source that is commonly used for PEALD. Ultraviolet to near-infrared spectroscopy and spatially resolved Langmuir probe measurements are employed to characterize a remote ICP system using nitrogen-based gas chemistries typical for III-nitride growth processes. Spectroscopy is used to characterize the relative concentrations of important reactive and energetic neutral species generated in the remote ICP as a function of gas flow rate, Ar/N2 flow fraction, and gas pressure. In addition, the plasma potential and plasma density for the same process parameters are examined using an RF compensated Langmuir probe downstream from the ICP source. The results are also discussed in terms of their impact on materials growth.

Area-selective atomic layer deposition (AS-ALD) of low temperature (300 °C) cobalt thin film using octadecyltrichlorosilane (ODTS) self-assembled monolayers (SAMs)

As the semiconductor industry advances, manufacturing technologies encounter challenges in achieving precise alignment and thickness control with smaller and more intricate 3D structures. Addressing this, Area-selective atomic layer deposition (AS-ALD) emerges as a promising “bottom-up” approach, offering an alternative to current nano-patterning techniques. To achieve AS-ALD, self-assembled monolayers (SAMs) are employed as inhibitor agents. In this study, we employed plasma-enhanced atomic layer deposition (PEALD) to promote self-limiting surface reactions and enable low-temperature processing, thereby facilitating the implementation of high purity cobalt (Co) film through AS-ALD using octadecyltrichlorosilane (ODTS) SAM as an inhibitor. The selective deposition is achieved by employing SAMs as an inhibitor, belonging to the deactivation process, a common method for realizing a bottom-up approach. SAMs can form a thin organic film on a solid surface, allowing for surface modifications to become hydrophobic or hydrophilic. Through the selective deposition of Co in the PEALD low-temperature process (300 °C), we successfully addressed the degradation issue of ODTS SAM and verified the successful achievement of a high-purity selectively deposited 13.4 nm Co film. Our findings highlight the potential of selective Co deposition for realizing complex 3D structures and narrow interconnection layers.

Nb Doping and Alloying of 2D WS2 by Atomic Layer Deposition for 2D Transition Metal Dichalcogenide Transistors and HER Electrocatalysts.

We utilize plasma-enhanced atomic layer deposition to synthesize two-dimensional Nb-doped WS2 and NbxW1-xSy alloys to expand the range of properties and improve the performance of 2D transition metal dichalcogenides for electronics and catalysis. Using a supercycle deposition process, films are prepared with compositions spanning the range from WS2 to NbS3. While the W-rich films form crystalline disulfides, the Nb-rich films form amorphous trisulfides. Through tuning the composition of the films, the electrical resistivity is reduced by 4 orders of magnitude compared to pure ALD-grown WS2. To produce Nb-doped WS2 films, we developed a separate ABC-type supercycle process in which a W precursor pulse precedes the Nb precursor pulse, thereby reducing the minimum Nb content of the film by a factor of 3 while maintaining a uniform distribution of the Nb dopant. Initial results are presented on the electrical and electrocatalytic performances of the films. Promisingly, the NbxW1-xSy films of 10 nm thickness and composition x ≈ 0.08 are p-type semiconductors and have a low contact resistivity of (8 ± 1) × 102 Ω cm to Pd/Au contacts, demonstrating their potential use in contact engineering of 2D TMD transistors.

Plasma-enhanced atomic-layer-deposited HfO2–SiO2 nanolaminates for broadband antireflection coatings

The ever-increasing demand for broadband antireflection (AR) coatings has led to a growing interest in nanolaminates (NLs) with tunable properties. However, achieving excellent optical performance in NLs can be challenging due to multiple interfaces and a rather thin sublayer. In this study, we systematically investigated the factor that deteriorates the optical performance, focusing on the sublayer thickness deviation, sublayer n deviation, and interfacial diffusion, to correct the n-profiles of NLs. A pre-correction strategy for the AR coating design is proposed and experimentally demonstrated via plasma-enhanced atomic layer deposition. The excellent fit of the spectrum demonstrates that the proposed design strategy can benefit structure-sensitive NL-based coatings.

Recent Achievements for Flexible Encapsulation Films Based on Atomic/Molecular Layer Deposition.

The purpose of this paper is to review the research progress in the realization of the organic-inorganic hybrid thin-film packaging of flexible organic electroluminescent devices using the PEALD (plasma-enhanced atomic layer deposition) and MLD (molecular layer deposition) techniques. Firstly, the importance and application prospect of organic electroluminescent devices in the field of flexible electronics are introduced. Subsequently, the principles, characteristics and applications of PEALD and MLD technologies in device packaging are described in detail. Then, the methods and process optimization strategies for the preparation of organic-inorganic hybrid thin-film encapsulation layers using PEALD and MLD technologies are reviewed. Further, the research results on the encapsulation effect, stability and reliability of organic-inorganic hybrid thin-film encapsulation layers in flexible organic electroluminescent devices are discussed. Finally, the current research progress is summarized, and the future research directions and development trends are prospected.

Study of Mid-Pressure Ar Radiofrequency Plasma Used in Plasma-Enhanced Atomic Layer Deposition of α-Al2O3

This study investigated the characteristics of radiofrequency, middle-pressure argon plasma used in the atomic layer deposition (ALD) of Al2O3 films. Based on the electrical characteristics—the current, voltage, and phase shift between them—and the stability of the plasma plume, the optimum plasma power, allowing reliable switching on of the plasma for any step of an ALD cycle, was determined. Spectral measurements were performed to determine the gas temperature and reactive species that could be important in the ALD process. The density of metastable argon atoms was estimated using tunable laser absorption spectroscopy. It was concluded that plasma heating of substrates did not affect film growth. The crystallization-enhancing effect of plasma observed in these experiments was due to the action of OH radicals produced in the plasma.

Atomic layer deposition for tuning the surface chemical composition of nickel iron phosphates for oxygen evolution reaction in alkaline electrolyzers

Transition metal phosphates are promising catalysts for the oxygen evolution reaction (OER) in alkaline medium. Herein, Fe-doped Ni phosphates are deposited using plasma-enhanced atomic layer deposition (PE-ALD) at 300 °C. A sequence of f Fe phosphate PE-ALD cycles and n Ni phosphate PE-ALD cycles is repeated x times. The Fe to Ni ratio can be controlled by the cycle ratio (f/n), while the film thickness can be controlled by the number of cycles (x times (n+f )). 30 nm films with an Fe/Ni ratio of ∼10% and ∼37%, respectively, are evaluated in 1.0 M KOH solution. Remarkably, a significant difference in OER activity is found when the order of the Ni and Fe phosphate PE-ALD cycles in the deposition sequence is reversed. A 20%–45% larger current density is obtained for catalysts grown with an Fe phosphate PE-ALD cycle at the end compared to the Ni phosphate-terminated flavour. We attribute this to a higher concentration of Fe centers on the surface, as a consequence of the specific PE-ALD approach. Secondly, increasing the thickness of the catalyst films up to 160 nm results in an increase of the OER current density and active surface area, suggesting that the as-deposited smooth and continuous films are converted into electrolyte-permeable structures during catalyst activation and operation. This work demonstrates the ability of PE-ALD to control both the surface and bulk composition of thin film electrocatalysts, offering valuable opportunities to understand their impact on performance.

Corrosion Behavior of Ta and TiN Double-Layer-Coated SUS316L for PEMFC Bipolar Plates Using Plasma-Enhanced Atomic Layer Deposition and Magnetron Sputtering

In this study, the corrosion behavior of Ta and TiN double-layered-coated SUS316L is investigated for proton-exchange membrane fuel cells (PEMFCs) bipolar plates. The surface of SUS316L is modified by depositing 4.5 μm of Ta and 200 or 400nm of TiN using magnetron sputtering and plasma-enhanced atomic layer deposition, respectively. The experimental results reveal that this coating significantly enhances the corrosion resistance and reduces the interfacial contact resistance of the bipolar plate. Under electrochemical conditions that are 500 times more acidic than those specified by the Department of Energy (DOE), the coated SUS316L achieves a corrosion current density of only 1.0µA/cm2 at 0.6 VSCE. The corrosion current density reduces up to more than two orders of magnitude, and the interfacial contact resistance with carbon paper is below 10 mΩcm2 at compression forces below 140N/cm2, thus meeting the DOE 2025 target value for both corrosion current density and interfacial contact resistance. Our findings suggest the potential of Ta and TiN double-layered-coated SUS316L as durable bipolar plate materials for PEMFCs.

Effect of Yttrium Treatment on Germanium-Oxide-Based Interfacial Layer of Ge P-Channel Metal–Oxide–Semiconductor Field-Effect Transistor Fabricated Through in Situ Plasma-Enhanced Atomic Layer Deposition

Effect of Yttrium Treatment on Germanium-Oxide-Based Interfacial Layer of Ge P-Channel Metal–Oxide–Semiconductor Field-Effect Transistor Fabricated Through in Situ Plasma-Enhanced Atomic Layer Deposition

Growth of conformal TiN thin film with low resistivity and impurity via hollow cathode plasma atomic layer deposition

Copper has been used as an interconnect material in integrated semiconductor devices because of its excellent conductivity, mechanical strength, and electromigration resistance. Introducing a diffusion barrier layer using transition metals such as Ti, Ta, W, Mo, and their nitrides can effectively prevent copper diffusion into the transistor region. TiN is widely used as the diffusion barrier. Plasma-enhanced atomic layer deposition (PEALD), which uses plasma to activate molecular reactions, can be used to fabricate high-quality thin films at lower temperatures than thermal atomic layer deposition. However, its high electrical resistivity and poor step coverage are disadvantageous for its adoption in highly scaled three-dimensional structures. In this study, TiN thin films were fabricated using PEALD with a hollow cathode plasma (HCP) source. The fabricated TiN exhibited a high density (5.29 g/cm3), which was very close to the theoretical density of TiN. Moreover, it has low electrical resistivity (132 μΩ cm) and excellent step coverage (>98%) in a trench pattern with a high aspect ratio of 32:1. These results suggest the possible application of the PEALD of TiN films using HCP sources in semiconductor device manufacturing.

Fabrication of the low-k films with tunable k value as spacers in advanced CMOS technology

In advanced CMOS technology, a suitable spacer scheme is crucial to alleviate the effects of increasing parasitic resistance and capacitance on device performance as the critical dimensions shrinking. Low dielectric constant (low-k) films, possessing a tunable k value ranging from 3.5 to 6.5, were fabricated using plasma-enhanced atomic layer deposition in a single chamber. The fabrication process involved the deposition of the SiN film via SiH2I2 with N2 plasma, as well as the deposition of the SiOX, SiOCN, and SiON films using diisopropylamino silane with O2, Ar/O2, and N2/O2 plasmas, respectively. The introduction of groups containing carbon (C) tended to loosen the film structure, due to its weak bond strength with Si, thus made distinctions in structural and electrical stability. We developed such a process which can adjust the C-group concentration and O, N content to tune the film k value. The SiOx, SiOCN, SiON, and SiN films had high breakdown strength of 9.04, 7.23, 9.41, and over 11 MV cm−1, and meanwhile low leakage current density of 2.42 × 10−9, 4.78 × 10−8, 1.29 × 10−9, and 9.26 × 10−10 A cm−2, respectively. The films exhibited remarkable thermal stability, enhanced breakdown strength, and suppressed leakage with annealing treatment, which could be attributed to the desorption of —CHX groups. Moreover, the low-k materials demonstrated excellent step coverage both in the inner-spacer cavity and on sidewalls, exploring the potential application as spacers in advanced CMOS structure.

High-performance MoS2 phototransistors with Hf1–x Al x O back-gate dielectric layer grown by plasma enhanced atomic layer deposition

Molybdenum sulfide (MoS2) as an emerging optoelectronic material, shows great potential for phototransistors owing to its atomic thickness, adjustable band gap, and low cost. However, the phototransistors based on MoS2 have been shown to have some issues such as large gate leakage current, and interfacial scattering, resulting in suboptimal optoelectronic performance. Thus, Al-doped hafnium oxide (Hf1–x Al x ) is proposed to be a dielectric layer of the MoS2-based phototransistor to solve this problem because of the relatively higher crystallization temperature and dielectric constant. Here, a high-performance MoS2 phototransistor with Hf1–x Al x O gate dielectric layer grown by plasma-enhanced atomic layer deposition has been fabricated and studied. The results show that the phototransistor exhibits a high responsivity of 2.2 × 104 A W−1, a large detectivity of 1.7 × 1017 Jones, a great photo-to-dark current ratio of 2.2 × 106%, and a high external quantum efficiency of 4.4 × 106%. The energy band alignment and operating mechanism were further used to clarify the reason for the enhanced MoS2 phototransistor. The suggested MoS2 phototransistors could provide promising strategies in further optoelectronic applications.

Investigation of atomic layer deposition methods of Al2O3 on n-GaN

In this work, three atomic layer deposition (ALD) approaches are used to deposit an Al2O3 gate insulator on n-GaN for application in vertical GaN power switches: thermal ALD (ThALD), plasma-enhanced ALD (PEALD), and their stacked combination. The latter is a novel method to yield the most ideal insulating layer. Also, the influence of an in situ NH3 or H2 plasma pre-treatment is studied. Planar MIS capacitors are used to investigate the electrical properties and robustness of the gate insulators. In vacuo x-ray photoelectron spectroscopy (XPS) is used to study the changes in chemical composition after every surface treatment. XPS shows that all plasma pre-treatments efficiently remove all carbon contamination from the surface, but only NH3 plasma is observed to additionally remove the native oxide from the n-GaN surface. The water precursor step in the ThALD process does not completely remove the CH3 ligands of the trimethylaluminum precursor step, which might electrically be associated with a reduced forward bias robustness. The O2 plasma step in the PEALD process is associated with the removal of carbon and a tremendous increase of the O content in the GaN surface region. Electrically, this strongly correlates to an enhanced forward bias robustness and an increased forward bias hysteresis, respectively. The ThALD/PEALD stack method mitigates the shortcomings of both ALD processes while maintaining its advantages. Electrical measurements indicate that the stack method alongside NH3 plasma pretreatment provides the best characteristics in terms of hysteresis, threshold voltage, forward bias robustness, and interface trap density of states.

Structural, optical and phonon properties of hafnium oxynitride thin films synthesized using plasma-enhanced atomic layer deposition

Hafnium Oxynitride belongs to the group IVB compounds with high permittivity and large acoustic impedance. In this work, hafnium oxynitride films have been synthesized using plasma-enhanced atomic layer deposition on Si and Quartz substrates. XRD results show the presence of mixed cubic and monoclinic phases with an optimum crystallization occurring at 850 °C. The thin films show strong absorption in the UV–visible spectrum suggesting semiconductor behaviour. The optical properties of the spectrophotometer and spectroscopic ellipsometry agree with the XRD observations. We also report the first observation of experimentally derived photoluminescence (PL) from hafnium oxynitride thin films synthesized using plasma-enhanced atomic layer deposition. The PL spectrum is consistent with the XRD results with two absorption peaks around 576 nm and 705 nm, corresponding to cubic and monoclinic phases, respectively. Also, the PL results match very well with the theoretical value of the band gap of cubic and monoclinic phases of Hf2ON2. The Raman spectrum shows a phonon band gap around 242–263 cm−1, consistent with the theoretically reported value for cubic Hf2ON2.

Suppressing substrate oxidation during plasma-enhanced atomic layer deposition on semiconductor surfaces

Plasma-enhanced atomic layer deposition (PE-ALD) is widely employed in microelectronics, energy, and sensing applications. Typically, PE-ALD processes for metal oxides utilize remote inductively coupled plasmas operated at powers of >200 W, ensuring a sufficient flux of oxygen radicals to the growth surface. However, this approach often leads to significant oxidation of chemically sensitive substrates, including most technological semiconductors. Here, we demonstrate that plasma powers as low as 5 W can effectively suppress substrate oxidation while maintaining the structural, optical, and electronic quality of the films. Specifically, we investigate the growth of titanium oxide (TiOx) using two commonly used metalorganic precursors, titanium isopropoxide and tetrakis(dimethylamino)titanium. Films deposited with 5 and 300 W oxygen plasma power are nearly indiscernible from one another, exhibiting significantly lower defect concentrations than those obtained from thermal ALD with H2O. The low plasma power process preserves desired physical characteristics of PE-ALD films, including large optical constants (n > 2.45 at 589 nm), negligible defect-induced sub-bandgap optical absorption (α < 102 cm−1), and high electrical resistivity (>105 Ω cm). Similar behavior, including suppressed interface oxidation and low defect content, is observed on both Si and InP substrates. As an example application of this approach, the assessment of InP/TiOx photocathodes and Si/TiOx photoanodes reveals a significant improvement in the photocurrent onset potential in both cases, enabled by suppressed substrate oxidation during low power PE-ALD. Overall, low power PE-ALD represents a generally applicable strategy for producing high quality metal oxide thin films while minimizing detrimental substrate reactions.