Remote Plasma-enhanced Atomic Layer Deposition Research Articles

Conductance modification of molybdenum oxide thin films through oxygen-vacancy engineering for visible-blind ultraviolet photodetection

We propose a simple approach to locally modify the conductance of molybdenum oxide thin films with thermal annealing in oxygen atmosphere at relatively low temperature for constructing a visible-blind ultraviolet photoconductor. The amorphous MoO x is grown by remote plasma enhanced atomic layer deposition (RPALD), and then crystallized into α-MoO x at 500 °C in argon atmosphere, which exhibits good conductance with resistivity of 3.9 × 10−3 Ω cm due to the formation of oxygen vacancies. Good ohmic contact between Ti and the crystallized MoO x is demonstrated with specific contact resistance of 9.74 × 10−4 Ω cm2. The lateral Au/Ti-MoO x -Ti/Au structures are defined and the conductance of the exposed MoO x channel is significantly modified by thermal annealing in oxygen atmosphere to form a photodetector, which shows obvious photoresponse at the wavelength of less than 372 nm with low dark current of 0.9 pA at 5 V, and the remarkable responsivity of 0.75 mA W−1 at 280 nm is achieved with a high ultravoilet/visible rejection ratio. The low dark current and incredible responsivity can be attributed to the good ohmic contacts of untreated MoO x and the reduction of number of oxygen vacancies in the MoO x channel. The key role of oxygen vacancy on the conductance of MoO x has been demonstrated. Those results suggest that the MoO x thin films are promising candidate for visible-blind ultraviolet photodetectors in a simple complementary metal oxide semiconductor (CMOS)-compatible process.

Plasma-enhanced atomic layer deposition of WO3-SiO2 films using a heteronuclear precursor

Tungsten oxide–silicon dioxide (WOx–SiOy) composite thin films were deposited for the first time via the remote oxygen plasma-enhanced atomic layer deposition (ALD) process using a novel metal-organic heteronuclear and heteroleptic precursor, bis(tert-butylimido)bis(trimethylsilylmethyl)tungsten. Self-limiting ALD growth was demonstrated over a wide temperature window of 203–328 °C with growth per cycle decreasing with increasing temperature from 0.75 to 0.4 Å/cycle, respectively. Residual gas analysis revealed ligand competition and showed that ligand reaction during ALD nucleation and growth was a function of deposition temperature, thereby affecting the film composition. As the temperature increased from 203 to 328 °C, the film composition [W/(Si + W)] ranged from 0.45 to 0.53. In addition, the carbon impurity content was reduced and the refractive index increased from 1.73 to 1.96, the density increased from 4.63 to 5.6 g/cm3, and the optical bandgap decreased from 3.45 to 3.27 eV. Grazing angle x-ray diffraction indicated that as-deposited films were amorphous. Upon annealing in O2 at 500 °C or higher, depending on deposition temperature, films are crystalized into the triclinic WO3 phase. At the same time, WO3 is sublimed from the surface and films are reduced in thickness.

High-quality remote plasma enhanced atomic layer deposition of aluminum oxide thin films for nanoelectronics applications

Here, we report comprehensive investigations of aluminum oxide (Al2O3) high-κ gate oxides deposited via remote plasma enhanced atomic layer deposition (Re-PEALD) with mesh configuration in a commercial 100 mm ALD reactor. Trimethylaluminum (Al(CH3)3), dioxygen (O2) plasma, and Argon (Ar) are used as the metal precursor, oxidant, and carrier/purge, respectively. The growth rate per cycle and non-uniformity of Al2O3 thin films is analyzed with the variation in duration of (Al(CH3)3) pulse, O2 plasma, post-precursor purge, post-oxidant purge, RF power, and substrate temperature. High-quality monolayer type Al2O3 thin films with a growth rate of ~ 1.1 Å/cycle are achieved for a wide temperature range from ~ 100 °C to ~ 300 °C suitable for various nanoelectronics applications ranging from flexible substrates to low thermal budget and high mobility alternate semiconductor substrates. Further, the Al/Re-PEALD-Al2O3/p-Si, metal-oxide-semiconductor (MOS) structures are investigated for capacitance-voltage, capacitance-frequency, and leakage current-voltage characteristics to demonstrate the quality of Re-PEALD-Al2O3 thin films. The Al/Re-PEALD-Al2O3/p-Si, MOS structures revealed excellent electrical characteristics with ultralow minimum interface trap density (Dit) ~ 9.9 × 109 eV−1cm−2, negative effective oxide charges (Neff) ~ 5.52 × 1012 cm−2, low leakage current density of ~ 4.1 nA/cm2 at −1 V, hysteresis-free, insignificant Vth shift, and trivial frequency dispersion. Moreover, the chemical analysis using XPS depth profiling disclosed that Re-PEALD deposited Al2O3 thin films results in a high-quality gradient Al2O3/SiOx/Si interface rather than an abrupt Al2O3/Si interface, and the oxygen rich thin films due to the oxygen (O2−) interstitials close to the interface are the sources of negative fixed oxide charges in Re-PEALD-Al2O3/Si, system. These results intend to boost the investigations of Re-PEALD Al2O3 ultrathin films for low thermal budget high mobility alternate semiconductor substrates for nanoelectronics applications.

Multiscale computational fluid dynamics modeling and reactor design of plasma-enhanced atomic layer deposition

Plasma-enhanced atomic layer deposition (PEALD) is one of the most widely adopted deposition methods in the semiconductor industry. It is chosen largely due to its superior ability to deliver ultra-conformal dielectric thin-films with high aspect-ratio surface structures, which are encountered more and more often in the novel design of metal-oxide-semiconductor field-effect transistors (MOSFETs) in the NAND (Not-And)-type flash memory devices. Compared with the traditional thermal ALD method, PEALD allows for lower operating temperature and speeds up the deposition process with the involvement of plasma species. Despite its popularity, the development of PEALD operation policies remains a complicated and expensive task, which motivates the construction of an accurate and comprehensive simulation model. While existing models have described the individual or partially coupled domains, none of these models has captured all three domains in the PEALD process: surface reaction, macroscopic gas transport, and plasma generation. In this work, a comprehensive multiscale computational fluid dynamics (CFD) model is developed for a remote PEALD reactor used in the deposition of HfO2 thin-films. First, a previously developed kinetic Monte-Carlo (kMC) model is adapted for the multiscale simulation to describe the surface reactions. Then, two macroscopic models, specifically tailored for the remote plasma reactor, are formulated to describe the dynamic behaviors of the plasma generation and bulk species transport domains, respectively. Additionally, an integrated message passing interface (MPI) scheme is built to couple and resolve the communication between different scales in the model. The model results are then validated with experimental data and an automated workflow is established for model calculations without human intervention. Finally, a set of baseline operating conditions derived from the model simulation results is proposed to guarantee the production of high-quality thin-films.

Plasmonic nanocomposites of zinc oxide and titanium nitride

The authors produce plasmonic ZnO-TiN nanocomposite films by depositing plasma-synthesized ZnO nanocrystals onto a substrate and then by infilling the nanocrystal network's pores with TiN via remote plasma-enhanced atomic layer deposition (PEALD). This ZnO-TiN nanocomposite exhibits a plasmonic resonance that is blueshifted compared to planar titanium nitride thin films. The authors study the effects of PEALD conditions and the ZnO film thickness on the plasmonic response of these nanocomposites and exploit the optimized film in a device that generates photocurrent at zero bias.

Comparison of Hafnium Dioxide and Zirconium Dioxide Grown by Plasma-Enhanced Atomic Layer Deposition for the Application of Electronic Materials

We report the growth of nanoscale hafnium dioxide (HfO2) and zirconium dioxide (ZrO2) thin films using remote plasma-enhanced atomic layer deposition (PE-ALD), and the fabrication of complementary metal-oxide semiconductor (CMOS) integrated circuits using the HfO2 and ZrO2 thin films as the gate oxide. Tetrakis (dimethylamino) hafnium (Hf[N(CH3)2]4) and tetrakis (dimethylamino) zirconium (IV) (Zr[N(CH3)2]4) were used as the precursors, while O2 gas was used as the reactive gas. The PE-ALD-grown HfO2 and ZrO2 thin films were analyzed using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and high-resolution transmission electron microscopy (HRTEM). The XPS measurements show that the ZrO2 film has the atomic concentrations of 34% Zr, 2% C, and 64% O while the HfO2 film has the atomic concentrations of 29% Hf, 11% C, and 60% O. The HRTEM and XRD measurements show both HfO2 and ZrO2 films have polycrystalline structures. n-channel and p-channel metal-oxide semiconductor field-effect transistors (nFETs and pFETs), CMOS inverters, and CMOS ring oscillators were fabricated to test the quality of the HfO2 and ZrO2 thin films as the gate oxide. Current-voltage (IV) curves, transfer characteristics, and oscillation waveforms were measured from the fabricated transistors, inverters, and oscillators, respectively. The experimental results measured from the HfO2 and ZrO2 thin films were compared.

Remote plasma-enhanced atomic layer deposition of gallium oxide thin films with NH3 plasma pretreatment

High quality gallium oxide (Ga2O3) thin films are deposited by remote plasma-enhanced atomic layer deposition (RPEALD) with trimethylgallium (TMG) and oxygen plasma as precursors. By introducing in-situ NH3 plasma pretreatment on the substrates, the deposition rate of Ga2O3 films on Si and GaN are remarkably enhanced, reached to 0.53 and 0.46 Å/cycle at 250 °C, respectively. The increasing of deposition rate is attributed to more hydroxyls (–OH) generated on the substrate surfaces after NH3 pretreatment, which has no effect on the stoichiometry and surface morphology of the oxide films, but only modifies the surface states of substrates by enhancing reactive site density. Ga2O3 film deposited on GaN wafer is crystallized at 250 °C, with an epitaxial interface between Ga2O3 and GaN clearly observed. This is potentially very important for reducing the interface state density through high quality passivation.

Critical Atomic-level Processing Technologies: Remote Plasma-enhanced Atomic Layer Deposition and Atomic Layer Etching

As feature sizes of devices shrink every year, deposition and etching processes change to be very challenge, especially for sub-7 nm technology node. The acceptable variability of feature size is expected to be several atoms of silicon/germanium in the future. Therefore, Remote Plasma-Enhanced Atomic Layer Deposition (RPE-ALD) and Atomic Layer Etching (ALE) change to be more and more important in the semiconductor fabrication. Due to their self-limiting behavior, the atomic-scale fidelity could be realized for both of them in the processes. Compared with traditional Physical Vapor Deposition (PVD) and Chemical Vapor Deposition (CVD) methods, atomic-scale thickness controllability and good conformality can be achieved by RPE-ALD. Unlike conventional plasma etching, atomicscale precision and excellent depth uniformity can be achieved by ALE. The fundamentals and applications of RPE-ALD and ALE have been discussed in this paper. Using the combination of them, atomic-level deposition/etch-back method is also mentioned for achieving high quality ultra-thin films on three dimensional (3D) features.

Remote plasma-enhanced atomic layer deposition of metallic TiN films with low work function and high uniformity

Thermal stability of metal/n-GaN contact is critical for its applications in microelectronic and optoelectronic devices. Metal Ti is generally used to make Ohmic contact on n-GaN after high temperature annealing, and the key factor is to form TiN at the interface. To reduce the processing temperature and improve the reliability, metallic titanium nitride (TiN) thin film has been proposed to substitute traditional metals (such as Ti) in the contact structures, due to its low work function and high blocking effect. For this novel approach, the first step is to fabricate high quality TiN films. Here, the authors adopted remote plasma-enhanced atomic layer deposition method to deposit TiN films under well-controlled conditions. Stoichiometric TiN films (Ti:N ∼ 1:1) with low oxygen contamination (<5%) have been deposited uniformly on 2 in. substrates in a large temperature range of 250–400 °C. The work function of TiN films is quite low (∼3.7 ± 0.1 eV) compared to metal Ti (∼4.33 eV), and almost independent to the growth temperature and substrates. Strong Fermi edge and high conductivity indicate excellent metallic property of the TiN films. This study of TiN film growth paves the way to establish a low temperature process and improve the thermal stability of Ohmic contacts for wide band gap semiconductor-based devices.

Tuning Material Properties of Oxides and Nitrides by Substrate Biasing during Plasma-Enhanced Atomic Layer Deposition on Planar and 3D Substrate Topographies.

Oxide and nitride thin-films of Ti, Hf, and Si serve numerous applications owing to the diverse range of their material properties. It is therefore imperative to have proper control over these properties during materials processing. Ion-surface interactions during plasma processing techniques can influence the properties of a growing film. In this work, we investigated the effects of controlling ion characteristics (energy, dose) on the properties of the aforementioned materials during plasma-enhanced atomic layer deposition (PEALD) on planar and 3D substrate topographies. We used a 200 mm remote PEALD system equipped with substrate biasing to control the energy and dose of ions by varying the magnitude and duration of the applied bias, respectively, during plasma exposure. Implementing substrate biasing in these forms enhanced PEALD process capability by providing two additional parameters for tuning a wide range of material properties. Below the regimes of ion-induced degradation, enhancing ion energies with substrate biasing during PEALD increased the refractive index and mass density of TiOx and HfOx and enabled control over their crystalline properties. PEALD of these oxides with substrate biasing at 150 °C led to the formation of crystalline material at the low temperature, which would otherwise yield amorphous films for deposition without biasing. Enhanced ion energies drastically reduced the resistivity of conductive TiNx and HfNx films. Furthermore, biasing during PEALD enabled the residual stress of these materials to be altered from tensile to compressive. The properties of SiOx were slightly improved whereas those of SiNx were degraded as a function of substrate biasing. PEALD on 3D trench nanostructures with biasing induced differing film properties at different regions of the 3D substrate. On the basis of the results presented herein, prospects afforded by the implementation of this technique during PEALD, such as enabling new routes for topographically selective deposition on 3D substrates, are discussed.

Atomic layer deposition of amorphous Ni-Ta-N films for Cu diffusion barrier

Novel Ni-doped TaN (Ni-Ta-N) films are deposited by remote plasma-enhanced atomic layer deposition (ALD) with pentakis(dimethylamino)tantalum, nickelocene, and NH3 precursors for Cu diffusion barriers. Various Ni-Ta-N films with different compositions are achieved by changing the deposition cycles (n) of Ni sublayer while fixing the deposition cycles of TaN sublayer at 2. As n increases from 1 to 6, the root-mean-square roughness of the deposited film increases from 0.150 to 0.527 nm, and the resistivity decreases from 0.18 to 1.1 × 10−2 Ω cm. After annealing at 400 °C for 30 min in the forming gas (N2/H2), these films still maintain an amorphous texture and demonstrate a negligible reduction of resistivity and a weak increase of density. Subsequently, the barrier effects of the Ni-Ta-N films with different compositions are compared against Cu diffusion after annealing. The results reveal that the Ni-Ta-N films with n ≤ 4 exhibit barrier effects comparable with the ALD TaN film even after annealing at 550 °C. Further, a 3 nm ultrathin Ni-Ta-N film with n = 4, corresponding to an addition of ∼22 at. % Ni to TaN, cannot only reduce the film resistivity by 78% but also effectively block Cu diffusion after annealing at 450 °C for 30 min.

The Cut-Off Phenomenon Effect on ZrO2 Growth Using Remote Plasma-Enhanced Atomic Layer Deposition

Remote plasma-enhanced atomic layer deposition (R-PEALD) of zirconium dioxide (ZrO2) experiments were conducted using tetrakis(dimethylamino)zirconium (TDMAZ) with O2 plasma as the oxidant. The reaction mechanisms of ZrO2 were studied using in situ quartz crystal microbalance (QCM) and in situ quadrupole mass spectroscopy (QMS). QMS revealed typical combustion byproducts such as CO2, CO, NO, and H2O during the O2 plasma process. In addition, Fourier transform infrared spectroscopy (FTIR) measurements were used to identify the bonds present in the thin film at different deposition temperatures. In our previous work, it was found that an increase in temperature resulted in a reduction of impurities in thin films. The influence of the deposition temperature on several possible surface reaction characteristics of the plasma process was studied. Such characteristics included composition of the film and growth per cycle. In particular, it was first demonstrated that the −C≡N group gave rise to cutoff phenomenon...

The α and γ plasma modes in plasma-enhanced atomic layer deposition with O2–N2 capacitive discharges

Two distinguishable plasma modes in the O2–N2 radio frequency capacitively coupled plasma (CCP) used in remote plasma-enhanced atomic layer deposition (PEALD) were observed. Optical emission spectroscopy and spectra interpretation with rate coefficient analysis of the relevant processes were used to connect the detected modes to the α and γ modes of the CCP discharge. To investigate the effect of the plasma modes on the PEALD film growth, ZnO and TiO2 films were deposited using both modes and compared to the films deposited using direct plasma. The growth rate, thickness uniformity, elemental composition, and crystallinity of the films were found to correlate with the deposition mode. In remote CCP operations the transition to the γ mode can result in a parasitic discharge leading to uncontrollable film growth and thus limit the operation parameters of the capacitive discharge in the PEALD applications.

Low-temperature remote plasma enhanced atomic layer deposition of ZrO2/zircone nanolaminate film for efficient encapsulation of flexible organic light-emitting diodes

Encapsulation is essential to protect the air-sensitive components of organic light-emitting diodes (OLEDs) such as active layers and cathode electrodes. In this study, hybrid zirconium inorganic/organic nanolaminates were fabricated using remote plasma enhanced atomic layer deposition (PEALD) and molecular layer deposition at a low temperature. The nanolaminate serves as a thin-film encapsulation layer for OLEDs. The reaction mechanism of PEALD process was investigated using an in-situ quartz crystal microbalance (QCM) and in-situ quadrupole mass spectrometer (QMS). The bonds present in the films were determined by Fourier transform infrared spectroscopy. The primary reaction byproducts in PEALD, such as CO, CO2, NO, H2O, as well as the related fragments during the O2 plasma process were characterized using the QMS, indicating a combustion-like reaction process. The self-limiting nature and growth mechanisms of the ZrO2 during the complex surface chemical reaction of the ligand and O2 plasma were monitored using the QCM. The remote PEALD ZrO2/zircone nanolaminate structure prolonged the transmission path of water vapor and smooth surface morphology. Consequently, the water barrier properties were significantly improved (reaching 3.078 × 10−5 g/m2/day). This study also shows that flexible OLEDs can be successfully encapsulated to achieve a significantly longer lifetime.

Microwave remote plasma enhanced-atomic layer deposition system with multicusp confinement chamber.

A microwave remote Plasma Enhanced-Atomic Layer Deposition system with multicusp confinement chamber is established at the Plasma and Beam Physics research facilities, Chiang Mai, Thailand. The system produces highly-reactive plasma species in order to enhance the deposition process of thin films. The addition of the multicusp magnetic fields further improves the plasma density and uniformity in the reaction chamber. Thus, the system is more favorable to temperature-sensitive substrates when heating becomes unwanted. Furthermore, the remote-plasma feature, which is generated via microwave power source, offers tunability of the plasma properties separately from the process. As a result, the system provides high flexibility in choice of materials and design experiments, particularly for low-temperature applications. Performance evaluations of the system were carried on coating experiments of Al2O3 layers onto a silicon wafer. The plasma characteristics in the chamber will be described. The resulted Al2O3 films-analyzed by Rutherford Backscattering Spectrometry in channeling mode and by X-ray Photoelectron Spectroscopy techniques-will be discussed.

Characterization of plasma-enhanced atomic layer deposition of Al2O3 using dimethylaluminum isopropoxide

In this research, Al2O3 films were grown by remote plasma-enhanced atomic layer deposition using a nonpyrophoric precursor, dimethylaluminum isopropoxide (DMAI), and oxygen plasma. After optimization, the growth rate was determined to be ∼1.5 Å/cycle within a growth window of 25–220 °C; the higher growth rate than reported for thermal atomic layer deposition was ascribed to the higher reactivity of the plasma species compared with H2O and the adsorption of active oxygen at the surface, which was residual from the oxygen plasma exposure. Both effects enhance DMAI chemisorption and increase the saturation density. In addition, a longer oxygen plasma time was required at room temperature to complete the reaction and decrease the carbon contamination below the detection limit of x-ray photoemission spectroscopy. The properties of the subsequent Al2O3 films were measured for different temperatures. When deposited at 25 °C and 200 °C, the Al2O3 films demonstrated a single Al-O bonding state as measured by x-ray photoemission spectroscopy, a similar band gap of 6.8±0.2 eV as determined by energy loss spectroscopy, a similar index of refraction of 1.62±0.02 as determined by spectroscopic ellipsometry, and uniform growth with a similar surface roughness before and after growth as confirmed by atomic force microscopy. However, the room temperature deposited Al2O3 films had a lower mass density (2.7 g/cm3 compared with 3.0 g/cm3) and a higher atomic ratio of O to Al (2.1 compared with 1.6) as indicated by x-ray reflectivity and Rutherford backscattering spectroscopy, respectively.

Low-temperature remote plasma-enhanced atomic layer deposition of graphene and characterization of its atomic-level structure

Atomic-resolution image of a graphene sheet synthesized by remote plasma-enhanced atomic layer deposition at low temperatures.

Structural, optical, electrical and resistive switching properties of ZnO thin films deposited by thermal and plasma-enhanced atomic layer deposition

In this study, we report on a systematical investigation on the crystal structure, optical and electrical properties of ZnO thin films grown by thermal and remote plasma-enhanced atomic layer deposition (Thermal ALD and PEALD) and their applications in resistive switching devices. The conductivity of ZnO films grown by Thermal ALD at 200°C is ∼169S/cm, demonstrating a good potential for the applications in transparent conducting films. It is possible to deposit ZnO films with good structural quality and few defects at lower temperatures by PEALD. The Al/PEALD-ZnO/Pt devices show good resistive switching properties, while the devices using Thermal ALD ZnO films failed to show any resistive switching behavior, but a perfect Ohmic behavior. The thickness ZnO active layer has a strong effect on the device properties. When the thickness of ZnO film is ∼23nm, the high state-resistance to low state-resistance ratio maintains at larger than 103, while the current compliance for safe operation is ∼1mA much smaller than those for devices with thick active layers. The results have demonstrated the PEALD grown ZnO films have the excellent properties for the applications in high-density 3D resistive random access memory.

Conformality of remote plasma-enhanced atomic layer deposition processes: An experimental study

In total, five metal oxide and one metal plasma-enhanced atomic layer deposition (PEALD) processes were studied with respect to the conformality of the coatings. The study reveals that also high aspect ratio structures (up to 60:1) can be coated conformally with remote PEALD. Oxides could relatively easily be deposited into demanding 3D structures with rather short cycle times but not the silver metal. The key factor in achieving excellent conformality seems to be that sufficient radical density is required to overcome the loss of radicals by recombination. In the case of metals where hydrogen plasma is applied the recombination of hydrogen radicals causes major difficulties in obtaining perfect conformality.

?Characteristics of HfN Films Deposited by Remote Plasma-enhanced Atomic Layer Deposition

?Characteristics of HfN Films Deposited by Remote Plasma-enhanced Atomic Layer Deposition