Thermal and plasma enhanced atomic layer deposition of TiO2: Comparison of spectroscopic and electric properties

We have employed plasma-enhanced and thermal atomic layer deposition (ALD) within the temperature range of 50–150°C for the deposition of ultra-thin (10–50 nm) Al2O3 films on 100Cr6 steel and aluminium Al2024-T3 alloys. [Al(CH3)3] was used as the precursor with either an O2 plasma or water as co-reactants. Neutral salt spray tests showed that the thicker films offered the best corrosion-resistance. Using cyclic voltametry, the 50 nm films were found to be the least porous (<0.5%). For 10 nm thick films, plasma-enhanced ALD afforded a lower porosity and higher film density than thermal ALD. ToF-SIMS measurements on 100Cr6 showed that the main ‘bulk’ of the films contained very few impurities, but OH and C were observed at the interfaces. TEM confirmed that the films were conformal on all substrates and the adhesion was excellent for the films deposited by plasma-enhanced ALD but not for thermal ALD, as delamination was observed. On the basis of these and other results, the prospects of the application of ALD films for corrosion protection, and the use of plasma-enhanced ALD to promote their nucleation, is discussed.

Herein, amorphous molybdenum oxide films are constructed by thermal atomic layer deposition (T‐ALD) and plasma‐enhanced atomic layer deposition (PE‐ALD). The physical and chemical properties of molybdenum oxide films prepared by the two methods are systematically compared by means of film growth law, atomic force microscope, scanning electron microscope, etc. The results show that the amorphous molybdenum oxide physical phase prepared by both ALD methods is MoO3. Compared with T‐ALD MoO3, the growth rate of MoO3 thin films prepared by PE‐ALD is higher. Compared to PE‐ALD MoO3, the MoO3 films prepared by T‐ALD did not have nucleation delayed to a laminar growth mode, resulting in smoother deposited films and contained less impurity carbon. The MoO3 prepared by PE‐ALD contains 7.4% impurity carbon. This carbon‐doped film significantly improves the conductivity of the MoO3 film and shows good electrochemical activity. As expected, the MoO3 films prepared by PE‐ALD show good electrocatalytic oxygen evolution reaction. The overpotential is only 259 mV at 10 mA cm−2 and continues to evolution oxygen for 60 h with almost no attenuation, indicating that carbon doping significantly improves the catalytic intrinsic activity and stability of MoO3.

This contribution will discuss the role and impact of ions during plasma-enhanced atomic layer deposition (ALD), in the context of the latest trends in nanoelectronic device fabrication. Due to the ongoing downscaling of semiconductor device structures, atomic-scale processing techniques such as plasma ALD are becoming increasingly important and more widely applied. Detailed insight into the role of ions is essential, now more than ever, for further advancing the atomic-level precision that plasma ALD offers.Among others, it will be presented that even ions with a low energy of <20 eV, as typical when using a grounded substrate and a remote plasma source, can considerably influence plasma ALD processes. This will be illustrated using plasma ALD of SiO2 and TiO2 as industry-relevant case studies. Specifically, it is observed that (low-energy) ions contribute to the film quality of SiO2,1 can induce crystallization during plasma ALD of TiO2,2 and can alter the growth per cycle by a factor of up to ~2 (for both SiO2 and TiO2). These effects can have important consequences for applications, for instance on the film conformality obtained on 3D nanostructures.Furthermore, the mechanisms governing the influence of ions on an elementary level will be discussed. An important topic here is the combined effect of ion energy, ion flux and plasma exposure time. These parameters can all have a different impact, depending on the plasma and material system. For plasma ALD of SiO2 and TiO2 the combined effect can be universally described by the ion energy dose (i.e., ion energy × flux × exposure time),3 where a minimal effect is obtained when supplying a dose of <1 eV nm-2 cycle-1, or a strong effect when supplying a dose of >100 eV nm-2 cycle-1.1,2 In conclusion, general insights into the role of ions during plasma ALD will be presented, which are particularly important for advancing the level of control over film thickness and material properties in the fabrication of (next-generation) nanoelectronics. Arts et al., Appl. Phys. Lett. 117, 031602 (2020).Arts et al., Impact of ions on film conformality and crystallinity during plasma-assisted atomic layer deposition of TiO2 (to be published).Faraz et al., Plasma Sources Sci. Technol. 28, 024002 (2019). Figure 1

The high-k materials are essential in thin-film transistors. A well-controlled thin film deposition that produces less electronic defects induced by charged vacancies is highly desirable for avoiding high leakage current and and providing an exceptional dielectric strength. This work addresses the use of atomic layer deposition (ALD), plasma-enhanced ALD (PEALD), and its variants to produce low-defective HfO2. The X-ray photoelectron spectroscopy (XPS) and Capacitance-Voltage (C-V) analysis revealed that the thermal ALD (TALD) samples produce electron emissions of ∼ 1 eV above the valence band maximum, negative flat band voltage shift of 1.51 V, and low dielectric breakdown strength (4.37 MV/cm). These properties confirm the high density of positive oxygen vacancies (1.2 × 1013 cm−2) acting as shallow traps, despite its O/Hf ratio (1.84) being higher than the Direct Plasma ALD (DPALD) sample. On the other hand, PEALD induces the formation of neutral vacancies promoted by the electric field of the plasma sheath. These defects are less detrimental to the capacitor performance as their flat band shifts are −0.25 and 1.01 V for remote plasma ALD (RPALD) and DPALD samples. Their dielectric breakdown strength increases by ∼ 1 MV/cm, and a reduced current density by 3 orders of magnitude less than TALD samples. The O/Hf ratio in DPALD samples is 1.80, confirming the benefits of using PEALD approaches.

Comparisons of alumina barrier films deposited by thermal and plasma atomic layer deposition

Growth characteristics and film properties of plasma-enhanced and thermal atomic-layer-deposited magnesium oxide thin films prepared using bis(ethylcyclopentadienyl)magnesium precursor

We report on an alternative, atomic layer deposited (ALD) TaN barrier scheme for Cu interconnects for 14nm technology node and beyond, i.e., 64nm pitch and/or smaller interconnects. With VLSI integration requiring denser packing of interconnects, conformal fill of progressively narrower trenches and vias with high aspect ratio, presents tough challenge for line-of-sight physical vapor deposition processes. ALD overcomes these gap-fill challenges but has disadvantages of low throughput, chemical residues and relatively lower density of ALD barriers for effective blocking of O2and Cu diffusion. From gap-fill perspective, ALD films enable ultrathin, conformal barrier with reduced problems of overhang and large bottom thickness, typical of physical vapor deposited (PVD) films. Reduced bottom-thickness enables via-contact resistance reduction and less overhang improves gap-fill, while maximizing Cu volume in a trench/via structure. Our blanket film studies show that ALD films are 10-15% less dense compared to Ta-rich PVD films, and more importantly only desired low-resistance alpha-Ta nucleates on ALD films vs. thin PVD films. The conformality of ALD TaN as well as the nucleation of alpha-Ta on it form the basis of via contact resistance reduction, leading to performance enhancement.A plasma-enhanced ALD (PEALD) process helps increase density and improves the hermeticity of the barrier. But PEALD can cause dielectric damage and lead to TDDB failures especially in smaller technology nodes. To maximize density while protecting low-k dielectric during deposition and maintaining low-contact resistance, we explored different flavors and combinations of thermal (tALD) and plasma-enhanced ALD (PEALD). In this work, we use a new, commercially available 40 MHz direct-plasma ALD tool and corresponding optimized processes to maximize throughput and minimize dielectric damage. Different ALD flavors, viz., tALD+post plasma(PP) treatment, tALD/PEALD bilayer films were evaluated for 14 nm technology groundrule interconnects in k=2.7 and k=2.55 dielectric levels. We were able to achieve via contact resistance reduction of 25-35%, with equivalent or better performance for yield, defectivity and electromigration (EM), time-dependent dielectric breakdown (TDDB) and stress migration (SM) reliability. In-line measured defect density for dual-damascene interconnects in k=2.55 dielectric was studied with a conservative ALD TaN thickness process window; the splits with 15-20A of tALDPP TaN barrier layers were found to have the lowest defectivity. Similar data for various ALD splits vs. PVD showed that the same tALDPP process with a certain thickness combination of the bilayer TaN/ Ta resulted in least defect density. This same optimized condition looked best for viachain yield for a macro with ~108via links at 14nm groundrule. We also confirmed that the same condition resulted in the lowest via contact resistance for fully landed vias for 45 chiplets across 3 wafers; where via bottom size variation was <10%. Another study with several bilayer ALD splits in k=2.55 dielectric, showed that the 5tALD/5PEALD condition with initial tALD layer protecting the low-k dielectric followed by denser PEALD to get a more effective barrier, yielded better than PVD TaN. The lowest via resistance data was also recorded for the same split. The EM stress results for both via and line-depletion at each of k=2.7 and k=2.55 levels were also studied. ALD splits were slightly worse than PVD condition with the exception of one stress direction, but still pass reliability targets scaled from the 22 nm technology node. The kinetics data for via depletion tests results in activation energy in excess of 1 eV. TDDB stress results were obtained for builds in both k=2.7 and k=2.55 dielectrics. The most significant impact of ALD on TDDB was the restoration of voltage acceleration parameter (gamma) for both levels. Gammas (slopes of lines) for ALD of all three devices were clearly higher. This confirmed that our optimized ALD condition does no damage to the dielectric. Lastly, impact of different liner processes on stress migration (SM) was investigated at 225oC stress for 1000 hours. There were no stress fails on any of the liner splits from the traditional plate and nose type SM structures. In summary, ALD TaN is shown to be a robust alternative barrier for Cu interconnect technology for technologies nodes like 14nm and smaller. The process can be optimized to give ~30% reduction in via contact reduction while preserving healthy yield, defect density and EM, TDDB and SM reliability.

Thermal atomic layer deposition (TALD) and plasma atomic layer deposition (PALD) were used for producing thin NiO x films from nickel(II) acetylacetonate Ni(acac)2, employing different oxidizing agents (deionized water H2O, ozone O3, and molecular oxygen O2). The films were deposited at 300 °C (TALD) and 220 °C (PALD) over glass substrates; their physical and chemical properties were considerably influenced by the choice of oxidizing agents. In particular, ALD(H2O) samples had a low growth per cycle (GPC) and a high concentration of defects. The best NiO x parameters were achieved with PALD(O2), featuring high GPC (0.07 nm/cycle), high optical transparency in the visible region, electrical resistivity (1.18 × 104 Ω·cm), good carrier concentration (8.82 × 1013 cm-3), and common mobility (5.98 cm2/V·s). The resulting NiO x films are polycrystalline and homogeneous in thickness and composition. According to ultraviolet photoelectron spectroscopy (UPS), work function φ and the valence band maximum E V can be tuned by the choice of the coreactant employed, with variations of up to ∼1 eV between TALD and PALD synthesis. Our results suggest that PALD permits one to achieve a better energy band alignment of NiO x and CsFAMAPbBrI perovskite, which is promising for solar cell applications.

Titanium dioxide (TiO 2 ) is a widely used material for photocatalytic, optical, electrical and medical applications. Atomic layer deposition (ALD) represents an excellent technique for the synthesis of thin films due to its precise thickness control, simplicity, high conformity of obtained films and reproducible growth of defect‐free films. It was shown recently that photo‐catalytic TiO 2 films grown on cellulose‐based and porous substrates can be used in water purification systems [1]. Its photo‐catalytic activity strongly depends on the crystal structure and the grain size of the film, i.e. the TiO 2 films must have a well‐defined anatase phase with large polycrystalline grains [2]. It was recognized that plasma enhanced ALD (PEALD) growth of the TiO 2 film can produce the anatase phase even at low deposition temperatures [3]. This result is important for the growth of thin polycrystalline films on temperature‐sensitive materials, such as organic substrates. On the other hand, the grain size is shown to depend critically on the type and the morphology of substrates [4]. We have investigated the effects of thin intermediate layers, grown by ALD on silicon substrates, on the grain size of the TiO 2 films, grown by thermal ALD and PEALD technique in a wide temperature range, from room temperature up to 300°C. Amorphous TiO 2 films were obtained with thermal ALD for temperatures below 150°C, while the anatase phase with crystalline aggregates has been identified on films synthesised with PEALD at low temperatures. We show that the size of crystallites can be greatly enlarged if grown on an intermediate layer of amorphous Al 2 O 3 . The films were characterised by a range of analytical techniques, including scanning electron microscopy with energy dispersive x‐ray spectroscopy, secondary ion mass spectrometry, x‐ray photoelectron spectroscopy and x‐ray diffraction.

Vanadium pentoxide was deposited by atomic layer deposition (ALD) from vanadyl-tri-isopropoxide (VTIP). Water or oxygen was used as a reactive gas in thermal and plasma-enhanced (PE) processes. For PE ALD, there was a wide ALD temperature window from 50 to . Above , VTIP decomposed thermally, resulting in the chemical vapor deposition (CVD) of vanadium pentoxide. The PE ALD reactions saturated much faster than during thermal ALD, leading to a growth rate of approximately 0.7 Å/cycle during PE ALD using or . Optical emission spectroscopy showed combustion-like reactions during the plasma step. X-ray diffraction was performed to determine the crystallinity of the films after deposition and after postannealing under He or atmosphere. Films grown with CVD at and PE ALD at were (001)-oriented as deposited, while thermal and PE ALD films grown at were amorphous as deposited. The crystallinity of the PE ALD could be correlated to its high purity, while the other films had significant carbon contamination, as shown by X-ray photoelectron spectroscopy. Annealing under He led to oxygen-deficient films, while all samples eventually crystallized into under .

Surface engineering of micro- and nanoparticles is of great importance in fields such as catalysis, energy and sensing. For many of these applications particles are required with different bulk and surface properties. A popular technique to achieve this is to coat the particle surface with a nanometer thick layer. Only a few techniques have been explored for depositing such thin conformal coatings. Chemical vapor deposition (CVD) has been used extensively for this purpose, but suffers from a lot of disadvantages, such as imperfect control over layer thickness and uniformity of the coating over all individual particles, particle agglomeration and formation of additional undesired particles due to gas phase reactions between the CVD reactants. In contrast, atomic layer deposition (ALD) is known as a reliable technique for covering complex 3D objects with ultrathin conformal coatings. However, to perform ALD on large quantities of powders, the individual particles need to be fluidized or agitated. Fluidized bed reactors are most often used for ALD on particles, but this reactor concept does not seem to be compatible with plasma enhanced ALD, which is advantages for e.g. coating on temperature sensitive polymer particles or deposition of metals and metal nitrides.In this work, a rotary reactor was used to agitate particles, enabling the deposition of conformal coatings by thermal and plasma-enhanced ALD. Particles ranging from nanometer size to millimeter size were successfully coated with layers of Al2O3, TiO2, AlN and TiN.[1]In-situ mass spectroscopy confirmed that ALD was performed by detecting the expected reaction products. By monitoring the formation of these reaction products over time, it was possible to optimize precursor and reactant usage, which is linearly dependent on the effective surface area of the particles. In the case of plasma enhanced ALD, in-situ optical emission spectroscopy confirmed the mass spectroscopy data. X-ray fluorescence revealed the expected linear relationship between the amount of ALD cycles and the deposited amount of material, while X-ray photo-electron spectroscopy was used to confirm the composition and purity of the coatings. Transmission electron spectroscopy finally showed that the individual particles were coated uniformly and conformally. Our results prove that the proposed rotary reactor enables conformal deposition on nano- and micropowders by thermal and plasma enhanced ALD. In this way, surface engineering of such particles can be achieved.[1] D. Longrie et al., Surface & Coating Technology 213 (2013) 183-191

We propose a deposition method capable of independently controlling the spatial density and average size of Ru nanocrystals by using both plasma-enhanced and thermal atomic layer deposition (ALD). Plasma-enhanced ALD is used to promote the nucleation of Ru nanocrystals, while thermal ALD is used to assist their growth. By the rigorous selection of each stage, we can demonstrate the formation of Ru nanocrystals with a density variation from 3.5 X 10 11 to 8.4 X 10 11 cm -2 and sizes from 2.2 to 5.1 nm, which is in the optimum density and size range of nanocrystal floating-gate memory application.

ABSTRACTAn electrical and analytical study was carried out to investigate TiW/ZnO Schottky contacts with 30 nm ZnO thin film layers deposited by pulsed laser deposition (PLD), plasma enhanced atomic layer deposition (PEALD), and thermal atomic layer deposition (TALD). Devices with ZnO layer deposited by TALD exhibit approximately linear behavior in their I-V measurements. However, both devices with ZnO layers deposited by PEALD and PLD behaved like Schottky rectifiers with barrier heights between TiW and ZnO of 0.51 eV and 0.45 eV respectively and ideality factors of 2.0 and 2.3 respectively. The PEALD deposited ZnO Schotty diodes demonstrated an on/off rectifying ratio of about 25 at ±1 V. The leakage current values of the PLD deposited ZnO Schottky diodes are significantly larger than those of PEALD, leading to a poor on/off rectifying ratio of ∼4. Due to the small thickness, a critical breakdown strength of 1.3 MV/cm was estimated for PEALD-ZnO thin films.

Formation of Ni silicide from atomic layer deposited Ni

The wide applications of ultrathin group IV metal oxide films (TiO2, ZrO2 and HfO2) probably expose materials to potentially reactive etchants and solvents, appealing for extraordinary chemical stability and corrosion resistance property. In this paper, TiO2 ultrathin films were deposited on Si at 200 °C while ZrO2 and HfO2 were grown at 250 °C to fit their growth temperature window, by thermal atomic layer deposition (TALD) and plasma-enhanced ALD (PEALD). A variety of chemical liquid media including 1 mol/L H2SO4, 1 mol/L HCl, 1 mol/L KOH, 1 mol/L KCl, and 18 MΩ deionized water were used to test and compare chemical stability of all these as-deposited group IV metal oxides thin films, as well as post-annealed samples at various temperatures. Among these metal oxides, TALD/PEALD HfO2 ultrathin films exhibit the best chemical stability and anti-corrosion property without any change in thickness after long time immersion into acidic, alkaline and neutral solutions. As-deposited TALD ZrO2 ultrathin films have slow etch rate of 1.06 nm/day in 1 mol/L HCl, however other PEALD ZrO2 ultrathin films and annealed TALD ones show better anti-acid stability, indicating the role of introduction of plasma O2 in PEALD and post-thermal treatment. As-deposited TiO2 ultrathin films by TALD and PEALD are found to be etched slowly in acidic solutions, but the PEALD can decrease the etching rate of TiO2 by ~41%. After post-annealing, TiO2 ultrathin films have satisfactory corrosion resistance, which is ascribed to the crystallization transition from amorphous to anatase phase and the formation of 5% Si-doped TiO2 ultrathin layers on sample surfaces, i.e. Ti-silicate. ZrO2, and TiO2 ultrathin films show excellent corrosion endurance property in basic and neutral solutions. Simultaneously, 304 stainless steel coated with PEALD-HfO2 is found to have a lower corrosion rate than that with TALD-HfO2 by means of electrochemical measurement. The pre-treatment of plasma H2 to 304 stainless steel can effectively reduce interfacial impurities and porosity of overlayers with significantly enhanced corrosion endurance. Above all, the chemical stability and anti-corrosion properties of IV group metal oxide coatings can be improved by using PEALD technique, post-annealing process and plasma H2 pre-treatment to substrates.