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In this Letter, the robust ferroelectric properties of low-temperature (350 °C) Hf0.5Zr0.5O2 (HZO) films are investigated. We demonstrate that the lower crystallization temperature of HZO films originates from a densified film deposition with an anhydrous H2O2 oxidant in the atomic layer deposition process. As a consequence of this densification, H2O2-based HZO films showed completely crystallinity with fewer defects at a lower annealing temperature of 350 °C. This reduction in the crystallization temperature additionally suppresses the oxidation of TiN electrodes, thereby improving device reliability. The low-temperature crystallization process produces an H2O2-based HZO capacitor with a high remanent polarization (Pr), reduced leakage current, high breakdown voltage, and better endurance. Furthermore, while an O3-based HZO capacitor requires wake-up cycling to achieve stable Pr, the H2O2-based HZO capacitor demonstrates a significantly reduced wake-up nature. Anhydrous H2O2 oxidant enables the fabrication of a more reliable ferroelectric HZO device using a low process thermal budget (350 °C). [ABSTRACT FROM AUTHOR]

A novel precursor, 1,1,1-tris(dimethylamino)disilane {TADS, [(H3C)2N]3Si2H3}, is used to deposit silicon dioxide (SiO2) films in a temperature range of 115–480 °C by thermal atomic layer deposition (tALD) and plasma-enhanced atomic layer deposition (PEALD) techniques. Compared to tris(dimethylamino)silane (TDMAS), the additional Si-Si bond in TADS is expected to enhance the reactivity of the molecule due to the polarization of the bond. In the tALD process, TADS gives a growth rate of 0.06 nm/cycle, which is approximately 20% higher than that of TDMAS, and an excellent conformality (>95% step coverage) in high aspect ratio nanotrenches (6:1). In the case of the PEALD process, TADS leads to not only a higher or at least comparable growth rates (0.11 nm/cycle), but also a higher bulk film density (∼2.38 g/cm3). As a result, the PEALD SiO2 films of TADS show a wet-etch rate down to 1.6 nm/min in 200:1 HF, which is comparable to that of the thermal oxide. Analyzed with Fourier-Transform Infrared (FTIR), the SiO2 films contain predominant Si−O bonds and a low level of Si−H and O−H bonds, consistent with the observed high wet-etch resistance. Furthermore, the PEALD SiO2 films deposited at 310 °C have at least 75% step coverage in high aspect ratio nanotrenches, suggesting that TADS is applicable for forming high-quality SiO2 films on both planar and patterned surfaces. [ABSTRACT FROM AUTHOR]

Since the first report on the unexpected ferroelectricity of fluorite‐structure oxides in 2011, this topic has provided a pathway for new research directions and opportunities. Based on theoretical calculations and experimental demonstrations, it is now well known that fluorite‐structure ferroelectrics are compatible with complementary metal–oxide–semiconductor technology and exhibit ferroelectric properties at extremely thin (<10 nm) thicknesses. It should be noted that the noncentrosymmetric orthorhombic phase, which is responsible for ferroelectric behavior, is formed even at low temperatures (400 °C or less). Herein, the various factors such as doping effects, deposition method, annealing method and conditions, and substrate material are reviewed, focusing on thermal budget, especially the low‐temperature annealing process for formation of the ferroelectric phase. These low‐thermal‐budget processes facilitate not only the integration of ferroelectric circuits in the back‐end‐of‐line to increase the effective memory area and add more functionalities but also applications for flexible and wearable electronics. [ABSTRACT FROM AUTHOR]

Since HfO2‐based ferroelectric films were reported in 2011, several doping/alloying elements have been introduced to secure interesting ferroelectric/antiferroelectric properties of Hf‐based fluorite‐structured thin films. Using a conventional approach by atomic layer deposition (ALD), an enormous number of experiments would be required to reveal the compositional effects of doping/alloying components in ternary and quaternary systems. Therefore, for a comprehensive study of the ferroelectric properties of HfxZr1−xO2, a novel combinatorial ALD technique that enables the fabrication of multicomponent films with a different composition ratio and thickness via saturated/non‐saturated ALD without changing the supercycle of each material is reported. The gradient of the amount of HfO2 over a 100 mm substrate is achieved using a lower Hf‐precursor temperature that results in an insufficient Hf‐precursor dose for saturated deposition. Systematic study on the HfxZr1−xO2 combinatorial library is carried out by spectroscopic ellipsometry, X‐ray photoelectron spectroscopy, and X‐ray diffraction. Furthermore, TiN/HfxZr1−xO2/TiN capacitors are fabricated to measure the remnant polarization. The obtained results clearly show the ferroelectric–antiferroelectric transition according to continuous composition change instead of discrete research. Therefore, a highly productive method for studying ferroelectricity changes in terms of a doping and a composition of HfO2‐based ferroelectric thin films through a novel ALD combinatorial approach is proposed. [ABSTRACT FROM AUTHOR]

In recent times, the requirements have become extremely stringent for employing silicon nitride (SiNx) films in various types of applications. For instance, high etch resistance coating is required for a film to act as an etch stop layer and gate spacer for nanoscale patterning for next-generation semiconductor devices. In this study, a chlorodisilane precursor, 1,1,1-trichlorodisilane (3CDS, Si2H3Cl3), was used to deposit SiNx films using a hollow cathode plasma-enhanced atomic layer deposition system and compared with the SiNx films deposited using hexachlorodisilane (HCDS, Si2Cl6) as well as pentachlorodisilane (PCDS, Si2HCl5). In the process temperature range of 310–435 °C, a self-limiting surface reaction behavior with 4 × 103 L of 3CDS exposure and 2 × 106 L of NH3 plasma exposure was observed. 3CDS particularly gives ∼45 and ∼20% higher growth per cycle than HCDS and PCDS, respectively. In addition, the SiNx films deposited using 3CDS at 480 °C have improved the wet etch rate (0.4 nm/min in 200:1 HF) and density (2.88 g/cm3). Analyzed with time-of-flight secondary ion mass spectrometry, the 3CDS-derived SiNx films contain less hydrogen than the SiNx films formed using HCDS under identical process conditions. These superior film properties can be attributed to the unique structural characteristics of 3CDS, where the three chlorine and three hydrogen atoms are localized on each of the two silicon atoms. The SiNx films deposited on nanotrenches with a high aspect ratio (6:1) at 390 and 480 °C showed >85% and >65% conformality, respectively, and high etch resistance (1.9 and 0.8 nm/min, respectively, in 200:1 HF), suggesting that high-quality SiNx films can be formed from 3CDS on both planar and patterned surfaces. [ABSTRACT FROM AUTHOR]

The change in the interplanar spacing (d-spacing) including the ferroelectric orthorhombic (O) phase in the low-temperature fabricated HfxZr1−xO2 (HZO) films was studied using synchrotron grazing-incidence wide-angle x-ray scattering analysis. The 10-nm-thick HZO films were fabricated by thermal and plasma-enhanced atomic layer deposition (TH- and PE-ALD) methods using H2O gas and O2 plasma as oxidants, respectively, and a post-metallization annealing (PMA) was performed at 300–400 °C. The d-spacing of the mixture of (111)-, (101)-, and (111)-planes of O, tetragonal (T), and cubic (C) phases, respectively, for the TH- and PE-ALD HZO films increased up to 2.99 Å with an increase in PMA temperature, while the d-spacing estimated by conventional x-ray diffraction was 2.92 Å regardless of the PMA temperature. The remanent polarization (2Pr= Pr+ − Pr−) of the HZO films increased as the PMA temperature increased. It is clear that the 2Pr value satisfied a linear relationship as a function of the d-spacing of O(111)/T(101)/C(111) phases. Furthermore, the wake-up effect was found to depend on the ferroelectric O phase formation. The wake-up effect was significantly reduced in both the TH- and PE-ALD HZO films after the PMA at 400 °C due to the increase in the ferroelectric O phase formation. The leakage current density (J)–electric field properties of the PE-ALD HZO film with the lowest d-spacing were divided into three steps, such as low, middle, and large J values, in the wake-up (103 cycles), pristine (100 cycle), and fatigue (107 cycles) states, respectively. Therefore, an analysis of the ferroelectric O phase is very important for understanding the ferroelectricity including endurance. [ABSTRACT FROM AUTHOR]

The ferroelectricity of metal–ferroelectric–metal capacitors with a ferroelectric HfxZr1−xO2/ZrO2 (HZO/ZO) bilayer thicker than 20 nm formed by atomic layer deposition and postdeposition annealing at 600 °C was investigated. The HZO/ZO capacitors exhibited a higher remanent polarization (2Pr = Pr+ − Pr−) and breakdown voltage (Vbd) than capacitors with a HfxZr1−xO2 (HZO) single layer. In particular, a HZO (15 nm)/ZO(10 nm) (HZ15Z10) capacitor exhibited excellent Vbd and 2Pr values of 6.7 V and 14 μC/cm2, respectively, which are much higher than those (4.3 V and 10 μC/cm2, respectively) for a HZO (15 nm) (HZ15) capacitor. The HZ15Z10 capacitor also exhibited higher endurance, a smaller wake-up effect (∼5%), and superior fatigue properties up to 108 switching cycles, compared to a HZ15 capacitor, which exhibited a large wake-up effect (∼15%) and large 2Pr degradation at 108 cycles. The wake-up behavior is attributed to domain depinning mainly related to the redistribution of oxygen vacancies and transformation from the nonferroelectric phase to the ferroelectric orthorhombic (O) phase during field cycling. The HZO/ZO bilayer grew a larger grain size with the ZO nucleation layer, which is twice as large as that of the HZO single layer, and the former structure exhibited more stable bulk-like ferroelectricity. Although the ferroelectric O phase in HZO decreased with increasing HZO thickness, the HZO/ZO structure had a larger fraction of the O phase than the HZO structure. Considering the manufacturing process of ferroelectric devices, these thick HZO/ZO bilayers are promising ferroelectric materials. [ABSTRACT FROM AUTHOR]

The ferroelectric (FE) properties of 10-nm-thick Hf0.5Zr0.5O2 (HZO) films deposited by an atomic layer deposition technique were improved by adopting O3 as an oxygen source instead of H2O. All HZO films were annealed at 400 °C for 1 min in an N2 atmosphere after TiN top electrode deposition. Regardless of the oxygen source, the HZO films exhibited the formation of a noncentrosymmetric orthorhombic phase, which is responsible for FE behavior with the suppression of the monoclinic phase. However, compared to the O3-based HZO film, it was confirmed that the H2O-based HZO film was more incorporated with hydrogen derived from H2O, thereby degrading FE polarization and leakage behavior. The results indicate that the strategy of using O3 as the oxygen source is useful for the fabrication and integration of FE HZO films for next-generation memory applications. [ABSTRACT FROM AUTHOR]

We report on atomic layer deposited Hf0.5Zr0.5O2 (HZO)-based capacitors which exhibit excellent ferroelectric (FE) characteristics featuring a large switching polarization (45 μC/cm2) and a low FE saturation voltage (~1.5V) as extracted from pulse write/read measurements. The large FE polarization in HZO is achieved by the formation of a non-centrosymmetric orthorhombic phase, which is enabled by the TiN top electrode (TE) having a thickness of at least 90 nm. The TiN films are deposited at room temperature and annealed at 400 ºC in an inert environment for at least 1 min in a rapid thermal annealing system. The room-temperature deposited TiN TE acts as a tensile stressor on the HZO film during the annealing process. The stress-inducing TiN TE is shown to inhibit the formation of the monoclinic phase during HZO crystallization, forming an orthorhombic phase that generates a large FE polarization, even at low process temperatures. [ABSTRACT FROM AUTHOR]

With the continued miniaturization of devices in the semiconductor industry, atomic layer deposition (ALD) of silicon nitride thin films (SiNx) has attracted great interest due to the inherent benefits of this process compared to other silicon nitride thin film deposition techniques. These benefits include not only high conformality and atomic-scale thickness control, but also low deposition temperatures. Over the past 20 years, recognition of the remarkable features of SiNx ALD, reinforced by experimental and theoretical investigations of the underlying surface reaction mechanism, has contributed to the development and widespread use of ALD SiNx thin films in both laboratory studies and industrial applications. Such recognition has spurred ever-increasing opportunities for the applications of the SiNx ALD technique in various arenas. Nevertheless, this technique still faces a number of challenges, which should be addressed through a collaborative effort between academia and industry. It is expected that the SiNx ALD will be further perceived as an indispensable technique for scaling next-generation ultra-large-scale integration (ULSI) technology. In this review, the authors examine the current research progress, challenges and future prospects of the SiNx ALD technique. [ABSTRACT FROM AUTHOR]

Aluminum nitride (AlN) thin films were grown using thermal atomic layer deposition in the temperature range of 175–350 °C. The thin films were deposited using trimethyl aluminum (TMA) and hydrazine (N2H4) as a metal precursor and nitrogen source, respectively. Highly reactive N2H4, compared to its conventionally used counterpart, ammonia (NH3), provides a higher growth per cycle (GPC), which is approximately 2.3 times higher at a deposition temperature of 300 °C and, also exhibits a low impurity concentration in as-deposited films. Low temperature AlN films deposited at 225 °C with a capping layer had an Al to N composition ratio of 1:1.1, a close to ideal composition ratio, with a low oxygen content (7.5%) while exhibiting a GPC of 0.16 nm/cycle. We suggest that N2H4 as a replacement for NH3 is a good alternative due to its stringent thermal budget. [ABSTRACT FROM AUTHOR]

The discovery of ferroelectricity in HfO2-based materials in 2011 provided new research directions and opportunities. In particular, for atomic layer deposited Hf0.5Zr0.5O2 (HZO) films, it is possible to obtain homogenous thin films with satisfactory ferroelectric properties at a low thermal budget process. Based on experiment demonstrations over the past 10 years, it is well known that HZO films show excellent ferroelectricity when sandwiched between TiN top and bottom electrodes. This work reports a comprehensive study on the effect of TiN top and bottom electrodes on the ferroelectric properties of HZO thin films (10 nm). Investigations showed that during HZO crystallization, the TiN bottom electrode promoted ferroelectric phase formation (by oxygen scavenging) and the TiN top electrode inhibited non-ferroelectric phase formation (by stress-induced crystallization). In addition, it was confirmed that the TiN top and bottom electrodes acted as a barrier layer to hydrogen diffusion into the HZO thin film during annealing in a hydrogen-containing atmosphere. These features make the TiN electrodes a useful strategy for improving and preserving the ferroelectric properties of HZO thin films for next-generation memory applications. [ABSTRACT FROM AUTHOR]

• Selection of oxygen source is one of the important factors to improve ferroelectricity. • Heavy water (deuterium water, D 2 O) is used as a tracer to pinpoint the origin of hydrogen. • Using a hydrogen-free oxygen source such as O 3 in the atomic layer deposition process improves the ferroelectric properties. Ferroelectric Hf 0.5 Zr 0.5 O 2 (HZO) thin films are mostly deposited with a thickness of less than 10 nm by an atomic layer deposition (ALD) process. Since the oxygen source used in the ALD process affects the residues in the deposited HZO films, the choice of oxygen source can be one of the important factors to improve ferroelectricity. From this point of view, the ferroelectric properties of 10-nm-thick ALD-HZO films according to the oxygen source (O 3 , H 2 O, and D 2 O) were comprehensively analyzed in this study. Heavy water (deuterium water, D 2 O) was used as a tracer to pinpoint the origin of hydrogen that could be derived from unreacted metal precursors or unreacted hydroxyl groups. As a result, it was revealed that the decrease in ferroelectric polarization and increase in leakage current observed in the H 2 O- and D 2 O-based HZO capacitors compared to the O 3 -based HZO capacitor were due to the oxygen source. These results highlight the importance of using O 3 as a hydrogen-free oxygen source in the ALD process to achieve better ferroelectricity. [ABSTRACT FROM AUTHOR]