Surface reaction of silicon chlorides during atomic layer deposition of silicon nitride

Yusup, Luchana L.; Park, Jaemin; Mayangsari, Tirta Rona; Kwon, Young–Kyun; Lee, Wonjun

doi:10.1016/j.apsusc.2017.06.060

Cited by 26 publications

(20 citation statements)

References 26 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…30,41,50−53 In terms of the monosilane type of ALD precursors, DFT calculation predicted that dichlorosilane (SiH 2 Cl 2 ) has a lower energy barrier than tetrachlorosilane (SiCl 4 ) for reactions on the surface terminated with amine groups (−NH 2 and −NH−). 50 The prediction is consistent with the experimental observation that SiH 2 Cl 2 showed a higher reactivity and higher growth per cycle (GPC) than SiCl 4 . The substitution of Cl atom with H atom can lower the steric hindrance, 54 to make the precursor molecule more easily accessible to the reactive sites on the surface with less physical interference from the adjacent ligands.…”

Section: ■ Introductionsupporting

confidence: 89%

“…Among the reported chlorosilane precursors, hexachlorodisilane (HCDS, Si 2 Cl 6 ) is a promising candidate because of its higher surface reactivity as well as the demonstration of a distinct self-limiting growth behavior in the ALD SiN x process. 10,30,50 According to the density functional theory (DFT) studies on the surface reactions of ALD SiN x , reducing the steric hindrance and the bond dissociation energies (BDEs) and increasing the electron densities of silicon precursors are three of the critical factors for lowering the energy barrier of precursor adsorption, to achieve a higher reactivity and a higher growth rate. 30,41,50−53 In terms of the monosilane type of ALD precursors, DFT calculation predicted that dichlorosilane (SiH 2 Cl 2 ) has a lower energy barrier than tetrachlorosilane (SiCl 4 ) for reactions on the surface terminated with amine groups (−NH 2 and −NH−).…”

Section: ■ Introductionmentioning

confidence: 99%

“…The use of chlorosilane precursors is also considered a practical approach for high-volume manufacturing. Among the reported chlorosilane precursors, hexachlorodisilane (HCDS, Si 2 Cl 6 ) is a promising candidate because of its higher surface reactivity as well as the demonstration of a distinct self-limiting growth behavior in the ALD SiN x process. ,, …”

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Hollow Cathode Plasma-Enhanced Atomic Layer Deposition of Silicon Nitride Using Pentachlorodisilane

Meng

Kim

Lucero

et al. 2018

ACS Appl. Mater. Interfaces

View full text Add to dashboard Cite

In this work, a novel chlorodisilane precursor, pentachlorodisilane (PCDS, HSiCl), was investigated for the growth of silicon nitride (SiN ) via hollow cathode plasma-enhanced atomic layer deposition (PEALD). A well-defined self-limiting growth behavior was successfully demonstrated over the growth temperature range of 270-360 °C. At identical process conditions, PCDS not only demonstrated approximately>20% higher growth per cycle than that of a commercially available chlorodisilane precursor, hexachlorodisilane (SiCl), but also delivered a better or at least comparable film quality determined by characterizing the refractive index, wet etch rate, and density of the films. The composition of the SiN films grown at 360 °C using PCDS, as determined by X-ray photoelectron spectroscopy, showed low O content (∼2 at. %) and Cl content (<1 at. %; below the detection limit). Fourier transform infrared spectroscopy spectra suggested that N-H bonds were the dominant hydrogen-containing bonds in the SiN films without a significant amount of Si-H bonds originating from the precursor molecules. The possible surface reaction pathways of the PEALD SiN using PCDS on the surface terminated with amine groups (-NH and -NH-) are proposed. The PEALD SiN films grown using PCDS also exhibited a leakage current density as low as 1-2 nA/cm at 2 MV/cm and a breakdown electric field as high as ∼12 MV/cm.

show abstract

Section: ■ Introductionsupporting

confidence: 89%

Section: ■ Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Hollow Cathode Plasma-Enhanced Atomic Layer Deposition of Silicon Nitride Using Pentachlorodisilane

Meng

Kim

Lucero

et al. 2018

ACS Appl. Mater. Interfaces

View full text Add to dashboard Cite

show abstract

“…Previously, the ALD and CVD of Si-containing materials have been performed using various Si precursors. Interestingly, when Si precursors of the same substituents with and without the Si–Si bond (e.g., SiH 4 vs Si 2 H 6 ; SiCl 4 vs Si 2 Cl 6 ) are applied under similar deposition conditions, those containing the Si–Si bond consistently exhibit significantly larger reactivity, in terms of either lower deposition temperature, larger growth rate, or a smaller activation barrier upon adsorption. − …”

Section: Results and Discussionmentioning

confidence: 98%

Thermal Atomic Layer Deposition of Device-Quality SiO₂ Thin Films under 100 °C Using an Aminodisilane Precursor

Kim

Lee

Jeong³

et al. 2019

Chem. Mater.

View full text Add to dashboard Cite

SiO2 is one of the most important dielectric materials that is widely used in the microelectronics industry, but its growth or deposition requires high thermal budgets. Herein, we report a low-temperature thermal atomic layer deposition (ALD) process to fabricate SiO2 thin films using a novel aminodisilane precursor with a Si–Si bond, 1,2-bis(diisopropylamino)disilane (BDIPADS), together with ozone. To compare the film quality, ALD SiO2 films grown at various temperatures from 250 down to 50 °C were systematically investigated. Our data suggest that even without the aid of plasma-enhanced or catalyzed surface reactions, high-quality SiO2 films with relatively high growth rates, high film densities, and low impurity contents compared to conventional Si precursors can be attained through our process at a low growth temperature (∼50 °C). Chemical analyses via Auger electron spectroscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy confirm the formation of stoichiometric SiO2 films without noticeable impurity contents of nitrogen and carbon, regardless of the growth temperature. However, low-temperature growth of the SiO2 film (≤80 °C) results in a slight ingress of SiH-related moieties during the ALD processes that is not observed at temperatures over 80 °C. Density functional theory calculations show that the Si–Si bond present in the BDIPADS precursor is easier to be oxidized compared to the Si–H bonds. Through electrical characterization of the SiO2 films grown at different temperatures, we confirm only slight degradation in the dielectric constants, leakage currents, and breakdown fields with decreasing growth temperature, which may be due to the slightly decreased film density and the increased defect density of SiH-related bonds.

show abstract

“…Geometry optimizations were performed for all of the structures with a convergence tolerance of total energy differences of 10 –6 Ha (Hartree, 27.21 eV) and an atomic force smaller than 2 × 10 –4 Ha/Å. Orbital occupancy was calculated using a smearing value of 9 × 10 –4 Ha …”

Section: Calculation Detailsmentioning

confidence: 99%

Catalyzed Atomic Layer Deposition of Silicon Oxide at Ultralow Temperature Using Alkylamine

et al. 2018

Self Cite

View full text Add to dashboard Cite

We report the catalyzed atomic layer deposition (ALD) of silicon oxide using SiCl, HO, and various alkylamines. The density functional theory (DFT) calculations using the periodic slab model of the SiO surface were performed for the selection of alternative Lewis base catalysts with high catalytic activities. During the first half-reaction, the catalysts with less steric hindrance such as pyridine would be more effective than bulky alkylamines despite lower nucleophilicity. On the other hand, during the second half-reaction, the catalysts with a high nucleophilicity such as triethylamine (EtN) would be more efficient because the steric hindrance is less critical. The in situ process monitoring shows that the calculated atomic charge is a good indicator for expecting the catalyst activity in the ALD reaction. The use of EtN in the second half-reaction was essential to improving the growth rate as well as the step coverage of the film because the EtN-catalyzed process deposited a SiO film with a step coverage of 98% that is better than 93% of the pyridine-catalyzed process. The adsorption of pyridine, ammonia (NH), or trimethylamine (MeN) salts was more favorable than that of EtN, n-PrN, or PrN salts. Therefore, EtN was expected to incorporate less amine salts in the film as compared to pyridine, and the compositional analyses confirmed that the concentrations of Cl and N by the EtN-catalyzed process were significantly lower than those by the pyridine-catalyzed process.

show abstract

Surface reaction of silicon chlorides during atomic layer deposition of silicon nitride

Cited by 26 publications

References 26 publications

Hollow Cathode Plasma-Enhanced Atomic Layer Deposition of Silicon Nitride Using Pentachlorodisilane

Hollow Cathode Plasma-Enhanced Atomic Layer Deposition of Silicon Nitride Using Pentachlorodisilane

Thermal Atomic Layer Deposition of Device-Quality SiO₂ Thin Films under 100 °C Using an Aminodisilane Precursor

Catalyzed Atomic Layer Deposition of Silicon Oxide at Ultralow Temperature Using Alkylamine

Contact Info

Product

Resources

About

Surface reaction of silicon chlorides during atomic layer deposition of silicon nitride

Cited by 26 publications

References 26 publications

Hollow Cathode Plasma-Enhanced Atomic Layer Deposition of Silicon Nitride Using Pentachlorodisilane

Hollow Cathode Plasma-Enhanced Atomic Layer Deposition of Silicon Nitride Using Pentachlorodisilane

Thermal Atomic Layer Deposition of Device-Quality SiO2 Thin Films under 100 °C Using an Aminodisilane Precursor

Catalyzed Atomic Layer Deposition of Silicon Oxide at Ultralow Temperature Using Alkylamine

Contact Info

Product

Resources

About

Thermal Atomic Layer Deposition of Device-Quality SiO₂ Thin Films under 100 °C Using an Aminodisilane Precursor