Thermal Atomic Layer Etching of Aluminum Oxide (Al2O3) Using Sequential Exposures of Niobium Pentafluoride (NbF5) and Carbon Tetrachloride (CCl4) : A Combined Experimental and Density Functional Theory Study of the Etch Mechanism

Thermal atomic layer etching (ALEt) of amorphous Al2O3 was performed by alternate exposures of niobium pentafluoride (NbF5) and carbon tetrachloride (CCl4). The ALEt of Al2O3 is observed at temperatures from 380 to 460 degrees C. The etched thickness and the etch rate were determined using spectroscopic ellipsometry and verified by X-ray reflectivity. The maximum etch rate of about 1.4 A/cycle and a linear increase of the removed film thickness with the number of etch cycles were obtained at a temperature of 460 degrees C. With the help of density functional theory calculations, an etch mechanism is proposed where NbF5 converts part of the Al2O3 surface into an AlF3 or aluminum oxyfluoride layer, which upon reacting with CCl4 is converted into volatile halide-containing byproducts, thus etching away the converted portion of the material. Consistent with this, a significant surface fluorine content of about 55 at. % was revealed when the elemental depth profile analysis of a thick NbF5-treated Al2O3 layer was performed by X-ray photoelectron spectroscopy. The surface morphology of the reference, pre-, and postetch Al2O3 surfaces was analyzed using atomic force microscopy and brightfield transmission electron microscopy. Moreover, it is found that this process chemistry is able to etch Al2O3 selectively over silicon dioxide (SiO2) and silicon nitride (Si3N4).Peer reviewe

Thermal gas-phase etching of titanium nitride (TiN) by thionyl chloride (SOCl2)

In this work, thermal based gas-phase etching of titanium nitride (TiN) is demonstrated using thionyl chloride (SOCl2) as a novel etchant. A single etchant is utilised in a pulsed fashion to etch TiN. This type of etching technique may also be considered as a chemical gas-phase or dry etching. The removed TiN amount was measured by various techniques like spectroscopic ellipsometry (SE), weighing balance and in some cases X-ray reflectometry (XRR). Additionally, the post-etch surfaces were analysed with X-ray photoelectron spectroscopy (XPS) and bright field transmission electron microscopy (BF-TEM). The surface roughness and morphology of before and after etching TiN films were measured using atomic force microscopy (AFM). The etch per cycle (EPC) was calculated and is plotted as a function of SOCl2 pulse time, purge time after SOCl2 exposure, number of etch cycles and etch temperature (T-etch). An increase in EPC with an increase in SOCl2 pulse time as well as etch temperature was observed. SOCl2 is able to etch TiN starting from 270 degrees C with an EPC of about 0.03 angstrom to almost 1.2 angstrom at 370 degrees C. Arrhenius plot determined the activation energy (E-a) of about 25 kcal/mol for TiN etching by SOCl2. In addition, the etch selectivity between different substrates such as silicon dioxide (SiO2), silicon nitride (Si3N4) and aluminum oxide (Al2O3) was investigated on blanket as well as 3D structures. Moreover, thermodynamic calculations were performed for various possible etch reactions. Titanium from TiN is proposed to be etched in the form of either titanium trichloride (TiCl3) or titanium tetrachloride (TiCl4). Nitrogen from TiN films may form volatile by-products such as diatomic nitrogen (N-2), nitrous oxide (N2O) and nitrogen dioxide (NO2).Peer reviewe

Combining Experimental and DFT Investigation of the Mechanism Involved in Thermal Etching of Titanium Nitride Using Alternate Exposures of NbF5 and CCl4, or CCl4 Only

Thermally activated chemical vapor-phase etching of titanium nitride (TiN) is studied by utilizing either alternate exposures of niobium pentafluoride (NbF5) and carbon tetrachloride (CCl4) or by using CCl4 alone. Nitrogen (N-2) gas purge steps are carried out in between every reactant exposure. Titanium nitride is etched in a non-self-limiting way by NbF5-CCl4 based binary chemistry or by CCl4 at temperatures between 370 and 460 degrees C. Spectroscopic ellipsometry and a weight balance are used to calculate the etch per cycle. For the binary chemistry, an etch per cycle of approximate to 0.8 angstrom is obtained for 0.5 and 3 s long exposures of NbF5 and CCl4, respectively at 460 degrees C. On the contrary, under the same conditions, the etch process with CCl4 alone gives an etch per cycle of about 0.5 angstrom. In the CCl4-only etch process, the thickness of TiN films removed at 460 degrees C varies linearly with the number of etch cycles. Furthermore, CCl4 alone is able to etch TiN selectively over other materials such as Al2O3, SiO2, and Si3N4. X-ray photoelectron spectroscopy and bright field transmission electron microscopy are used for studying the post-etch surfaces. To understand possible reaction products and energetics, first-principles calculations are carried out with density functional theory. From thermochemical analysis of possible reaction models, it is found that NbF5 alone cannot etch TiN while CCl4 alone can etch it at high temperatures. The predicted byproducts of the reaction between the CCl4 gas molecules and TiN surface are TiCl3 and ClCN. Similarly, TiF4, NbFCl3, and ClCN are predicted to be the likely products when TiN is exposed to both NbF5 and CCl4. A more favorable etch reaction is predicted when TiN is exposed to both NbF5 and CCl4 (Delta G = -2.7 eV at 640 K) as compared to exposure to CCl4 only (Delta G = -2 eV at 640 K) process. This indicates that an enhanced etch rate is possible when TiN is exposed alternately to both NbF5 and CCl4, which is in close agreement with the experimental results.Peer reviewe

Atomic-layer-deposited WNxCy thin films as diffusion barrier for copper metallization

The properties of WNxCy films deposited by atomic layer deposition (ALD) using WF6, NH3, and triethyl boron as source gases were characterized as a diffusion barrier for copper metallization. It is noted that the as-deposited film shows an extremely low resistivity of about 350 muOmega cm with a film density of 15.37 g/cm(3). The film composition measured from Rutherford backscattering spectrometry shows W, C, and N of similar to48, 32, and 20 at. %, respectively. Transmission electron microscopy analyses show that the as-deposited film is composed of face-centered-cubic phase with a lattice parameter similar to both beta-WC1-x and beta-W2N with an equiaxed microstructure. The barrier property of this ALD-WNxCy film at a nominal thickness of 12 nm deposited between Cu and Si fails only after annealing at 700 degreesC for 30 min. (C) 2003 American Institute of Physics

Erratum: History of atomic layer deposition and its relationship with the American Vacuum Society (Journal of Vacuum Science and Technology A: Vacuum, Surfaces and Films (2013)31 (050818) DOI: 10.1116/1.4816548)

The authors of this review article published in 20131 would like to correct some text and references relating to the first observations and publications on molecular layering. In Sec. II, “Early Years of Atomic Layer Processes” in the original article,1 the first two sentences of the fourth paragraph should instead say “The ALD principle, where surface reactions follow a binary sequence of self-limiting half-reactions, was reported under the name ‘molecular layering’ in the 1960s by S. I. Kol’tsov from Leningrad Technological Institute.2–6 These experiments were conducted under the scientific supervision of V. B. Aleskovskii. The ‘framework hypothesis,’ an antecedent to molecular layering, was proposed by V. B. Aleskovskii in 1952.6” In addition, again in this same section and paragraph, the last two sentences should instead say “In the 1969 article,3 the authors report that the initial reaction between TiCl4 and Si–OH tends to involve 3 Si–OH, forming one Ti–Cl, whereas after the first water step, the second TiCl4 exposure reacts with 2 Ti–OH, forming Ti–Cl2 groups. In the 1969 paper,3 a planar thin film was not produced or evaluated, although nanolayers were prepared by molecular layering at that time.6” These corrections do not affect other sections or the conclusions drawn in the article

Atomic Layer Deposition of Silicon Nitride from Bis(<i>tert</i>-butylamino)silane and N₂ Plasma

Atomic layer deposition (ALD) of silicon nitride (SiN_<i>x</i>) is deemed essential for a variety of applications in nanoelectronics, such as gate spacer layers in transistors. In this work an ALD process using bis­(<i>tert</i>-butylamino)­silane (BTBAS) and N₂ plasma was developed and studied. The process exhibited a wide temperature window starting from room temperature up to 500 °C. The material properties and wet-etch rates were investigated as a function of plasma exposure time, plasma pressure, and substrate table temperature. Table temperatures of 300–500 °C yielded a high material quality and a composition close to Si₃N₄ was obtained at 500 °C (N/Si = 1.4 ± 0.1, mass density = 2.9 ± 0.1 g/cm³, refractive index = 1.96 ± 0.03). Low wet-etch rates of ∼1 nm/min were obtained for films deposited at table temperatures of 400 °C and higher, similar to that achieved in the literature using low-pressure chemical vapor deposition of SiN_<i>x</i> at >700 °C. For novel applications requiring significantly lower temperatures, the temperature window from room temperature to 200 °C can be a solution, where relatively high material quality was obtained when operating at low plasma pressures or long plasma exposure times

History of atomic layer deposition and its relationship with the American Vacuum Society

This article explores the history of atomic layer deposition (ALD) and its relationship with the American Vacuum Society (AVS). The authors describe the origin and history of ALD science in the 1960s and 1970s. They also report on how the science and technology of ALD progressed through the 1990s and 2000s and continues today. This article focuses on how ALD developed within the AVS and continues to evolve through interactions made possible by the AVS, in particular, the annual International AVS ALD Conference. This conference benefits students, academics, researchers, and industry practitioners alike who seek to understand the fundamentals of self-limiting, alternating binary surface reactions, and how they can be applied to form functional (and sometimes profitable) thin film materials. The flexible structure of the AVS allowed the AVS to quickly organize the ALD community and create a primary conference home. Many new research areas have grown out of the original concepts of "Atomic Layer Epitaxy" and "Molecular Layering," and some of them are described in this article. The people and research in the ALD field continue to evolve, and the AVS ALD Conference is a primary example of how the AVS can help a field expand and flourish