Etching Of Silicon Dioxide Research Articles

Enhancing Si3N4 Selectivity over SiO2 in Low-RF Power NF3-O2 Reactive Ion Etching: The Effect of NO Surface Reaction.

Highly selective etching of silicon nitride (Si3N4) and silicon dioxide (SiO2) has received considerable attention from the semiconductor community owing to its precise patterning and cost efficiency. We investigated the etching selectivity of Si3N4 and SiO2 in an NF3/O2 radio-frequency glow discharge. The etch rate linearly depended on the source and bias powers, whereas the etch selectivity was affected by the power and ratio of the gas mixture. We found that the selectivity can be controlled by lowering the power with a suitable gas ratio, which affects the surface reaction during the etching process. X-ray photoelectron spectroscopy of the Si3N4 and QMS measurements support the effect of surface reaction on the selectivity change by surface oxidation and nitrogen reduction with the increasing flow of O2. We suggest that the creation of SiOxNy bonds on the surface by NO oxidation is the key mechanism to change the etch selectivity of Si3N4 over SiO2.

High-rate etching of silicon oxide and nitride using narrow-gap high-pressure (3.3 kPa) hydrogen plasma

We investigated the etching behavior of silicon oxide (SiO x ) and silicon nitride (SiN x ) in narrow-gap, high-pressure (3.3 kPa) hydrogen (H2) plasma under various etching conditions. Maximum etching rates of 940 and 240 nm min−1 for SiO x and SiN x , respectively, were obtained by optimizing the H2 gas flow rate. The dependence of the etching rate on gas flow rate implied that effective elimination of etching products is important for achieving high etching rates because it prevents redeposition. The sample surfaces, especially the oxide surfaces, were roughened and contained numerous asperities after etching. Etching rates of both SiO x and SiN x decreased as the temperature was raised. This suggests that atomic H adsorption, rather than H-ion bombardment, is an important step in the etching process. X-ray photoelectron spectroscopy revealed that the etched nitride surface was enriched in silicon (Si), suggesting that the rate-limiting process in high-pressure H2 plasma etching is Si etching rather than nitrogen abstraction. The etching rate of SiO x was three times higher than that of SiN x despite the higher stability of Si–O bonds than Si–N ones. One reason for the etching difference may be the difference between the bond densities of SiO x and SiN x . This study presents a relatively non-toxic, low-cost, and eco-friendly dry etching process for Si-based dielectrics using only H2 gas in comparison with the conventional F-based plasma etching methods.

Understanding the contributions of F–, HF, and HF2– to the etching of SiO2 and unveiling the reaction kinetics to represent etching behavior of SiO2 up to pH 5

Understanding of the silicon dioxide (SiO2) etching mechanism in hydrofluoric acid (HF) solutions is important in semiconductor manufacturing processes. A study on the previous SiO2 etching mechanism claimed that only difluoride (HF2–) participated in SiO2 etching. However, in this study, it was observed that the etching of SiO2 occurred in the HF solution, where difluoride barely existed. Hence, a new SiO2 etching mechanism and reaction rate were proposed. Various concentrations of HF and ammonium fluoride (NH4F) under varying pH conditions were used to etch SiO2, leading to an SiO2 etching rate of 510[F–] + 610[HF] + 2890[HF2–] (Å/min). HF2– was the primary contributor to SiO2 etching; however, unlike the previous SiO2 etching mechanism, the effects of F– and HF on the etching of SiO2 were included in the rate of SiO2 etching. The SiO2 etching rate, considering the reactions between various fluorine species with varying SiO2 surface states, effectively represented the SiO2 etching behavior under various conditions over a broader pH range, up to pH 5. Controlling the ratio of the fluorine species, F–, HF, and HF2–, our etching model could also be extended to the selective etching of SiO2.

Large area nanoscale patterning of functional materials using organosilicate ink based nanotransfer printing

This paper presents a versatile nanotransfer printing method for achieving large-area sub-micron patterns of functional materials. Organosilicate ink formulations combined with effective release layers have been shown to facilitate patterning of materials through the commonly used patterning approaches—lift off, physical etching and chemical etching. In this paper, we demonstrate that organosilicate ink formulations function as an effective resist owing to its superior physico-chemical stability whereas the release layers ensure clean removal of the resist post patterning. We successfully demonstrate patterning of sub-micron structures (800 nm feature sizes) of chromium metal through the lift off approach, silicon through reactive ion etching technique and silicon dioxide through wet chemical etching technique illustrating the versatility of the reported method. This patterning methodology represents a significant advancement in enabling nanostructure fabrication within resource-constrained laboratories. The approach requires nothing more than a master mold containing the desired structures, a spin coater, a low-temperature hotplate, and a desktop reactive ion etch tool.

Highly Selective Etching of Silicon Dioxide Over Aluminum Using Mixtures of Sulfuric Acid and Hydrofluoric Acid

Highly Selective Etching of Silicon Dioxide Over Aluminum Using Mixtures of Sulfuric Acid and Hydrofluoric Acid

Topographically-selective atomic layer etching of SiO2 using radical fluorination of the surface followed by Ar ion bombardment

The chemical nature of surface fluorination followed by ion bombardment has been explored to achieve a topographically selective atomic layer etching of silicon dioxide at RT. In this work, a two-step low-pressure sulfur hexafluoride (SF6) remote plasma modification (without any ion bombardment) followed by argon (Ar) ion bombardment is presented. In situ investigations of the surface bonding confirmed the modification during the half-reaction steps and spectroscopic ellipsometry data reveal the thickness change while suggesting an incubation period prior to obtaining a uniform etch per cycle of 0.14 nm with a synergistic 30 s fluorination of the surface followed by a 60 s Ar bombardment. The etch profile of the trenched structured sample displays the isotropic etch for the two-step process, as well as the feasibility of a topo-selective top-and-bottom etch by bias application in the Ar bombardment step.

Tapered Silicon Oxide Etching for Creation of Capacitor Structures for Measurement of Dielectric Characteristics

Tapered Silicon Oxide Etching for Creation of Capacitor Structures for Measurement of Dielectric Characteristics

Gas-phase etching mechanism of silicon oxide by a mixture of hydrogen fluoride and ammonium fluoride: A density functional theory study

We report the selective etching mechanism of silicon oxide using a mixture of hydrogen fluoride (HF) and NH4F gases. A damage-free selective removal of native oxide has been used in semiconductor manufacturing by forming and removing the ammonium fluorosilicate [(NH4)2SiF6] salt layer. A downstream plasma of NF3/NH3 or a gas-phase mixture of HF and NH4F was used to form (NH4)2SiF6. We modeled and simulated the fluorination of silicon oxide and the salt formation by density functional theory calculation. First, we simulated the successive fluorination of silicon oxide using SiO2 slab models. The fluorination reactions of SiO2 surfaces by the mixture produced a volatile SiF4 molecule or a surface anion of –OSiF4−* with an NH4+ cation with low activation energies. Unlike HF, NH4F produced surface salt species consisting of a surface anion and an ammonium cation. Next, we simulated the (NH4)2SiF6 formation from the two reaction products on fluorinated SiO2 surfaces. (NH4)2SiF6 can be formed exothermally with low activation energies (0.27 or 0.30 eV). Finally, we compared silicon with SiO2 to demonstrate the inherently selective etching of silicon oxide. The fluorination reactions of silicon by the mixture showed the activation energies significantly higher than the SiO2 cases, 1.22–1.56 eV by HF and 1.94–2.46 eV by NH4F due to the less stable transition state geometries. Therefore, the selective salt formation on silicon oxide, not on silicon, is expected in near-room temperature processing, which enables selective etching of silicon oxide.

Selective etching mechanism of silicon oxide against silicon by hydrogen fluoride: a density functional theory study.

Selective etching of silicon oxide (SiO2) against silicon (Si) using anhydrous hydrogen fluoride (HF) vapor has been used for semiconductor device fabrication. We studied the underlying mechanism of the selective etching by density functional theory (DFT) calculation. We constructed surface slab models of SiO2 or Si with different degrees of fluorination and simulated the four steps of fluorination. The calculations show relatively low activation energies of 0.72-0.79 eV for the four steps of fluorination of SiO2, which are close to ∼0.69 eV observed in the experiment. The four-membered ring structure of -Si-O-H-F- in all transition states stabilized the system, resulting in relatively low activation energies. Thus, continuous etching of SiO2 by HF is plausible at near-room temperature. In contrast, the fluorinations of Si showed relatively high activation energies ranging from 1.22 to 1.56 eV due to the less stable transition state geometries. Thus, negligible etching of silicon by HF is expected by the near-room temperature process. Our calculation results explain well the experimental observation of the selective etching of SiO2 against Si by HF vapor.

Control of silicon dioxide etching rate in hydrogen microwave plasma by addition of oxygen

Hydrogen plasma treatment of thin films and bulk silica is important process for surface cleaning, smoothing and patterning. We studied etching of SiO2 plates in H2 + O2 microwave plasma at moderate pressures at high temperatures in the range of 790–1300 °C. A low-coherent optical interferometer was used for simultaneous in situ measurement of etch rate (ER) and the SiO2 temperature. We show that even a small addition of O2 (<1%) in microwave H2 plasma can effectively reduce the SiO2 ER due to redox reaction. Using an optical profilometry and atomic force microscopy we observed not only a strong etching inhibition by O2 addition in gas, but a significantly smoother etched surface as well. The activation energies Ea = 128 ± 8 kJ/mol and 276 ± 23 kJ/mol are found for the etching in pure H2 and H2 + 0.4 %O2 plasmas, respectively. An exponential dependence of ER on O2 content in gas is established, particularly, the O2 concentration as small as 2.6 % is sufficient to reduce the ER by 100 times. The effect of oxygen induced etching slow-down is supported by thermodynamic consideration of the surface reactions involved. The experiments were complimented with the plasma diagnostics by optical emission plasma spectroscopy to detect volatile etching products, and other species such as OH, and correlate the Si emission intensity with the measured ER. Our results confirm the efficiency of oxygen to control in a wide range the etch rate and surface topography upon atomic hydrogen etching in a microwave plasma.

Molecular dynamics simulation of oxide-nitride bilayer etching with energetic fluorocarbon ions

In 3D NAND devices, the number of stacked layers dictates the storage capacity. In the fabrication of such devices, hole channels with a high-aspect ratio (HAR) are etched through these layers. The higher the aspect ratio becomes, the more difficulties the HAR etching faces. In this study, molecular dynamics simulation was performed to examine the etching of silicon dioxide (SiO2), silicon nitride (SiN), and oxide-nitride (ON) stacked layers by energetic fluorocarbon ions. Good agreement of etching yields obtained from the simulations and ion beam experiments was observed for the etching of SiO2 and SiN by CF3+ ions for the incident ion energy ranging from 200 to 2000 eV. As to the etching of the ON bilayer, the SiO2 and SiN layers were observed to be etched with their own etch rates at low ion incident energy. However, at sufficiently high incident ion energy, the oxide and nitride layers were mixed by energetic ion impact and the depth of the mixing layer exceeded the thickness of the top SiO2 layer thickness, resulting in a single etch rate limited by the etch rate of a much deeper underlying SiN material. This suggests that if the incident ion energy is high enough such that the thicknesses of the multilayers are lower than the ion penetration depth, the ON stacked layer exhibits a single etch rate determined by the mixed material of the oxide and nitride.

Area-selective plasma-enhanced atomic layer etching (PE-ALE) of silicon dioxide using a silane coupling agent

A novel route to achieve an ideal plasma-enhanced atomic layer etching of silicon dioxide with self-limiting deposition and area-selective feature over silicon nitride is demonstrated in this work using a silane coupling agent and argon plasma. While monitoring the film thickness of silicon dioxide, self-limiting characteristics in both modification and etching steps are attained. Moreover, the dosing step revealed the selective formation of a modification layer on the oxide over the nitride film. In situ infrared spectroscopy results suggest the surface functionalization of the hydroxyl terminal groups of the oxide with the silane coupling agent to form the self-limiting modification layer at a relatively low substrate temperature. Compared to the previously reported fluorocarbon precursors, a higher etch yield for SiO2 was calculated, showing a promising option to meet the increasing demands in semiconductor production.

Effect of hydrofluorocarbon structure of C3H2F6 isomers on high aspect ratio etching of silicon oxide

In this study, using three isomers (1,1,1,3,3,3-hexafluoropropane (HFC-236fa), 1,1,1,2,3,3-hexafluoropropane (HFC-236ea), 1,1,2,2,3,3-hexafluoropropane (HFC-236ca)) having the same chemical composition of C3H2F6, effects of chemical branch structure of three C3H2F6 isomers on the plasma characteristics and etch characteristics of high aspect ratio ACL patterned SiO2 were investigated. During the etching of SiO2 and amorphous carbon layer (ACL) using the three isomers mixed with oxygen, different etch characteristics and plasma characteristics were observed. In the plasmas, more CF2 and H but, less F were related to the formation of a fluorocarbon polymer layer on the surface, while lower high mass ion species such as C3HF4+ and, C3H2F5+ were related to the ion bombardment in the order of HFC-236fa, HFC-236ea, and HFC-236ca consequently leading to a lower SiO2 etch rate. Therefore, when C3H2F6 was used, even with the same chemical composition, the chemical branch structure of the compound affected the plasma properties and etch characteristics significantly depending on chemical branches in the compound. We believe that, for other hydrofluorocarbon compounds mixed with a critical oxygen flow rate, plasma properties and SiO2 etch characteristics can be estimated through properties of chemical branches attached in these compounds.

Atomic layer etching of SiO2 using trifluoroiodomethane

Herein, atomic layer etching (ALE) of silicon dioxide (SiO2) was performed using trifluoroiodomethane (CF3I) in a capacitively coupled plasma reactor. First, a fluorocarbon polymer was deposited using CF3I plasma to fluorinate the SiO2 surface. Second, the deposited polymer and fluorinated SiO2 were removed using O2 plasma. By optimizing various process variables, an etch rate per cycle of 9.3 Å was obtained with a controlled source power of 300 W. In addition, a self-limiting characteristic was confirmed during the CF3I exposure for the polymer deposition in the first step, as well as during the O2 exposure for polymer removal in the second step. Finally, the remnant iodine on the etched substrate was analyzed because CF3I contains iodine. Iodine compounds were generated during the SiO2 ALE process.

Hydrogen microwave plasma etching of silicon dioxide at high temperatures with in situ low-coherence interferometry control

We used a low-coherence interferometry (LCI) to measure in situ the etch rate of silica surfaces in H2 microwave plasma at high temperatures of 970–1480 °C. The method allows collection of kinetic data on a single sample without switching-off the plasma, moreover, the LCI provides simultaneous measurements of the sample thickness and temperature evolution. The etching rates up to ∼80 nm/min are measured, and activation energy for SiO2 reaction with atomic hydrogen is determined. Appearance of Si atoms in the plasma as a result of the etching was monitored with optical emission spectroscopy, and a very good correlation of intensity of Si lines at 288 и 390 nm wavelengths in the spectra with the etching rate is demonstrated. The data on the surface relief modification caused by the etching are presented.

ВЛИЯНИЕ ПАССИВИРУЮЩЕГО ПОКРЫТИЯ НА СТРУКТУРУ АЛЮМИНИЕВОЙ МЕТАЛЛИЗАЦИИ НА КРЕМНИИ

The surface quality of the metallized contact pads on the crystal plays an important role in the production of semiconductor devices. This paper presents experimental studies of the effect of a protective passivation film of silicon oxide on the surface structure of aluminum metallization in the field of forming contact pads. Plasma chemical deposition of passivation layer SiO2 from gas phase (PECVD method) was carried out on prepared samples of silicon with aluminum metallization using a high-frequency power source with a frequency of 13.56 MHz. After that, chemical etching of precipitated silicon oxide was carried out to simulate the process of forming contact areas of semiconductor device crystals. The resistance of the metallization surface to plasma processes was studied by raster electron microscopy. It is shown that as a result of the process cycle, defects of the dislocation type are generated in the applied film Al. The nature of the observed defects has been found to be different. The revealed large square-shaped pits with a size of ~ 1 μm at the places where dislocations come to the surface are of a single nature and appear independently of the processes of applying passivation coatings, which is determined by the orienting action of a single-crystal substrate having some low dislocation density. While the second type of defects, shown by the presence of etching pits measuring ~ 100-300 nm, is characterized by a higher surface density. Moreover, the exclusion of the passivation process with silicon oxide did not lead to the appearance of this type of defects, which determined their nature associated with the ion bombardment of the Al layer during the plasma chemical deposition of silicon oxide from the gas phase. It is also shown that a feature of this type of defects is their disorientation both with respect to the first type of defects and with respect to each other. Detection of the structure of the metallization layers was carried out by X-ray diffraction, the results of which show the polycrystallinity of the formed aluminum metallization. The preferred orientation of the aluminum film corresponds to the substrate Si (111).

Cyclic etching of silicon oxide using NF3/H2 remote plasma and NH3 gas flow

AbstractSelective isotropic cyclic dry etching of silicon oxide (SiO2) was investigated using a three‐step cyclic process composed of hydrogen fluoride (HF) adsorption by NF3/H2 remote plasma and reaction with NH3 gas flow to form ammonium fluorosilicate ((NH4)2SiF6), and desorption by heating. The variation of the ratio of NF3:H2 (2:1 to 1:3) and adsorption time (10–180 s) showed the highest etch selectivity of SiO2 over Si3N4 at 1:2 ratio of NF3:H2 and with the adsorption time of 20 s. The etch selectivity higher than 40 was observed with 20 s of adsorption time with a 1:2 ratio of NF3:H2 remote plasma and the total etch depth was linearly increased with the increase of cycles with the SiO2 EPC of ~7.5 nm/cycle.

Fabrication of a silicon μDicer for uniform microdissection of tissue samples

Generating uniform tissue microfragments is important in many applications, including disease diagnostics, drug screening, spatial-omics, and fundamental wound healing and tissue regeneration studies. Common mechanical dissection methods, such as manual mincing, are imprecise and result in fragments with a broad range in size. This work aims to develop a microscale dicing device, referred to as the “μDicer,” consisting of a hollow array of blades spaced hundreds of micrometers apart. A tissue pushed through this array is diced into many microfragments simultaneously. The focus of this paper is on the fabrication process of the μDicer using a combination of isotropic and anisotropic etching in silicon. A single silicon oxide etch mask is used in a dry silicon etcher for both a tapered etch to form the microblades, and an anisotropic etch to form the through-holes in the hollow blade array. The use of a single mask reduces the mask fabrication time by more than twofold compared with two-mask approaches often used to generate similar etch features. The etch parameters and the design of the etch mask control the blade angles and the edge profiles of the blades. Specifically, the incorporation of “notches” in the two-dimensional mask design generates three-dimensional microserrated features on the blade edges. A custom, open-source etching model is also developed to facilitate the prediction of the etch profiles. Finally, a proof-of-concept application of the μDicer to dissect soft materials and tissues is demonstrated.

The investigation of DARC etch back in DRAM capacitor oxide mask opening

Opening the silicon oxide mask of a capacitor in dynamic random access memory is a critical process on a capacitive coupled plasma (CCP) etch tool. Three steps, dielectric anti-reflective coating (DARC) etch back, silicon oxide etch and strip, are contained. To acquire good performance, such as low leakage current and high capacitance, for further fabricating capacitors, we should firstly optimize DARC etch back. We developed some experiments, focusing on etch time and chemistry, to evaluate the profile of a silicon oxide mask, DARC remain and critical dimension. The result shows that etch back time should be controlled in the range from 50 to 60 s, based on the current equipment and condition. It will make B/T ratio higher than 70% meanwhile resolve the DARC remain issue. We also found that CH2F2 flow should be ~15 sccm to avoid reversed CD trend and keep inline CD.

Molecular Dynamics Simulation of Silicon Dioxide Etching by Hydrogen Fluoride Using the Reactive Force Field.

In this study, we develop a reactive force field (ReaxFF) for a Si/O/H/F system to perform etching simulations of SiO2 with an HF etchant. Quantum mechanical (QM) training sets from density functional theory calculations, which contain structures of reactant/product and energies with bond dissociation, valence angle distortions, and reactions between SiO2 clusters and SiO2 slab with HF gases, are used to optimize the ReaxFF parameters. Structures and energies calculated using the ReaxFF match well with the QM training sets. Using the optimized ReaxFF, we conduct molecular dynamics simulations of the etching process of SiO2 substrates with active HF molecules. The etching yield and number of reaction products with different incident energies of the HF etchant are investigated. These simulations show that the developed ReaxFF offers insights into the atomistic surface reaction of the SiO2 etching process.