Selective isotropic etching of SiO2 over Si3N4 using NF3/H2 remote plasma and methanol vapor.

In this study, an isotropic etching process of SiO2 selective to Si3N4 using NF3/H2/methanol chemistry was investigated. HF was formed using a NF3/H2 remote plasma, and in order to remove the F radicals, which induces spontaneous etching of Si-base material, methanol was injected outside the plasma discharge region. Through this process, etch products were formed on the surface of SiO2, and then the (NH4)2SiF6 was removed by following heating process. When the H and F radicals were abundant, the highest SiO2 etch per cycle (EPC) was obtained. And, the increase of H2 and methanol percentage in the gas chemistry increased the etch selectivity by decreasing the F radicals. The etch products such as (NH4)2SiF6 were formed on the surfaces of SiO2 and Si3N4 during the reaction step and no noticeable spontaneous etching by formation of SiF4 was observed. By optimized conditions, the etch selectivity of SiO2 over Si3N4 and poly Si higher than 50 and 20, respectively, was obtained while having SiO2 EPC of ~ 13 nm/cycle. It is believed that the cyclic process using NF3/H2 remote plasma and methanol followed by heating can be applied to the selective isotropic SiO2 etching of next generation 3D device fabrication.

Atomic layer etching of Sn by surface modification with H and Cl radicals.

Sn is the one of the materials that can be used for next generation extreme ultraviolet (EUV) mask material having a high absorption coefficient and, for the fabrication of the next generation EUV mask, a precise etching of Sn is required. In this study, the atomic layer etching (ALE) process was performed for the precise etch thickness control and low damage etching of Sn by the formation SnHxClycompounds on the Sn surface using with H and Cl radicals during the adsorption step and by the removal of the compound using Ar+ions with a controlled energy during the desorption step. Through this process, optimized ALE conditions with different H/Cl radical combinations that can etch Sn at ∼2.6 Šcycle-1were identified with a high etch selectivity over Ru which can be used as the capping layer of the EUV mask. In addition, it was confirmed that not only the Sn but also Ru showed almost no physical and chemical damage during the Sn ALE process.

Etch characteristics of magnetic tunnel junction materials using H2/NH3 reactive ion beam.

Magnetic tunneling junction (MTJ) materials such as CoFeB, Co, Pt, MgO, and the hard mask material such as W and TiN were etched with a reactive ion beam etching (RIBE) system using H2/NH3. By using gas mixtures of H2 and NH3, especially with the H2/NH3( 2:1) ratio, higher etch rates of MTJ related materials and higher etch selectivities over mask materials (>30) could be observed compared to those etching using pure H2( no etching) and NH3. In addition, no significant chemical and physical damages were observed on etched magnetic materials surfaces and, for CoPt and MTJ nanoscale patterns etched by the H2/NH3( 2:1) ion beam, highly anisotropic etch profiles >83° with no sidewall redeposition could be observed. The higher etch rates of magnetic materials such as CoFeB by the H2/NH3( 2:1) ion beam compared to those by H2 ion beam or NH3 ion beam are believed to be related to the formation of volatile metal hydrides (MH, M = Co, Fe, etc) through the reduction of M-NHx( x = 1 ∼ 3) formed in the CoFeB surface by the exposure to NH3 ion beam. It is believed that the H2/NH3 RIBE is a suitable technique in the etching of MTJ materials for the next generation nanoscale spin transfer torque magnetic random access memory (STT-MRAM) devices.

Reactive ion etching of an ovonic threshold switch (OTS) material using hydrogen-based plasmas for non-volatile phase change memories.

Etch characteristics of ovonic threshold switch (OTS) materials composed of Ge-As-Te for a phase-change random access memory (PCRAM) has been investigated using reactive ion etching via hydrogen-based gases such as H2, CH4, NH3, CH4 + H2, and CH4 + NH3. Among the investigated hydrogen-based gases, NH3 showed the highest etching rate of about 0.52 nm s-1, but the formation of nitride compounds and the increased roughness were observed on the OTS surface by nitrogen. The use of other hydrogen-based gases such as CH4 and CH4 + H2 showed the deposition and low OTS etch rate, respectively, due to the presence of carbon in CH4. Even though H2 showed the better etch characteristics due to the no surface residues or compounds on the OTS surface related to carbon or nitrogen in the etch gases, the best OTS etch characteristics such as the second highest etch rate of 0.45 nm s-1, the lowest surface roughness of 0.21 nm, and no surface residues or compounds were observed with CH4 + NH3 due to the removal of carbon and nitrogen on the surface by the formation of volatile CN compounds while maintaining a high hydrogen atomic concentration in the plasma.

Plasma functional polymerization of dopamine using atmospheric pressure plasma and a dopamine solution mist.

By using DBD-type atmospheric pressure plasmas and a dopamine solution mist formed by a piezoelectric module, the possibility of depositing functional polymer films showing the physical and chemical characteristics of polydopamine without breaking the functional group of the dopamine has been investigated for different plasma voltages. The higher DBD voltages up to 3.0 kV decreased the functional groups such as catechol and amine (N/C ratio) relative to dopamine in the deposited polymer by increasing the dissociation of dopamine into atoms and small molecules due to higher electron energies. In contrast, the lower DBD voltages up to 1.5 kV increased the functional group and N/C ratio of dopamine in the deposited polymer by keeping the molecular structures of the dopamine due to lower electron energies. Therefore, the polymer deposited at the lower DBD voltages showed lower contact angles and higher metal absorption properties which are some of the surface modification characteristics of polydopamine. When the metal absorption properties of the polydopamine-like film deposited using the atmospheric pressure plasma of a low DBD voltage with a dopamine solution mist were compared with other metal absorbers for Cu, As, and Cr, the polydopamine-like film exhibited superior metal absorption properties. It is believed that this atmospheric pressure plasma process can be also applied to the plasma polymerization of other monomers without breaking the functional groups of the monomers.