Graphite is highly noteworthy for next-generation pellicles due to its high emissivity (>0.3), and Young's modulus (4.1 GPa) which provides high thermal and mechanical stability. The widely used graphite synthesis is chemical vapor deposition on thick metal catalyst, which involves several disadvantages such as hard to control of thickness uniformity and damage during wet-transfer processes. To overcome these problems, we propose a direct synthesis of graphite film(< 30 nm) on insulating substrate at low temperature about 500°C starting from the amorphous carbon (a-C) on catalyst metal film, which is named as graphite-metal induced crystallization of a-C (G-MICA). We finally demonstrate the formation of a graphite with uniform thickness below 30 nm on 8-inch SiNx/Si wafer with an annealing at 500°C for 1 h. In order to reveal the origin of thickness uniformity of G-MICA, we closely observe the microstructure evolution of graphite as a function of annealing temperature (400~800°C) and time (0.25~180 min) using Cs corrected transmission electron microscopy. We believe that the nucleation of graphite starts to form at the interface between Ni and a-C and so vertical growth of graphite is limited by the thickness of Ni, which is somewhat differ from previously reports. To evaluate EUV characteristic, we removed the SiNx layer under the graphite through dry etching as thin as possible and made it in the form of a membrane. The G-MICA pellicle with thickness of 18 nm showed EUV transmittance of 88%, and emissivity of 0.3. Therefore, we confirmed the possibility of low-temperature G-MICA as a pellicle synthesis.
The power of EUVL (extreme ultraviolet lithography) scanner continues to increase, making the heat dissipation characteristics of EUV pellicles increasingly crucial. The thermal and chemical stability of the EUV pellicles, which have a multilayer thin film structure, relies on the capping layer, and the thermal stability of the capping layer is determined by its emissivity (ε). However, it is challenging to directly measure the ε of an ultrathin film, such as the capping layer of the EUV pellicle. Although a method to obtain the ε of a target material is employed which measure the ε of the whole layer with a target material on a support membrane having low ε, no approach has been proposed to exclude the measurement changes caused by the support membrane. In this study, a methodology for obtaining the ε of a multilayer nanomembrane is proposed. Ruthenium (Ru) with a high ε at nanoscale was deposited on SiNx membranes to have varying thicknesses. The ε of SiNx film and Ru deposited SiNx film were precisely characterized by infrared spectroscopy according to Kirchhoff's law. Based on transfer matrix method (TMM), the ε of Ru layers was theoretically calculated, fitting by DrudeLorentz oscillator model. Finally, reliability was verified by comparing the measurement results through a free-standing membrane without a support. In this way, if the contribution of a single element to the ε of a multilayer or composite membrane can be derived, engineering for a high-emissive layer that combines various components will be possible and used as EUV pellicle and further application research.
As the power of EUVL (extreme ultraviolet lithography) scanners increases, the thermal load and hydrogen plasma environment applied to the pellicle become harsher. If the core material of the pellicle membrane is unstable in the EUV environment, reliability depends on the top-most layer (capping). However, the loss of EUV transmission restricts the thickness of the capping and raises concerns related to hydrogen radicals or protons. In our previous report, we introduced molybdenum carbide (Mo2C) as a new pellicle material with high EUV transmittance (91.4 %), transmission uniformity (3σ=0.49 %, 5×5 mm2), and chemical stability against a hydrogen plasma. In this report, we demonstrate the stability against high-intensity (30 W/cm2) EUV irradiation and hydrogen plasma for Mo2C membranes. Large-area (≥5×5 cm2) Mo2C membranes with high EUV transmittance (≥88 %) were fabricated using MEMS technology. The membranes were tested for thermal load test using an 808 nm infrared laser under the same conditions producing up to 3000 wafers in the EUV scanner. The chemical properties of the membranes were evaluated using an inductively coupled plasma device in a high-temperature (<900 °C) hydrogen gas and plasma environment. Furthermore, the EUV transmittance for the Mo2C membrane and the difference after thermal load and hydrogen plasma evaluation were characterized by EUV coherence scattering microscopy. Consequently, we show the feasibility of high-volume manufacturing (HVM) Mo2C pellicles by fabricating the membrane over 5 × 5 cm2.
As the EUV source power increases, the industry requires new pellicle materials with high EUV transmittance and chemical stability under EUV irradiation environments. We demonstrate a molybdenum carbide (Mo2C) membrane as a new pellicle material which exhibits high EUV transmittance (≥ 88 %). The stability of Mo2C membranes was confirmed under high temperature and hydrogen plasma. Through this study, the possibility of Mo2C as a candidate material for EUV pellicle was confirmed.
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