Characterization of Post-etch Residue Clean By Chemical Bonding Transformation Mapping
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1 Characterization of Post-etch Residue Clean By Chemical Bonding Transformation Mapping Muthappan Asokan, Oliver Chyan*, Interfacial Electrochemistry and Materials Research Lab, University of North Texas Cheng-Hsien Wu +, Chih-Cheng Shih, Ting-Chang Chang, Departments of Physics, + Department of Materials and Optoelectronic Science, National Sun Yat-Sen University, Kaohsiung, Taiwan Present to SPCC-2018, *chyan@unt.edu
2 Objective: Utilize MIR-IR to optimize RIE etching and post RIE cleaning with minimum dielectric damages New MIR-IR Metrology Polymer residues Method for Wafer Characterization", U.S. Patent , ILD damages
3 Common Characterization Tools for ILD Nanostructure Physical Tools SEM: Decorated DHF Etch No Chemical Info TEM/EEL Labor intensive, Destructive. XPS : best for blanket wafer Atomic concentration % to assess F removal, take-off angle analyses to assess part of the side wall. Electrical Tools Hg Probe Non-contact, Contamination issues, For blanket wafer. MOS Structure Costly, Difficult locating sources of defects.
4 Ultra-clean Silicon Wafer Surface Preparation Front end (FEOL) Cleans MIR-R 4
5 Detect Trace organics (< ppb) Contamination in HF Solution Organics contamination MIR-IR Front end (FEOL) Cleans
6 MIR-IR : Apply to BEOL Processing Patterned ILD Wafer 6
7 MIR-IR is a Very Powerful Substantive Tool--- Isolate Low-k Film Stack only Spectra Oxide (50nm) Dense Low-k (50nm) Porous Low-k (300nm) Si sub ( ) Low-k Stack Si substrate Sample Spectrum Vs. Background Spectrum Low-k stack only Spectrum 7
8 Absorbance Chemical Bonding Transformation Map for Porous Low-k NanoStructure Carbon Doping a-ch 3 Low-k damage Residue removal Si-O cage Carbon Doping Si-O network Si-CH 3 (bend) Low-k Low-k Damage Si-CH 3 (rock Si-OH CH 2 O-SiH x SiH x Chyan, et al, ECS Solid State Lett., 3, N1 (2014) Wavenumber cm -1
9 Absorbance Identify Lowest Low-k Damage from four Strip Processes Four oxidative plasma strip processes screened by either adjusting process gases or by modulating chamber pressure for reduced O radical content Strip 1 Strip 2 Strip 3 Strip 4 Si-OH Strip process 1 induces minimal damage (lowest silanol) retaining maximal C-doping (highest CH 3 ) a-ch 3 Peak Heights (mabs) Strip 1 Strip 2 Strip 3 Strip 4 Strip 1 Highest Carbon Dopping Lowest Water Sensitivity Si-OH Wavenumber (cm -1 )
10 Identify Chemical Bonding Structure and Explore Cleaning Processes for Post-Etch Residues Patterned ILD Wafer 10
11 Absorbance (a.u.) Chemical Bonding Structure of Etch Residues 1x6nm 5x 28nm C=O FC=CF F 2 C=CF C=CF.... CF 3 t. Teflon (CF. 2 ). as (CF2 ) s CF. i 3 (CF 2 ) def (am). Polytetrafluoroethylene (Teflon) Wavenumber (cm -1 ) Mainly fluoropolymer backbone Significant branching/cross-linking Olefinic unsaturation (fluorinated) Carbonyl functional groups ECS Solid State Lett., 2, N11 (2013)
12 Monitor Wet Clean Efficiency on Post-etch Residue CF x, 1234 cm -1 CF x, 1234 cm -1 Post etch residues 1X Polymer
13 Evaluate Low-K Damages from Wet Clean Process Si-CH 3, 1278 cm -1 Si-CH 3, 1278 cm -1 Si-O-Si Si-O-Si Post etch residues Cleaning agent attacks ULK within 1 min of treatment. 1X Polymer
14 Quantitative Evaluation of Wet Clean Process Cleaning Efficiency Loss of Si-CH 3 Loss of ULK MIR-IR gives cleaning process evolution insights
15 Explore New Cleaning Processes for Post-Etch Residues Patterned ILD Wafer 15
16 UV-assisted Cleaning on Post-etch Residues No UV 10sec UV UV induced Polymer Residue Removal Hydrophobic No Wet Clean Hydrophilic Wet Clean workable UV UV How to access clean result?
17 MIR-IR can Assess UV Cleaning Process CF x =CF x Hydrophilic Wet Clean workable How effective? Low-k damages? Process evolution insights shorten R&D cycles 17
18 Super Critical Cleaning for Post-etch Residues (a) CF 4, CO 2 MUTHU: Search ther papers for a picture or scheme for SCC set up (3000 psi) H 2 O, H 2 O 2, Acetone (a) Reference: RSC Adv., 2017, 7, (b) Reference: Appl. Phys. Lett. 104, (2014)
19 Comparison of three SCC-CO 2 Cleans (Differentials) SSC CO 2 SSC CO 2 + H 2 O SSC CO 2 + H 2 O + UV
20 Exploring new SCC-CF 4 Cleans (TEM Data) SSC-CF 4 + UV
21 Goal: Achieve better understanding of fundamental materials properties at the critical interfaces of practical applications. Group members: Muthappan Asokan Josh Caperton Issac Goutham, Kanwal JitSingh Alan M Myers Ian Brown Intel Intel TEL (now with SCREEN) 21
22 MIR-IR Applications in Advanced IC Fabrication FEOL, BEOL etching and cleaning, formulation development Monitor Post-etch residue removal & minimize Low-k damages Optimize Plasma Etch/Strip/Clean Process integration Monitor Low-k damages and optimize restoration process UV curing on porous Low-k dielectrics materials Evaluate TiN hard mask for Low-k pattern fabrication Flowable low-k dielectrics for gap filling in nanostructure Atomic Layer Deposition/Etching : provide critical interfacial chemical bonding info for better atomic layer control. PI: Oliver Chyan*, Chyan@unt.edu
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