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Consequences of Implanting and Surface Mixing During Si and SiO2 Plasma Etching* Mingmei Wang1 and Mark J. Kushner2 1Iowa State University, Ames, IA 50011 USA [email protected] 2University of Michigan, Ann Arbor, MI 48109 USA [email protected] http://uigelz.eecs.umich.edu 36th ICOPS, June 2009, San Diego, CA *Work supported by Tokyo Electron Ltd. Micron Inc. and the SRC. MINGMEI_ICOPS09_01 AGENDA Implanting, mixing and photoresist (PR) erosion Processes Molecular ion dissociation on surfaces Small ion penetration and mixing PR cross-linking Description of Model Scaling of Mixing and Implantation Concluding Remarks MINGMEI_ICOPS09_02 University of Michigan Institute for Plasma Science & Engr. IMPLANTATION AND MIXING DURING PLASMA ETCHING Bulk Plasma Diamond structure of Si CxFy+ Cx-1Fy-1 + Polymer Ar+ + Si + O + O2 + F 2 + + O,F F C Si Ar O,F O Substrate (SiO2, Si or PR) C O F Si Ar Small ions accelerated by the sheath implant into the wafer surface forming weakly bonded or interstitially trapped species. Implanting causes surface mixing which produces damage during plasma etching. MINGMEI_ICOPS09_03 University of Michigan Institute for Plasma Science & Engr. PHOTORESIST (PR) EROSION Bulk Plasma Ions C H O PR PR Photoresist defines the features to be etched – usually a hydrocarbon polymer. SiO2 PR is sputtered by energetic ions. Fragmented PR segments are more easily eroded. Profile of high aspect ratio (HAR) features can be modified due to PR erosion. MINGMEI_ICOPS09_04 University of Michigan Institute for Plasma Science & Engr. APPROACHES AND GOALS OF INVESTIGATION Consequences of implantation and mixing are poorly characterized in modeling of plasma etching. Usually only included in compute-intensive molecular dynamics simulations. Incorporate implantation, mixing, and sputtering into Monte-Carlo Feature Profile Model coupled to equipment scale plasma models. Investigate: Scaling of implantation, mixing, and etching selectivity. Degradation and cross-linking of PR surface due to energetic bombardment. Goals Characterize mixing damage during etching. Develop strategies to preserve pattern transferring while minimizing damage. MINGMEI_ICOPS09_05 University of Michigan Institute for Plasma Science & Engr. DESCRIPTION OF MODEL Hybrid Plasma Equipment Model (HPEM) Sources Fields Transport coefficients Si SiO2 Plasma Chemistry Monte Carlo Model (PCMCM) Fluxes Energy angular distributions Sputtering Yields Range of Ions Monte Carlo Feature Profile Model (MCFPM) Implantation / Mixing MINGMEI_ICOPS09_06 University of Michigan Institute for Plasma Science & Engr. IMPLANTATION MODEL Ar+,F+,Si+ C+,O+ Pushed out n<N* in Stopping range = f(in) Mixing Yes 4 Move to next cell Implant 2 3 4 No 5 Within one cell: out= in exp(-a/) Where in = incident energy; out = left energy. a = Actual length that the particle travels. = Calculated stopping range f(in). *n = mixing step; N = allowed maximum mixing step. MINGMEI_ICOPS09_07 Implant Mixing End SiO2,Si or PR i=1 No a 3 5 Surface reaction Yes out 2 No Implant Start a j=1 Gas-solid surface interaction /in R* Yes Exchange identity *R = Random number University of Michigan Institute for Plasma Science & Engr. SURFACE REACTION MECHANISM Etching of SiO2 is dominantly through a formation of a fluorocarbon complex. SiO2(s) + CxFy+(g) SiO2*(s) + CxFy(g) SiO2*(s) + CxFy(g) SiO2CxFy(s) SiO2CxFy (s) + CxFy+(g) SiFy(g) + CO2 (g) + CxFy(g) Further deposition by CxFy(g) produces thicker polymer layers. Example reaction of surface dissociation. M(s) + CxFy+(g) M(s) + Cx-1Fy-1(g) + C(g) + F(g) Sputtering of PR and redeposition. PR(s) + Ar+(g) PR2(s) + Ar(g) + H(g) + O(g) PR(s) + CxFy+(g) PR(s) + CxFy(g) PR(g) + SiO2CxFy(s) SiO2CxFy(s) + PR(s) *PR2 = cross-linked PR MINGMEI_ICOPS09_08 University of Michigan Institute for Plasma Science & Engr. FLUOROCARBON ETCHING OF SiO2 DC augmented single frequency capacitively coupled plasma (CCP) reactor. DC: Top electrode RF: Substrate Plasma tends to be edge peaked due to electric field enhancement. Plasma densities in excess of 1011 cm-3. Ar/C4F8/O2 = 80/15/5, 300 sccm, 40 mTorr, RF 1 kW at 10 MHz, DC 200 W/-250 V. MINGMEI_ICOPS09_09 University of Michigan Institute for Plasma Science & Engr. ION ENERGY ANGULAR DISTRIBUTIONS (IEADs) Peak of ion energy ranges from 300 to 1200 eV for 1 – 4 kW bias power. Angle distribution spreads from -10 to 10 degree . Stopping range ranges from 0 to 70 Å. MINGMEI_ICOPS09_10 University of Michigan Institute for Plasma Science & Engr. STOPPING RANGE IN PR, POLYMER, Si, AND SiO2 Stopping range increases with increasing energy. At specific energy, implanting depth: PR(PMMA*) > SiO2 > Si > Polymer *PMMA = Polymethylmethacrylate Data from SRIM (the Stopping and Range of Ion in Matter) Stopping range = f(incident) MINGMEI_ICOPS09_11 University of Michigan Institute for Plasma Science & Engr. IMPLANTING AND MIXING DEPTH vs BIAS POWER After 5 s (a) (b) MINGMEI_ICOPS09_12 Etch rates, degree of mixing and depth of implantation increase with bias power. After same etch level University of Michigan Institute for Plasma Science & Engr. IMPLANTING AND MIXING DEPTH vs ENERGY Only polymer deposition occurs at 1 eV. Sputtering, implanting and deposition coexist at 10 eV. Depth of implantation and mixing increases with increasing ion energy (100 eV~10 keV). MINGMEI_ICOPS09_13 University of Michigan Institute for Plasma Science & Engr. ETCHING SELECTIVITY Etch stop occurs at Si surface due to low reaction rate with CFx. 3 nm Etching selectivity for SiO2/PR(PMMA) is around 10. 30 nm The roughness of SiO2 surface is due to non-uniform polymer deposition. Micro-masking Micro-trenching Ar/C4F8/O2 = 80/15/5, 4 kW, 300sccm, 40mTorr, DC 200W/-250V. MINGMEI_ICOPS09_14 University of Michigan Institute for Plasma Science & Engr. MECHANISM FOR DEGRADATION AND CROSS-LINKING OF PR Structure of PR(PMMA) CH3 …CH2 CH3 C C CH2 O CH3 C C CH2 O CH2… C C O O O CH3 CH3 CH3 O PR molecule is degraded due to energetic ion sputtering. Degraded PR segments are more easily eroded. Newly formed dangling bonds are recombined (cross-linking), and cross-linked PR forms a “hard crust”. Sputtering yield is calculated using SRIM. MINGMEI_ICOPS09_15A University of Michigan Institute for Plasma Science & Engr. DEGRADATION OF PR (SPUTTERING) CH3 …CH2 CH3 C C CH2 O CH3 C C CH2 O CH2… C C O O O CH3 CH3 CH3 O Broken Bond MINGMEI_ICOPS09_15B University of Michigan Institute for Plasma Science & Engr. DEGRADATION OF PR (SPUTTERING) H CH3 …CH2 CH2 C C CH2 O CH3 C C CH2 O CH2… C C O O O CH3 CH3 CH3 O Broken Bond MINGMEI_ICOPS09_15C University of Michigan Institute for Plasma Science & Engr. INTER-MOLECULE CROSS-LINKING CH3 …CH2 CH3 C C CH2 O O C C O CH2 H CH3 CH2 CH2 O CH2… C C O O CH3 H Broken Bond New Bond MINGMEI_ICOPS09_15D University of Michigan Institute for Plasma Science & Engr. INTER-MOLECULE CROSS-LINKING H H CH3 …CH2 CH2 C C CH2 O O C C O CH2 H CH2 CH2 CH2 O CH2… C C O O CH3 H Broken Bond New Bond MINGMEI_ICOPS09_15E University of Michigan Institute for Plasma Science & Engr. INTER-MOLECULE CROSS-LINKING H H CH3 …CH2 O C CH2 CH2 C C CH2 CH2 O C CH2 O H C CH2 O CH2… C O O H CH3 Broken Bond New Bond MINGMEI_ICOPS09_15F University of Michigan Institute for Plasma Science & Engr. INTRA-MOLECULE CROSS-LINKING CH3 …CH2 C C Molecule A CH3 CH2 O Broken Bond New Bond MINGMEI_ICOPS09_15G CH2 O CH2… C C O O O H CH2 H CH2 CH2 H H CH2 H CH2 CH2 H …CH2 C C Molecule B C C O CH3 CH2 O C C CH2 O CH2… C C O O O CH3 CH3 CH3 O INTRA-MOLECULE CROSS-LINKING Molecule A CH3 …CH2 C C CH3 H Broken Bond New Bond …CH2 MINGMEI_ICOPS09_15H CH2 O CH2 H C CH2 O CH3 C C CH3 O C Molecule B CH3 CH2 O C O O CH2 CH2 C C CH2 O CH2… C O CH3 H CH2… C C O O O CH3 CH3 CH3 O ETCHING SELECTIVITY vs ENERGY (a) (b) (c) Etching rate for SiO2 increases with increasing ion energy. Balance between sputtering and cross-linking (more resistive to etching) on PR(PMMA) surface results in similar etching rate for all energies. Surface roughness of SiO2 increases as etching proceeds due to micromasking. Etching selectivity (SiO2/PR): 100 eV, 6; 500 eV, 18; 1000 eV, 23. MINGMEI_ICOPS09_16 University of Michigan Institute for Plasma Science & Engr. ETCHING SELECTIVITY vs RF BIAS POWER 4 kW 1 kW 4 kW 4 kW No mixing, no sputtering PR Si At similar etching level of PR, aspect ratio (AR) of the trench increases with bias power. SiO2 Etching selectivity increases when PR is cross-linked. Si AR = 9 14 13 Ar/C4F8/O2 = 80/15/5, 300 sccm, 40 mTorr, 10 MHz, DC 200 W/-250 V. MINGMEI_ICOPS09_17 Si is damaged during overetch by implantation and mixing. University of Michigan Institute for Plasma Science & Engr. CONCLUDING REMARKS Algorithms have been incorporated into the MCFPM to predict implanting and mixing. Depth of implanting and mixing increases with increasing bias power and ion energy. More damage is obtained at higher etching rate. PR surface is cross-linked due to sputtering. At higher bias power and ion energy, etching selectivity for SiO2/PR is better. Strategies to be developed for high power processing: Protect pattern transferring at higher etching rate. Reduce damage during over-etch. MINGMEI_ICOPS09_18 University of Michigan Institute for Plasma Science & Engr.