SIMULATION OF POROUS LOW-k DIELECTRIC SEALING BY COMBINED He AND NH 3 PLASMA TREATMENT * Juline Shoeb a) and Mark J. Kushner b) a) Department of Electrical.

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SIMULATION OF POROUS LOW-k DIELECTRIC SEALING BY COMBINED He AND NH 3 PLASMA TREATMENT * Juline Shoeb a) and Mark J. Kushner b) a) Department of Electrical and Computer Engineering Iowa State University, Ames, IA b) Department of Electrical Engineering and Computer Science University of Michigan Ann Arbor, Ann Arbor, MI ICOPS, June 2009 *Work supported by Semiconductor Research Corporation JULINE_ICOPS09_01

 Low-k Dielectrics  Modeling Platforms  Modeling of Porous Low-k Sealing  Goals and Premises for Sealing Mechanism  Sealing Mechanism  Surface Site Activation by He plasma pre-treatment  Sealing by Ar/NH 3 Treatment  Sealing Efficiency Dependence  Porosity and Interconnectivity  Treatment time and Pore Radius  Concluding Remarks AGENDA JULINE_ICOPS09_02 University of Michigan Institute for Plasma Science & Engr.

POROUS LOW-k DIELECTRIC  Metal interconnect lines in ICs run through dielectric insulators.  The capacitance of the insulator contributes to RC delays.  Porous oxides, such as C doped SiO 2 (with CH n lining pores) have a low dielectric constant which reduces the RC delay.  Porosity is  0.5. Inter- connected pores open to surface offer pathways to degrade k-value by reactions. JULINE_ICOPS09_03 Ref: University of Michigan Institute for Plasma Science & Engr.

GOALS AND PREMISES OF SEALING MECHANISM  To prevent the degradation of low- k materials pores open to the surface has to be sealed.  He followed by NH 3 plasma treatment has been shown to seal the pores.  He + and photons break Si-O bonds while knocking off H atom from CH n. JULINE_ICOPS09_04 Ref: A. M. Urbanowicz, M. R. Baklanov, J. Heijlen, Y. Travaly, and A. Cockburn, Electrochem. Solid-State Lett. 10, G76 (2007). PlasmaTreatment Time (s) Function He20Surface Activation NH 3 20 ( Post-He) Sealing  Subsequent NH 3 exposure seals the pores by adsorption reactions forming C-N and Si-N bonds.  Experimental results from the literature were used to build the sealing mechanism. University of Michigan Institute for Plasma Science & Engr.

MODELING : LOW-k PORE SEALING  Hybrid Plasma Equipment Model (HPEM)  Plasma Chemistry Monte Carlo Module (PCMCM)  Monte Carlo Feature Profile Model (MCFPM) JULINE_ICOPS09_05 Energy and angular distributions for ions and neutrals He PLASMA Porous Low-k Coils Wafer Substrate Metal Plasma Ar/NH 3 PLASMAS University of Michigan Institute for Plasma Science & Engr.

HYBRID PLASMA EQUIPMENT MODEL (HPEM) JULINE_ICOP09_06 EMM Maxwell equations are solved EΦ,BEΦ,B EETM Electron energy equations are solved STeμSTeμ FKM Continuity, momentum, energy equations; and Poisson’s equation are solved NESNES PCMCM S Energy and angular distributions for ions and neutrals; includes photon species  EEM (Electromagnetics Module)  EETM (Electron Transport Module)  FKM (Fluid Kinetics Module)  SCM (Surface Chemistry Module) SCM Calculates energy dependent surface reaction probabilities E  PCMCM (Plasma Chemistry Monte Carlo Module) University of Michigan Institute for Plasma Science & Engr. MCRTM Addresses resonance radiation transport  MCRTM (Monte Carlo Radiation Transport Module)

MONTE CARLO FEATURE PROFILE MODEL (MCFPM)  The MCFPM resolves the surface topology on a 2D Cartesian mesh to predict etch profiles.  Each cell in the mesh has a material identity. (Cells are 4 x 4  ).  Gas phase species are represented by Monte Carlo pseuodoparticles.  Pseuodoparticles are launched towards the wafer with energies and angles sampled from the distributions obtained from the PCMCM.  Cells identities changed, removed, added for reactions, etching deposition. JULINE_ICOPS09_07 PCMCM Energy and angular distributions for ions and neutrals HPEM MCFPM Provides etch rate And predicts etch profile University of Michigan Institute for Plasma Science & Engr.

 80 nm wide and 30 nm thick porous SiO 2  CH 3 groups line the pores  Average pore radius: nm  Pores open to surface need to be sealed  Will be exposed to successive He and NH 3 plasmas. INITIAL LOW-k PROFILE FOR SIMULATION JULINE_ICOPS09_08 University of Michigan Institute for Plasma Science & Engr.

SURFACE ACTIVATION IN He PLASMA  He + and photons break Si-O bonds and removes H from CH 3 groups.  Bond Breaking He + (g) + SiO 2 (s)  SiO(s) + O(s) + He(g) He + (g) + SiO(s)  Si(s) + O(s) + He(g) hν + SiO 2 (s)  SiO(s) + O(s) hν + SiO(s)  Si(s) + O(s)  Activation He + (g) + CH n (s)  CH n-1 (s) + H(g) + He(g) hν + CH n-1 (s)  CH n-2 (s) + H(g) He + (g) + CH n (s)  CH n-1 (s) + H(g) + He(g) hν + CH n-1 (s)  CH n-2 (s) + H(g)  Reactive sites assist sealing in the subsequent Ar/NH 3 treatment. JULINE_ICOPS09_09 University of Michigan Institute for Plasma Science & Engr.

SEALING MECHANISM IN Ar/NH 3 PLASMA  N/NH x species are adsorbed by activated sites forming Si-N and C- N bonds to seal pores.  Further Bond Breaking M + (g) + SiO 2 (s)  SiO(s) + O(s) + M(g) M + (g) + SiO(s)  Si(s) + O(s) + M(g)  N/NH x Adsorption NH x (g) + SiO n (s)  SiO n NH x (s) NH x (g) + Si(s)  SiNH x (s) NH x (g) + CH n (s)  CH n NH x (s) NH x (g) + C(s)  CNH x (s)  SiNH x -NH y /CNH x -NH y compounds help seal the pores where end nitrogens are bonded to either Si or C atom by Si-C/Si-N bond NH y (g) + SiNH x (s)  SiNH x -NH y (s) NH y (g) + CNH x (s)  CNH x -NH y (s) JULINE_ICOPS09_10 University of Michigan Institute for Plasma Science & Engr.

He AND Ar/NH 3 PLASMAS  He + and photons in He plasma break Si-O bonds and activate CH n groups.  He Plasma Species: He He* He + hν e  Ar/NH 3 = 25/75 treatment seals the surface pores.  Ar/NH 3 Plasma Species: Ar Ar* Ar + e NH 3 NH 2 NH H N NH 3 + NH 2 + NH 4 + NH + JULINE_ICOPS09_11 University of Michigan Institute for Plasma Science & Engr.

He PLASMA PRE-TREATMENT  Ion density: 3.8 x cm -3.  Porous low-k was exposed for 30s to the plasma.  20V substrate bias assisted ablating H and Si-O bond breaking.  Conditions: He, 10 mTorr, 300 W ICP, 20V Bias JULINE_ICOPS09_12 University of Michigan Institute for Plasma Science & Engr.

Ar/NH 3 PLASMAS  Total ion density: 1.0x cm -3  Ion densities (cm -3 ): NH x NH x NH x NH x H x  Neutral densities (cm -3 ): NH x NH x NH 1.6 x N 2.4 x Ar 6.0 x JULINE_ICOPS09_13  Conditions: Ar/NH 3 = 25/75, 10 mTorr, 300 W ICP University of Michigan Institute for Plasma Science & Engr.

PORE-SEALING BY SUCCESSIVE He AND NH 3 /Ar TREATMENT  Surface pore sites are activated by 30s He plasma treatment.  Successive 20s NH 3 treatment seals the pores forming Si-N and Si-C bonds. Initial Surface Pores Site Activation Employing He Plasma Sealing Employing Ar/NH 3 Plasmas JULINE_ICOPS09_14 University of Michigan Institute for Plasma Science & Engr. Animation Slide-GIF

SEALING: POROSITY AND INTERCONNECTIVITY  Sealing efficiency is independent of porosity and interconnectivity, optimizing at 75-80%  With higher porosity, the number of open pores to the surface increases.  If pore radius remains the same, sealing efficiency is constant.  With higher porosity but a fixed pore radius, number of surface pores increases.  The fixed probabilities of C-N, Si-N and N-N bond formation result in a constant sealing efficiency. JULINE_ICOPS09_15 University of Michigan Institute for Plasma Science & Engr.

SEALING: TREATMENT TIME DEPENDENCE  Without He plasma treatment, Ar/NH 3 plasmas seal only 45% of pores.  NH x ions are unable to activate all the surface sites to complete the sealing.  Sealing efficiency increases with He treatment time for 30s, then saturates.  30s treatment breaks all surface Si-O bonds and activates all surface CH 3 groups.  Sealing efficiency of pores increases for 20s of Ar/NH 3 treatment, then saturates – all dangling bonds on the surface are passivated. JULINE_ICOPS09_16 University of Michigan Institute for Plasma Science & Engr.

SEALING: He TREATMENT TIME DEPENDENCE  He plasma is responsible for Si-O bond breaking and removing H from CH 3 groups to create reactive sites.  Increasing He plasma treatment time increases sealing efficiency until all of the surface sites are activated. JULINE_ICOPS09_17 Ar/NH 3 Treatment Without He Pre-treatment Ar/NH 3 Treatment With He Pre-treatment University of Michigan Institute for Plasma Science & Engr. Animation Slide-GIF

SEALING: Ar/NH 3 TREATMENT TIME DEPENDENCE  NH x species are adsorbed by reactive sites produced by He plasma to form Si-C and Si-N bonds.  80% of surface pores are sealed within 20s…all surface activated sites are passivated by C-N/Si-N bonds. JULINE_ICOPS09_18 Pore Sealing by Ar/NH 3 Plasmas 0s 2s 5s 10s University of Michigan Institute for Plasma Science & Engr. Animation Slide-GIF

SEALING EFFICIENCY: PORE RADIUS  Sealing efficiency decreases with increasing pore size.  Sealing efficiency drops below 70% as for pore radius > 1.0 nm.  C-N and Si-N are “first bonds.”  Sealing requires N- N bonding, which has limited extent.  Too large a gap prevents sealing. JULINE_ICOPS09_19 14A Pore 10A Pore 8A Pore University of Michigan Institute for Plasma Science & Engr. Animation Slide-GIF

CONCLUDING REMARKS  Simulation of porous low-k material sealing was investigated employing successive He and NH 3 plasma treatment.  Si-N and C-N bonds formed by adsorption on active sites followed by one N-N bond linking C or Si atoms from opposite pore walls.  Pore sealing efficiency is independent of porosity and interconnectivity, while dependent on both He and NH 3 plasma treatment time.  The sealing efficiency degrades when the pore radius is greater than 1 nm.  Sealing efficiency will improve if the pore radius standard deviation can be maintained low. JULINE_ICOPS09_20 University of Michigan Institute for Plasma Science & Engr.