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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.

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Presentation on theme: "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."— Presentation transcript:

1 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 50011 jshoeb@eecs.umich.edu b) Department of Electrical Engineering and Computer Science University of Michigan Ann Arbor, Ann Arbor, MI 48109 mjkush@umich.edu http://uigelz.eecs.umich.edu ICOPS, June 2009 *Work supported by Semiconductor Research Corporation JULINE_ICOPS09_01

2  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.

3 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: http://www.necel.com/process/en/images/porous_low-k_e.gif University of Michigan Institute for Plasma Science & Engr.

4 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.

5 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.

6 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)

7 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.

8  80 nm wide and 30 nm thick porous SiO 2  CH 3 groups line the pores  Average pore radius: 0.8-1.4 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.

9 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.

10 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.

11 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.

12 He PLASMA PRE-TREATMENT  Ion density: 3.8 x 10 10 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.

13 Ar/NH 3 PLASMAS  Total ion density: 1.0x 10 11 cm -3  Ion densities (cm -3 ): NH 3 + 2.6 x 10 10 NH 4 + 2.9 x 10 10 NH 2 + 1.0 x 10 10 NH + 1.4 x 10 09 H + 1.6 x 10 10  Neutral densities (cm -3 ): NH 3 5.30 x 10 13 NH 2 2.40 x 10 13 NH 1.6 x 10 12 N 2.4 x 10 12 Ar 6.0 x 10 12 JULINE_ICOPS09_13  Conditions: Ar/NH 3 = 25/75, 10 mTorr, 300 W ICP University of Michigan Institute for Plasma Science & Engr.

14 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

15 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.

16 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.

17 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

18 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

19 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

20 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.

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