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Introduction of MAPS (Mecaro’s Advanced Precursors System)

2018. 11. 28. Mecaro Corporation

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Confidential What is MAPS ?

MAPS ≡ Mecaro’s Advanced Precursors System (Also it implies that we can find desired material quickly in a map of semiconductor materials)

Design Concept • Heteroleptic ligand system : shows good step coverage (S/C) • Higher thermal stability : Wider ALD windows

Metallic Center : TARGET

Ligand : VARIABLE - Enabling metal supply - Enabling metal vaporization - Enabling ALD reaction

M

Confidential Used Precursors @ Semiconductor Industry

Increasing structures complexity of DRAM, 3D-NAND Need higher (> 100:1) aspect ratio The importance of ALD precursors is increased

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BEOL

ALD processes are increased drastically with miniaturization : more than 30% increased at 7 nm compared to 10 nm

Used Precursors @ Logic device

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Group 4 Group 5 Group 6 Group 8

High-k materials

AZM, MAP-Hf01, MAP-Hf02

(ZrO2, HfO2)

Diffusion barrier

MAP-Ti01 (Ti/TiN)

MAP-Nb01 (NbN, Nb2O5)

MAP-Ta01 (Ta/TaN)

MAP-W01 (WN)

MAP-W02 (WN)

Electrode Materials

(Capping or Liner)

MAP-Ti01 (Ti/TiN)

Under development

FFW*

MAP-Co1 (Co)

Spacer or Etc.

MAP-Ti02 (thermal TiO2)

Developed MAPS

High-k : AZM, next Zr, Hf, La source (MAP-Hf01, MAP-Hf02) Diffusion barrier : MAP-Ti01, MAP-Nb01, MAP-Ta01, MAP-W01, MAP-W02 Electrode materials : MAP-Ti01, MAP-Co01 Spacer or etc. : MAP-Ti02

Confidential What is AZM?

High-k materials for ZrO2 : good ALD precursor - Higher thermal stability (vs. CpZr) : TGA/DSC data analysis - Very good uniform coating : non-uniformity ≤ 2% - Wider stable ALD windows (vs. CpZr) : 340 360 ℃

CpZr AZM

Structure

FW (g/mol) 288.54 300.56

Boiling point (℃/torr) 86/0.1 90/0.1

Vapor pressure (torr/℃) 1.5/100 1.35/100

Phase (R.T) Light yellow liquid Light yellow liquid

Density (g/mL) 1.17 (@24℃) 1.26 (@15℃)

Viscosity (cPs) 9 (@23℃) 15 (@23℃)

TGA (T1/2, ℃) 179 200

TGA (residue, %) 3.0 5.4

DSC (Tdec., ℃) 245 265

Confidential AZM Patent

Korea patent : KR 10-1263454, KR 10-1395644 US patent : US 8,946,096 Worldwide : PCT WO2012/124913 Japan: 5957017 (2016.6.24)

Confidential Next high k Materials : MAP-Hf01, Hf02

New high-k candidate : ZrO2, HfO2, La2O3, (SrTiO3, BST : long term) etc.

- ZrO2 : New organic ligand design

- HfO2 : Wider ALD window (275~375℃) expected

- La2O3 : Under development of Liquid precursor

AZM CpHf(NMe2)3 MAP-Hf01 MAP-Hf02

Structure Confidential Confidential

FW (g/mol) 300.56 375.82 Confidential Confidential

Boiling point (℃/torr)

90/0.1 70 / 0.06 94 / 0.04 78 / 0.06

Phase (R.T) Light yellow

liquid Light yellow

liquid yellow liquid Light yellow liquid

Density (g/mL) 1.26 1.43 1.41 1.49

Viscosity (cPs) 15 (@23℃) 15.5 (@22℃) 27.1 (@22℃) 25.5 (@22℃)

TGA (T1/2, ℃) 195 189 217 195

TGA (residue, %) 3.0 3.4 3.2 0.4

DSC (Tdec., ℃) 265 210 239 219

Confidential Diffusion barrier (V) : MAP-Nb01, MAP-Ta01

MAP-Nb01 MAP-Ta01

Structure confidential confidential

F.W. (g/mol) confidential confidential

Boiling Temp. (℃) 102℃/0.03torr 110℃/0.05torr

Phase (r.t.) Yellow liquid Light yellow liquid

Purity (by NMR) 99.5% 99.7%

Viscosity (cPs) 58.27 (@23℃) -

TGA (T=1/2) (℃) 231 242

TGA (residue, %) 1.39 1.04

DSC (Tdec., ℃) 256 271

Application : NbN, TaN barrier materials for Cu line Phase (shape) : MAP-Nb01 = yellow liquid, MAP-Ta01 = light yellow liquid Expectation : Good ALD precursor for NbN, TaN Current status :

• MAP-Nb01 : Under Cu barrier test • MAP-Ta01 : Under scale-up & deposition test

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Application : WN barrier materials for Cu line Phase (shape) : MAP-W01 = yellow liquid, MAP-W02 = red liquid Expectation : Good ALD precursor for W or WN Current status :

• MAP-W01 : Resistivity ~810-4 ·㎝ for WNx, impurity ~ 10 atomic% C

GPC = 0.7~1.0 Å /cycle

• MAP-W02 : Under deposition test

MAP-W01 MAP-W02

Structure confidential confidential

FW (g/mol) confidential confidential

Boiling point (℃/torr) 120/0.1 90/0.1

Vapor pressure (torr/℃) 0.02/45 -

Phase (R.T) Yellow liquid Red liquid

Density (g/mL) - -

Viscosity (cPs) 77(@23℃) 15(@23℃)

TGA (T1/2, ℃) 235 207

TGA (residue, %) 2.2 2.9

DSC (Tdec., ℃) 238 250

Diffusion barrier (VI) : MAP-W01, MAP-W02

Confidential Electrode material : MAP-Ti01, MAP-Co01

Application : TiN, Co etc. electrode (substitution W plug) or barrier materials Expectation : Good ALD precursor for Ti/TiN, Co metal Current status :

• MAP-Ti01 : possible mass production • MAP-Co01 : Under deposition test

MAP-Ti01 MAP-Co01

Structure confidential confidential

FW (g/mol) confidential confidential

Boiling point (℃/torr) 70/0.06 85/0.04

Vapor pressure (torr/℃) 1.20/70 -

Phase (R.T) Reddish liquid Red brown liquid

Density (g/mL) 1.14 g/cm³ -

Viscosity (cPs) 15.63 (@23℃) 5.40 (@23℃)

TGA (T1/2, ℃) 219 202

TGA (residue, %) 3.54 7.8

DSC (Tdec., ℃) 245 198

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Thank you for your attention!