DONGJIN SEMICHEM Co., Ltd

Jae-Woo LEE, Jungyoul LEE, Sooyoung HAN, Hyungkeun LEE, Jaehyun KIM

Directed Self-Assembly Process

and Materials Development

1 IntroductionIntroduction

2 DSA Process, DSA Process, graphographo and and chemoepitaxychemoepitaxy

3 DSA Materials, BCP, NL and guide PR DSA Materials, BCP, NL and guide PR

Contents

5 SummarySummary

4 DongjinDongjin DSADSA

Introduction

� DSA tech. is a contact point of top-down and bottom-up tech.

� Low-cost process without additional financial input for infra.

What’s Directed Self Assembly ?

Photoresist

guide patterning

Self-assembly of BCP

moleculesDSA patterning

www.themegallery.com

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HP 20nm

Introduction

Self-assembly of BCP molecules

� Chemically incompatible polymeric blocks

� Limited phase separation.

���� Formation of nanostructures.

� Shape and size of nanodomains.

���� Relative volume fraction, molecular

weight.

Phase diagram of Block Copolymer

Guide-Patterning Method

Graphoepitaxy method

Bare

ARC or HM

Neutral layer

Photoresist

Resist imaging

PEB / Dev

Resist hardening

coating / annealing

Low power /O2-RIE

Bare

ARC or HM

Neutral layer

Bare

ARC or HM

Neutral layer

Bare

ARC or HM

Neutral layer

Bare

ARC or HM

Neutral layer

193nm Dry 193nm Exposure

Graphoepitaxy

- guide-patterning by topological geometry

- photoresist-pattern topology act as guide-pattern.

- efficient guiding property.

- DSA pattern loss in guide-pattern.

To align BCP nanostructures to target point, adequate guiding should be applied.

Guide-Patterning Method

Chemoepitaxy method (Lift-off process)

Resist imaging Resist hardening Low power /O2-RIE

TMAH development

Bare

ARC or HM

Photoresist

PEB / Dev coating / annealing

Bare

ARC or HM

Bare

ARC or HM

Bare

ARC or HM

Bare

ARC or HM

Bare

ARC or HM

Bare

ARC or HM

NL Coating193nm Dry

Chemoepitaxy

- guiding by surface property change.

- high patterning density, patterning also in guide-pattern area

- conformal coating of NL

DSA Material development target Dongjin materials

Guide-PRDry/wet ArF, EUVL

-. High chemical and thermal resistance-. High resolving power-. Wide process margin and low LER

DPG- 001 (L/ S)DPG- 003 (C/ H)

NL

-. To control interactions with both domains of BCP.-. High chemical and thermal resistance-. Short bake time. (60~180s)-. Conformal coating without rinse process

FTN- 002 (chemoepitaxy)FTN- 006 (graphoepitaxy)

BCP

-. PS-b-PMMA, cylinder and lamella type

-. Controlled polymerization, low pdi <1.1

-. Impurity control

DBP - L003DBP - L007DBP – C004

DSA Materials

Dongjin Semichem materials for DSA process

NL development

Normal brush-type NL process

NL Coating

Solvent rinse BCP coating

Bare

Bake BCP annealingBake /solvent remove

BareBareBare Bare Bare

NL Coating

Solvent rinse BCP coating

Bare

Bake BCP annealingBake /solvent remove

BareBareBare Bare Bare

Dongjin NL materials, x-linking type

Simplified process.

Action of NL

Determination of BCP molecules orientation

on NL surfaceDomain A Domain B

BCP molecules are composed of two different domains.

sub

NL

sub

NL

Vertical orientation of BCP molecules

���� layered structure

Parallel orientation of BCP molecules

���� vertical lamella structure

-. One-side interaction -. Equal interaction

NL Materials Property

Surface property of NL is one of the key factors to determine self-

assembly of BCP molecules.

TFN-001 TFN-002 TFN-003

TFN-004 TFN-005 TFN-006

Neutral layer Type Type A Type B

Neutral layer TFN-001 TFN-002 TFN-003 TFN-004 TFN-005 TFN-006

Contact angle (°) 72.1 77.8 81.9 75.5 80.2 83.2

Application Lift-off Process Graphoepitaxy

� Surface property (CA) : 77.8 ~ 83.2°°°°

△△△△ △△△△○○○○

○○○○△△△△XXXX

Graphoepitaxial L/S Patterning

Graphoepitaxy L/S patterning process

Bare

ARC or HM

FTN-006

Photoresist

Resist imaging

PEB / Dev

Resist hardening

coating / annealing

Low power /O2-RIE

Bare

ARC or HM

FTN-006

Bare

ARC or HM

FTN-006

Bare

ARC or HM

FTN-006

Bare

ARC or HM

FTN-006

193nm Dry 193nm Exposure

3.0 Lo3.0 Lo3.0 Lo3.0 Lo

After Resist hardening After BCP annealing

Lo = 39.2nmL / S = 73nm / 105nm� Guide resist :

DPG-001 / FT 100nm

� Neutral layer :

FTN-006 / FT 8nm

� BCP material :

DBP-L003 / FT 45nm

After O2 RIE etching Pattern CD : 22.1nmBCP FT = 45nm

After Resist hardeningPattern CD : 91.7nmResist FT = 100nm

CDU (L/S)

3σσσσ = 3.19nm

CDU (L/S)

3σσσσ = 6.86nm

DSA pattern CD uniformity

Graphoepitaxial L/S Patterning

Resist imaging Resist hardening Low power /O2-RIE

TMAH development

Bare

ARC or HM

Photoresist

PEB / Dev coating / annealing

Bare

ARC or HM

Bare

ARC or HM

Bare

ARC or HM

Bare

ARC or HM

Bare

ARC or HM

Bare

ARC or HM

NL Coating193nm Dry

Chemoepitaxial Patterning: Lift-off

Chemoepitaxy L/S patterning process

� Guide resist :

DPG-001 /FT 100nm

� Neutral layer :

FTN-002 / FT 8nm

� BCP material :

DBP-L007 / FT 40nm

L / S = 128.4 / 46.6L / S = 84.3nm/90.7nm

After Resist hardening

After annealingAfter Lift-off

Lo = 31.3nm

1um

Cell Center Cell edge

Left

Bulk Cell edge

Right

Bulk

� Chemoepitaxy L/S pattern image.

� efficient Pattern-guiding in Cell area by lift-off space

� Self-assembly control in Bulk region is under developing.

Chemoepitaxy L/S process

Chemoepitaxial Patterning: Lift-off

Bare

ARC or HM

Chemoepitaxial Patterning: Lift-off

After Lift-off

After BCP

annealing

Lo = 31.3nm 2.23 Lo 2.00 Lo 1.69 Lo 1.49 Lo 1.26 Lo 1.09 Lo

� Lift-off space CD shows great effect on DSA efficiency.

� The most effective point is 1.5Lo and DSA patterning margin has

appeared in 1.26Lo~1.69Lo.

� ���� Guide-patterning process margin : ≥≥≥≥ ±±±± 12.6%

Lift-off space CD vs Lo

Space CD (nm) 69.7 62.5 53.0 46.6 39.3 34.1

Contact hole pattern shrink

Bare

ARC or HM

FTN-006

Photoresist

Resist imaging Resist hardening

coating / annealing

Acetic acid Wet etching

PEB / Dev

Bare

ARC or HM

FTN-006

Bare

ARC or HM

FTN-006

193nm Dry

Bare

ARC or HM

FTN-006

193nm Exposure

Bare

ARC or HM

FTN-006

After Resist hardening After wet etching

� Guide resist :

DPG-003 /FT 100nm

� Neutral layer :

FTN-006 /FT 8nm

� BCP material :

DBP-C004 /FT 30nm

30.6nm90.8nm

Graphoepitaxial C/H Shrinkage

CDU (C/H)

3σ = 3.66nmCDU (C/H)

3σ = 7.68nm

DSA pattern CD uniformity

Graphoepitaxial C/H Shrinkage

After Wet etchingPattern CD : 30.4nmBCP FT = 30nm

After Resist hardeningPattern CD : 90.8nmResist FT = 100nm

Summary

We have discussed grapho- and chemoepitaxial DSA processes

and neutral layer materials...

<Graphoepitaxy>

���� Photoresist-pattern topology act as guide-pattern.

���� efficient guiding property, 22nm L/S DSA, 6.86nm CDU

���� hole-shrink application, 90nm to 30nm C/H

<Lift-off>

���� simple process

���� space roughness control

���� space CD closely correlated with the size of BCP, 1.5Lo guiding space CD

was the best.

<Neutral Layer>

���� NL materials are one of the key ones in DSA

���� Surface polarity control

���� Multifunctional NL for efficient DSA process are under control.

Acknowledgments

This works are supported by Korea Government R&D Program,

Material Break-through Technology Development Project

directed by Ministry of Knowledge Economy.