basf soft particles for metal cmp - cmp...

Vijay Raman and Claus Poppe, BASF SE, Semicon West 2010 1

BASF Soft Particlesfor Metal CMP

Vijay Raman1

Claus Poppe2

Bastian Noller3

Michael Lauter2

Yuzhuo Li2

BASF SE, Ludwigshafen, Germany

1 Global Polymer Research – Polymer Colloids2 Global Business Unit Electronic Materials3 Competence Center Formulation Technologies

BASF SE, Ludwigshafen, Germany

2Vijay Raman and Claus Poppe, BASF SE, Semicon West 2010

BASF – The Chemical CompanyThe world's leading chemical company

Chemistry is about every aspect of life.

We are connected to deliverintelligent and sustainable solutions.

Sales 2009: €50,693 mill.

EBIT 2009: €3,677 mill.

Employees (December 31, 2009):104,779

About 1,300 new patents filed

6 Verbund sites and about 380production sites


Electronic Materials by BASFWorldwide Presence

MalaysiaService Center

SingaporeProduction,Sales & Marketing

KoreaSales& Marketing

ChinaProduction,Service Center

JapanSales& Marketing

TaiwanProduction,Development,Sales & Marketing

GermanyGlobal Headquarters,R&D, Production,Sales & Marketing

North AmericaProductionand Sales& Marketing

Hong KongRegionalHeadquarters


State-of-the-art R&Dand application facilities in Europe and Asia

Presently approx. 100 employees dedicatedto the development activitiesin Electronic Materials

Part of approx. 9,300 employeesin BASF’s R&D and technology network

Collaboration: commercial,academic partners and tool manufacturers

Some of our R&D projects:

Advanced cleaning formulations

Copper electroplating

New CMP slurries

Electronic Materials by BASFR&D to meet customer needs


Overview of BASF CMP Activities

CMP Slurries

• Cu CMP for 3D TSV

• Front and back side

• Cu CMP for Interconnect

• Barrier CMP for Interconnect

• Interlayer dielectric (ILD)

• Shallow trench isolation (STI)

•Nitride and poly Si stopping

• High K metal Gate

•Poly Si opening


BASF’s intelligent chemistry for CMP:Functional and Adaptive Particles for DynamicConditions

Morphology(form / shape)

ComplexSimple

No

ne

Hig

h

Fu

ncti

on

ality

Co

mb

ine

d

A

changingconditions

AA

AA

AA A A

BB

BB

BB B B

B

Functionality on demand

Enhance CMP performance viaSoft Abrasive DesignFunctionalityComplex Morphology andTrigger response ability

Morphology on demand


Silica Particle Functional Polymer Particle BASF Adaptive Organic Particle

Wafer

Stress-free

Stress-free

Stress-free

Compressed duringCMP



Pad

NoDeformation

DeformationDissociationWafer

Pad

Wafer

Pad

©KT 2008

New Soft Abrasives for CMP

Elasticcore


Concept: Soft Functional PolymerParticles in CMP

Deformation

During CMP

Soft Particle Soft Functional Particle

Improved mechanics

Improved chemical/mechanicalbalance in CMP

Immobilizedcomplexing groups

Solublecomplexing agent

•Passivation•Improved tribology•Reduced corrosion events

Mainly etching

Immobilizedcomplexing groups

Solublecomplexing agent

•Passivation•Improved tribology•Reduced corrosion events

Mainly etching


Designing Polymer Particles via EmulsionPolymerization

Current applications: Adhesives, Paints, Paper and Construction

BASF capacity: > 1 million tons per year

New market opportunity CMP

10-500 nm

R•

dif

fusio

n

initiatorradicalwatersoluble

micelleswollen with monomer

monomer dropletstabilized with emulsifier

dispersion particlesstabilized with emulsifier

1-10 µm 10-500 nm

R•R•

dif

fusio

n

initiatorradicalwatersoluble

micelleswollen with monomer

monomer dropletstabilized with emulsifier

dispersion particlesstabilized with emulsifier

1-10 µm


BASF Polymerization Technologies:Versatile Functionalities and Morphologies

new functionalized polymer particles with different morphologies

Non-Functional Particles Functional Particles Core-Shell


Overview: Functional Polymer

Particles for CMP

shell:

functional (R)

— R

— R

Portfolio / Properties

particle size: 10nm to 500nm

Tg: -30°C to 180°C

crosslinking: up to 30%

functionality (R): cationic, anionic and

non-ionic

solids: up to 60%

surfactant: low as 0,5 %

stability: thermal stability >350°C

coagulum: < 10 ppm possible

very low VOC < 10 ppm

— R

core:

highly cross-linked


Proof of Concept: Soft FunctionalPolymer Particles in CMP

Lower chemical etching (SER)

Increased mechanical contribution (MRR)

Improved Chemical/Mechanical balance

MR

R/H

ot

SE

R(A

.U)

-30%

+ 200%


Tunable CMP Performance via SurfaceFunctionality

CMP performance can be tuned via surface functionality

Functional particle significantly improves the chemical-mechanical balance

Performance significantly better than non-functionalized silica

Tunable CMPperformance

MR

R/H

ot

SE

R(A

.U)

-30%

500%


CMP Fundamental Investigations:Interfacial Phenomena

Polymer Particle +Surface Interactions

Polymer Particle +Slurry Component

Interactions

-Mechanics (AFM – HigherHarmonics)

-Surface Adsorption (AFM, QCM)

-(In-situ) IR, XPS

-Optical observations

-NMR

-UV-vis, light scattering

To develop a complete understanding of CMPinteractions and mechanisms

Polymer Particle- Surface- Slurry Component Interactions

+

•Oxidizer

•Complexing Agents


paraparai

ii

cTT

,

0,

11

Relaxivity, depends on paramagneticspecies, solvent, magnetic field

Interactions of Functional PolymerParticles with Slurry Components

5mM Cu(NO3)2

Reference

Relaxivity of water protons in presence of paramagnetic species

NMR T2 measurements


Functionalized Particles a VersatileComponent: Offers a Range ofInteractions in Slurry

0

0,001

0,002

0,003

0,004

0,005

0,006

0,007

0,008

GK19

09/1

17

GK19

09/1

18

Gk2

020/

110

Gk2

020/

112

GK20

19-4

3

1/T

2[1

/ms

]

Water 5 mM Cu2+ 5 mM Cu2+

10 mM glycine5 mM Cu2+

10 mM 1,2,4-triazole

5 mM Cu2+

1% functionalizedabrasive particles

Cu2+-glycine1:2-complex

Cu2+-triazole1:2-complex


Higher Harmonic AFM: New Insights Into

Mechanical Property of Nanoparticles Adsorbed

on Surfaces

Higher Harmonics: Coupling the normal force onthe tip into a torsional motion of the cantilever

tapping

torsional deflection

O. Sahin et al., Nature Nanotechnology (2007) 2: 507 - 514AFM & Nanomechanics Lab – Dr. Sugiharto (GKP/O)

Normal AFM Cantilever

2020 µµmm

Mechanics possible only on flat surfaces/ particles immobilized on tips

Mechanics on individual particles adsorbed onsurfaces – CMP conditions


Higher Harmonic AFM: Mechanics at

CMP conditions21.6 GPa

0.0 GPa

23.7 GPa

0.0 GPa

Mean elastic modulus:4.3 (±0.4) GPa; n=4

Mean elastic modulus:3.5 (±0.3) GPa; n=4

Mica (10 GPa)

* E-modulus: 2.4-4 GPa

Functionalized Particles

Non-Functionalized Particles

Hydroplasticizedlayer


Composite Abrasive

Elasticcore

Elasticcore

Elasticcore

Elasticcore


Conventional High Purity Colloidal Silica (HPCS)vs.

BASF High Purity Composite Abrasive (HPCA)

Conventional Synthesis via TEOS or ionexchange

High cost due to limited number of suppliers

High purity

30-100 nm available

Relatively hard

Non-compressible

Well controlled polymerization process:BASF IP

Cost effective: HVM for other applications

High purity possible

30 – 100 nm available

Hardness and morphology tunable

Compressible => low defect?

Typical Colloidal Silica BASF Composite Abrasive


Conventional High Purity Colloidal Silicavs. BASF Composite Abrasive

0

20

40

60

80

100

120

Target Particle 1 Particle 2 Particle 3

Slurry type

Defe

cts

(Arb

ita

ryU

nit

s)

HPCS BASF CompositeAbrasive

Target

Excellent Defectivity Levels Achieved on Metal Layers


Conclusions

BASF Soft Abrasive Design to Improve CMP performance

Functional Polymer Particles – a new component for Cu CMP slurry design

with improved chemical-mechanical balance

tunable CMP performance – via surface functionality

Composite abrasive

Industrially feasible composite structures

Excellent defectivity with balanced removal rate

Fundamental Mechanistic Understanding

AFM higher harmonics – to understand mechanics of particles under CMPconditions

Particle-slurry component interactions – functional abrasives offer a range ofversatile interactions for slurry design (NMR)


Acknowledgments

BASF SE (CAE, Germany)

Mr. Roland Lange

Mrs. Elisabeth Selzer

Mr. Kenneth Rushing

BASF (CAE, Asia)

Mr. Daniel Shen

Mr. William Chiu

STLN, Clarkson University

Mr. Yongqing Lan

Dr. Changxue Wang

BASF SE (Polymer Research, Germany)

Dr. Jörg Nieberle

Dr. Maxim Peretolchin

Dr. Monika Haberecht

Dr. Hans-Joachim Haehnle

Dr. Markus Brym

Dr. Alexsandro Berger

Dr. Bas Lohmeijer

Dr. Nikkolaus Nestle

Dr. Brands, Dr. Gubaydullin and Dr. Zacharias

Mr. Sciandrone, Mr. Hyunh, Mrs. Dammert, Mrs. Merz, Mr.Dyga

Mrs. Diana Franz and Mrs. Bettina Drescher

basf soft particles for metal cmp - cmp...

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