Processing and Characterization of PMSSQ Based Materials for Nanoporous Low-K Dielectrics

P. Lazzeri1, L. Vanzetti1, M. Bersani1, M. Anderle1, J.J. Park2, Z. Lin2,, R.M. Briber2, G.W. Rubloff2, R.D. Miller3
1 ITC-irst, v. Sommarive 18, 38050 Povo, Trento, Italy 2 University of Maryland, 2145 A.V. Williams Building College Park, MD 3 IBM Almaden Research Center, San Jose, CA

Device Shrinkage and Interconnect Delay

Increased line resistance and capacitive coupling Interconnect delay dominates overall circuit delay

Low K materials

Al / SiO2
SiO2 (K = 4.0) Al ( 3.0 cm)

Cu / Low K
Low k (k ~ 2.0) Cu ( - 1.7 cm)

(organic, silica based materials)

Nano porous low K materials

Nanoporous PMSSQ

2003/11/03

Low polarizability matrix (K ~ 2.7) Nano porous low K (K 2.0) Low water uptake (<1%), thermal stability, mechanical strength. AVS 2003 - MS - MoM3

Strategy for Nanoporous Low K

Matrix Porogen Spin on (Solution)

RT

Characterizing surface and bulk

Matrix cross link, Nano phase separation

- ToF SIMS - XPS

Characterizing volatile product

- TDMS (Thermal Desorption Mass Spectrometry)

Thermal Cycle
Porogen Volatilization

Compare surface to gas phase Compare precursor recipe

- Low SiOH and high SiOH PMSSQ
Fully cured Cross link Nanopores

450 C
2003/11/03

AVS 2003 - MS - MoM3

Thermal Reaction Goal

Matrix cross link

Porogen release

RT
2003/11/03 AVS 2003 - MS - MoM3

T, t

Max 450C

Nanoporous PMSSQ Materials

Matrix material Porogen materials

Backbone

SiO1.5CH3

PMMA DMAEMA unit: contains N

PMSSQ

Methyl group Hydroxyl group

Non-polar, hydrophobic and space-occupying Cross linking of matrix Hydrogen bonding with OH in Matrix Miscibility between matrix and porogen

PMMA-co-DMAEMA
2003/11/03

Tertiary amino group

AVS 2003 - MS - MoM3

Low K film Processing

low-k matrix resin (PMSSQ) porogen (PMMA co-DMAEMA) solvents

450C, 2Hrs Rpm = 3000 Time = 20 sec Thickness ~ 1 m

initial cure template formation final cure

ToF SIMS
Static-SIMS (Ga+ @ 11-25 keV) Surface Spectroscopy, Surface Imaging

Matrix cross linking Heat

Pseudo-Dynamic SIMS (sputtering by Cs+) Depth Profiling

XPS TDMS

Material Degree of polymerization Thermal behavior of porogen material Interaction between matrix and porogen Matrix precursor chemistry effect

Thermal decomposition of fingerprint and molecular structure porogen material

Designing nanoporous lowK materials for electrical performance

2003/11/03 AVS 2003 - MS - MoM3

PMSSQ Finger Print Analysis

O
5 x10 O Si

O
CH3

SSIMS, negative SI
O

Si

Si CH3

O
O Si O O
x600

Si

CH3 O Si O

CH3 Si O O Si CH3 O O

CH3 Si O Si CH3 O O

CH3 Si O

8.0

O O
7.0 Si

Si CH3

Si CH3

Si CH3

Si CH3

O
O

CH3 Si O

CH3 Si O O

CH3 Si O

6.0

O
5.0 intensity

Si O

Si CH3

Si CH3

cleavage of the parent ion (i.e. by loss of SiO2)

3.0

4.0

n=0

n=1

n=2 n=1 n=2

2.0

1.0

200 400 600 Peak assignments are well matched to experimental results. mass Compression Peaks are Factor : 52 @ 50 C x 3 by a monomer unit. regularly spaced PMSSQ + curing Fragmentation pattern depends on chemical structure and is sensitive to cross linking.

0.0

2003/11/03

AVS 2003 - MS - MoM3

Precursor Chemistry
CH 3 O Si O C H3 Si O O Si O O CH 3 Si O O CH 3 Si O O CH 3 Si O C H3 Si O O CH 3 Si O O O CH 3 Si O

x10

SSIMS, negative SI

SSIMS, negative SI
Si O Si
x10 6 O

8.0

Low SiOH PMSSQ

x700

High SiOH PMSSQ

x700

Si

Si

Si

CH3
7.0 6.0

CH 3 n

CH 3

1.0

1.98 amu 3 CH OH
n

CH 3

0.8

5.0 intensity
intensity 0.6

4.0

Twin peaks
0.4

3.0

2.0
0.2

1.0

0.0 200 Compression Factor : 52 400 600 mass

0.0 200 Compression Factor : 52 400 600 mass

Mass spectrum of high SiOH PMSSQ has a twin peak near the key species with mass difference 1.98 amu by replacing CH3 group with OH group.

[SiOH]high ~ 2 * [SiOH]low
2003/11/03 AVS 2003 - MS - MoM3

Polymerization of High SiOH PMSSQ

1.2 1 0.8 Intensity 0.6 0.4 0.2 0 50 125 175 225 275 325 450 Temperatrure [C]

Cross linking reaction

ToF-SIMS
Major crosslinking 100C 200C
Si4O6C3H9 Si5O7C5H15 Si6O9C5H15 Si7O10C7H21 Si8O12C7H21 Si9O13C9H27

H2O desorption product

TDMS
1.50E-08 Intensity [amp] 1.10E-08 7.00E-09 3.00E-09 -1.00E-09 50 150 250 350 450 Temperature [C] MASS( 18 )

Mass spectrometer

Remaining crosslinking

Water signal from pure PMSSQ

Major crosslinking 100200C, completed at 450C. Dehydration occurs as OH groups crosslinks.

2003/11/03 AVS 2003 - MS - MoM3

High SiOH vs. Low SiOH

1.2

1.2
RELATIVE INTENSITY

Si5O8C5H15
1

1 0.8 0.6 0.4 0.2 0 50 125 175 225 275

Si4O7C3H9 Si4O7C3H9

Si6O10C5H15

Low SiOH

RELATIVE INTENSITY

Small size fragments

0.8

High SiOH
325 450

0.6

Low SiOH
RELATIVE INTENSITY

1.2

TEMPERATURE [C]

Si7O11C7H21
1

0.4

Si8O13C7H21

0.8

0.2

0.6

High SiOH
50 125 175 225 275 325 450

0.4

Low SiOH High SiOH

50 125 175 225 275 325 450

Large size fragments

0.2

TEMPERATURE [C]

TEMPERATURE [C]

High SiOH PMSSQ crosslinks faster than low SiOH PMSSQ. Reaction rate depends on the concentration and proximity of SiOH end groups. 2003/11/03 AVS 2003 - MS - MoM3

Porogen : Surface Analysis (XPS)

High SiOH

As deposited
Photoemission Intensity (a.u.)
0% Porogen 30% Porogen
Backbone (C-OH) DMAEMA (C-N)

Photoemission Intensity (a.u.)

Fully cured
0% Porogen 30% Porogen

C 1s

C 1s

292

290

288

286

284

282

280

292

290

288

286

284

282

280

Binding Energy (eV)

Binding Energy (eV)

Porogen related components : Backbone and DMAEMA Porogen materials completely volatilized at T = 450C
2003/11/03 AVS 2003 - MS - MoM3

Porogen : Surface Analysis

1.4

ToF SIMS

Porogen in High SiOH matrix

1.2

PMMA (CH3O)

RELATIVE INTENSITY

0.8

0.6

DMAEMA (CN)

0.4

0.2

0 50 125 175 225 275 325 450

TEMPERATURE [C]

2003/11/03

DMAEMA ligand : Cleavage and evolution 225C - 325C (90%) Remaining material desorbs by > 325 C PMMA ligand : No apparent transformation until > 325 C Backbone : Behavior follows that of PMMA ligand No porogen agglomeration observed in high SiOH matrix.
AVS 2003 - MS - MoM3

Porogen : Gas phase analysis

3.00E-08 2.50E-08 Intensity [amp] 2.00E-08 1.50E-08 1.00E-08 5.00E-09 0.00E+00 Temperature [C]
225C 325C
H3C

DMAEMA ligand
CH3 H3C CH

7.00E-09 6.00E-09 5.00E-09 Intensity [amp] 4.00E-09 3.00E-09 2.00E-09

PMMA and backbone

Backbone
MASS( 85)

MASS( 58 )

PMMA
MASS( 100 )

C O H2C

CH2 N CH3

1.00E-09 0.00E+00

Temperature [C]
225C 325C 350C 450C

Mass spectrometer detected fragment of DMAEMA (mass 58) and PMMA parent ion (mass 100). The decomposition temperature range for DMAEMA is 225C ~ 325C ,and PMMA 350C ~ 450C. Good agreement with ToF SIMS result. 2003/11/03 AVS 2003 - MS - MoM3

Thermal Behavior of Nanoporous PMSSQ

High -SiOH

Low SiOH

Porogen backbone

PMMA

Matrix cross link

DMAEMA

100
2003/11/03

200
AVS 2003 - MS - MoM3

300

450 T [C]

Conclusion
ToFSIMS, XPS, and TDMS were used to analyze the thermal behavior of porogen-containing PMSSQ Polymerization kinetics of PMSSQ Matrix
Polymerization of PMSSQ was observed mainly at 100C 200C, and water was detected as a byproduct by mass spectrometry Rate of polymerization depends on the concentration of OH functional groups: high SiOH PMSSQ shows faster polymerization

Porogen behavior upon thermal processing

Porogen materials decompose at higher temperatures than PMSSQ polymerization temperatures ( > 225C) DMAEMA and PMMA thermally decompose at different temperatures (225C 300C , PMMA and backbone > 325C)

2003/11/03

AVS 2003 - MS - MoM3

Particles Containing Porogen Materials (AVS 02 Denver)

imaging ToF-SIMS, negative SI

POROGEN AGGLOMERATES
agglomerate density depends on curing T

225 C < curing < 450 C

agglomerate composition (PMMA/DMAEMA ligand/backbone) depends on curing T

Field of view: 10.0 x 10.0 m2 2 m

Porogen particles are observed only in low SiOH PMSSQ film. Slow cross linking process of low SiOH PMSSQ allows diffusion of porogen material. Low concentration of OH with less hydrogen bonding with DMAEMA does not hinder phase separation. 2003/11/03 AVS 2003 - MS - MoM3