Ellipsometry Porosimetry for Ultra Low K Material - Nanolab · Ellipsometry Porosimetry for Ultra...

1

Ellipsometry Porosimetry for Ultra Low K Material

Dr Dorian ZAHORSKI

SOPRA

www.sopra-sa.com

UCLA July 2006

2

Excellent dielectric properties of SiO2 have been the cornerstone for microelectronic revolution during the past 30 years.

⎟⎟

⎠

⎞

⎜⎜

⎝

⎛+= 2

22242 T

LPL

okRC ερ

Better Interconnects require:

1. Metals with low resistivity (Cu)2. Dielectrics with low dielectric

constant (low-k)

Technology challenge: reduce RC delay

ρ - metal resistivityk - relative dielectric constantL - line lengthP - metal pitchT - metal/dielectric thickness

ULK characterization with EP

Introduction of porous low K materials

3

ULK characterization with EP

Adrien Darragon - Product Manager, SOPRA – [email protected]

•EP is a unique technology to characterize CVD and spin coated porous ultra low K.

•EP measures the change of the optical propertiesand thickness of the materials during adsorption and desorbtion of an organic solvent.

•The analysis gives:•porosity of the Low K•pore size distribution•Average pore size•For both microporous and mesoporous, cumulative surface area, pore interconnectivity, Young modulus, thickness and refractive index.

•EP qualifies the sealing layer of both patterned and blanket wafers.

+ solvant

Porous material

4

Outline

1. Principle and measurement setup2. Porosity and Pore size measurements

• Mesoporous • Microporous

3. Young modulus4. Pore killers and sealing

• Blanket wafers• Patterned wafers• Interconnectivity

5

Porosity measurement

From the thickness and refractive index measurements on the basis of Lorentz-Lorenz equation:

From adsorption/desorption isotherms : Porositypore interconnectivity

no need to know the dense skeleton material properties

6

ELLIPSOMETRY is a method based on measurement of the change of the polarisation state of light after reflection at non normal incidence on the surface to study.

Substrate (ns, ks)

Thin Film 1 (n1, k1, T1)Thin Film 2 (n2, k2, T2)

Ambient (n0, k0)

foES

EiEP

rs

rp

Er

linear polarisation

Ein

EpEs

Eout=r EinEp rpEs rs

elliptical polarisation

Eout=r Ein = (TanY eiDelta) Ein Ellipsometry measures TanY and Cos D

Principle of Spectroscopic Ellipsometry

7

Experimental Measurement=

Model Simulation?

No, proposition for new parameters

Yes

Cos D

TanY

Experimental Measurement Physical ModelWith an estimated sample structure

- Film Stack and structure- Material n, k, dispersion- Composition Fraction of Mixture

Cos D

TanY

Calculated values

Film structure and optical properties proposedare correct.

Advanced minimization algorithms

for quick convergence

Physical parameters n,k Thickness

8


nre: refractive index measured when pores are emptynrl: refractive index measured when pores are fillednads: refractive index of the solvent

Lorentz-Lorenz equations

9


No need to know the refractive index of the skeletonV is the volume of open pores

nre: refractive index measured when pores are emptynrl: refractive index measured when pores are fillednads: refractive index of the solvent

10

Measurement principle

Acquisition of SE spectra

Analysis of SE spectra:Calculation of Thickness / Refractive index

0.0 0.2 0.4 0.6 0.8 1.00.393

0.394

0.395

0.396

0.397

0.398

0.399

0.400

0.401

Chemnitz LK3 SOPRA

Thic

knes

s, µ

m

Relative IPA Pressure

Ads. Des.

0.0 0.2 0.4 0.6 0.8 1.0

1.30

1.32

1.34

1.36

1.38

1.40

1.42

1.44

Chemnitz LK3 SOPRA

Ref

ract

ive

Inde

x


Ads. Des.

P/Po=1

(P/Po) (P/Po)

time

Pres

sure

Thickness vs partial pressure Refractive index @ 633nm vs partial pressure

11

Measurement principle

0.0 0.2 0.4 0.6 0.8 1.00.393

0.394

0.395

0.396

0.397

0.398

0.399

0.400

0.401

Thic

knes

s, µ

m

Relative solvent Pressure

B E

0.0 0.2 0.4 0.6 0.8 1.0

1.30

1.32

1.34

1.36

1.38

1.40

1.42

1.44

Ref

ract

ive

Inde

x


C F

Lorentz-Lorentz Equations=> Solvent volume vs rel.pressure

0.0 0.2 0.4 0.6 0.8 1.00.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

Solv

ent V

olum

e

Relative Solvent Pressure

B D

Porosity = 31%

12

From pores volume to PSDMeso Pores: KelvinPore size with diameter form 2 to 50nm(IUPAC classification)The solvent is in a liquid phase Po : equibrium vapor pressure

P/Po: relative equilibrium vaporpressure above meniscus

g : Surface tension of adsorptiveVL : molar volume of adsorptiverk : mean radius of curvatureq : wetting angle

)/ln(2

0PPRTVr Lγ

=:radiusPore

EP gives a distribution of pores for every relative pressure not a distribution a posteriori.

0.0 0.2 0.4 0.6 0.8 1.00.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

Sol

vent

Vol

ume

Relative Solvent Pressure

B D

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

0.1 1.0 10.0Pore Radius (nm)

dV/d

(lnR

)

AdsDesMicro AdsMicro DesTOLUENE

)01

11 /ln(.

2PPRT

Vr γ=

)0/ln(.2

PPRTVr

n

nn

γ=

)00/ln(.2

PPRTVr Lγ=

13

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4


dV/d

(lnR

)


Mesoporous material

0.0 0.2 0.4 0.6 0.8 1.00.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

Solv

ent V

olum

e


B D

Kelvin

Kelvin

From Solvent volume to Pore Size Distribution :Hysteresis in the isotherms=> mesoporous material (r >1nm)

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0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4


dV/d

(lnR

)


Mesoporous material

Kelvin

The pore radius for the adsorption is 2.5nm (cavities) and the pore radius for desorption is 1.9nm (connections)

15

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.0 0.2 0.4 0.6 0.8 1.0

Relative Pressure of Solvent

Solv

ent v

olum

e

Ads

Des

TOLUENE

0.09

Microporous materialMicro pores: Dubinin RadushkevichPore size with diameter below 2nm (IUPAC classification)The solvent is in a gaz phase

[ ]{ }22 )/()/ln(exp/ OO EPPRTWoW β−= W/Wo: fractional filling of the micropore volume: Woβ: scaling factor (affinity coeff.)Eo: characteristic energyr: pore radius, nm, normal Distribution, average radius

Pore radius: r = 6/Eo

Microporous total volume : 20.5%Microporous percentage : 73%Microporous average radius : 0.62nm

Ln(V) Ln²(p0/p)-6.36838614267765 60.965412465549-4.67839007262632 49.221408284231-5.16160802779383 41.3724559950233-5.21082991099096 34.9376351838247-4.12715216177882 26.8730040292041-4.06884111672946 22.37662106353-3.63299473960852 17.2037913967749-3.05876043728472 11.4797802777917-2.76752532211873 6.90585739520692-2.56657315455311 4.17480130899704

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0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.0 0.2 0.4 0.6 0.8 1.0


Solv

ent v

olum

e

Ads

Des

TOLUENE

Solvent Volume / P/P0

Microporous material

0.09

0.0

0.1

0.1

0.2

0.2

0.3

0.3

0.4

0.4

0.5

0.5


dV/d

(lnR

)


Mesoporous volume: 3.5%

Microporous volume: 20%Pore size: 0.75nm

Mesoporous distribution calculated with kelvin equation

• Total Porous Volume: microporous volumemesoporous volume

• Average pore size• Pore size distribution

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Why distribution is important

Same average density however different PSDRandom porosity Periodic pore structure

Courtesy of Dr. Shirataki. Asahi Kasei Corporation

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PSD control for best integration

0.0 0.2 0.4 0.6 0.8 1.00.00

0.02

0.04

0.06

0.08

IPA

Vol

ume


Ads Des

1 100.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

dV/d

(lnR

)

Pore Radius (nm)

Ads Des

0.0 0.2 0.4 0.6 0.8 1.00.00

0.05

0.10

0.15

0.20

0.25

Tolu

ene

Volu

me

Relative Toluene Pressure

Ads Des

1 100.0

0.2

0.4

0.6

0.8

1.0

1.2

dV/d

(lnR

)

Pore Radius (nm)

Ads Des

Tail of the distribution is very important as PSD can lead to problems in the integration

Low percentage of pores for R > 2 nm

Wide distribution

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Exemple of porosity

0.0 0.2 0.4 0.6 0.8 1.00.00

0.05

0.10

0.15

0.20

0.25

IPA

Volu

me


B D

1 100

2

4

6

8

10

dV/d

(lnR

)

Pore Radius, nm

B D

28% , 1.1nm

1 100

5

10

15

20

dV/d

(lnR

)

Pore Radius, nm

B D

0.0 0.2 0.4 0.6 0.8 1.00.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

IPA

Vol

ume


B D

36% , 1.8nm

0.0 0.2 0.4 0.6 0.8 1.00.00

0.02

0.04

0.06

0.08

0.10

0.12

IPA

Volu

me

B D

1 100

2

4

6

8

10

12

dV/d

(lnR

)

Pore Radius, nm

B D 12% , 1.0nm

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Ultra thin Ultra low K: 600A

Porosity = 19.8 % Pore radius = 1.0 nm

0.1 1 100.0

0.2

0.4

0.6

0.8

1.0dV

/d(ln

R)

Pore Radius (nm)

Ads Des

0.0 0.2 0.4 0.6 0.8 1.0

0.0612

0.0614

0.0616

0.0618

0.0620

0.0622

0.0624

0.0626

0.0628

0.0630

Thic

knes

s (µ

m)

Relative Methanol Pressure

Ads Des

0.0 0.2 0.4 0.6 0.8 1.0

1.38

1.39

1.40

1.41

1.42

1.43

1.44

1.45

1.46

1.47

Ref

ract

ive

Inde

x


Ads Des

0.0 0.2 0.4 0.6 0.8 1.00.00

0.05

0.10

0.15

0.20

Met

hano

l Vol

ume


Ads Des

21

BDII - K = 2.5

0.0 0.2 0.4 0.6 0.8 1.0

0.3475

0.3480

0.3485

0.3490

0.3495

0.3500

0.3505

0.3510

0.3515

Thic

knes

s (µ

m)


Ads Des

0.0 0.2 0.4 0.6 0.8 1.0

1.32

1.34

1.36

1.38

1.40

1.42

1.44

Ref

ract

ive

Inde

x


Ads Des

0.0 0.2 0.4 0.6 0.8 1.00.00

0.05

0.10

0.15

0.20

0.25

0.30

IPA

Volu

me


Ads Des

•Open Porosity = 26.4%• Pore Radius = 1.1 nm

PALS results:Porosity: 26.6%Pore radius: 1nm

1 100.0

0.2

0.4

0.6

0.8

1.0

1.2

dV/d

(lnR

)

Pore Radius (nm)

Ads Des

22

300mm Mapping

(0,60)

(0,-60)

(0,0)(-60,0)

(60,0)

Position Thickness

(µm) Porosity

(%) Pore Radius

(nm) Top 295.8 ± 0.3 33.1 1.9 Left 296.0 ± 0.3 33.8 1.9

Center 292.4 ± 0.7 32.8 1.7 Right 299.6 ± 1.0 34.0 2.0

Bottom 299.4 ± 0.7 34.4 1.9

EP features:• Small spot of 250x250um to achieve edge exclusion

better than 2mm• Field viewing camera• Mapping stage for 300mm and 200mm• Sites coordinates are recipe parameters

23

Sealing of porous materials

Sealing Techniques

Additive Surface densification

-By plasma-By e-beam-By Giant Ion Clusters-By UV

Plasma deposition

Atomic Layer

Deposition

•Ta/TaN•Dielectric•Polymer

•TaN•WCN•TiNetc.

Wet Chemicals

•Micelles•Silanols•Thiols•Siloxanes

Source: M Baklanov - IMEC

or

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Measurement on Pattern -sealing

Sample:Trenches: lines of 140nm 1/1 ratioSio2 (250nm) /ULK (300nm) /SiC (50nm)

Continuous change in SE spectra during adsorption cycle.The solvent fills in the materials inside the trench (through pore killers)

P/P0=1

25

Measurement on Pattern -Sealing

The solvent fills the trenches at saturated pressureChange in Tan Psi only for P/P0 close to 1.The Solvent condenses on the trenches

P/P0=1

Sample:Trenches: lines of 140nm 1/1 ratioSio2 (250nm) /ULK (300nm) /SiC (50nm)

26

Measurement on Pattern –Sealing

0.0 0.2 0.4 0.6 0.8 1.0

2.04

2.06

2.08

2.10

2.12

2.14

2.16

2.18

2.20

2.22

2.24

Tan(

Psi

) Pea

k P

ositi

on, e

V


Ads. Des.

Change in Tan Psi only forP/P0 >0.8

Pore sealing treatment is efficient

0.0 0.2 0.4 0.6 0.8 1.0

2.15

2.20

2.25

2.30

2.35

2.40

2.45

2.50

Tan(

Psi

) Pea

k P

ositi

on, e

V


Ads. Des.

Continuous change inTan Psi

Pore sealing treatment is not effective

NOYES

27

Pore sealingThe piece of wafer is placed in the vacuum.

Initial vacuum 60 sec under Solvent vapor

150 sec under Solvent vapor

The solvent diffuses only through the edge and not from theTop of the film. => The porous layer is sealed.

28

Pores Sealing



=> The porous layer is NOT sealed.

If the barrier is fully continuous, toluene cannot penetrate

In the case of not fully dense barrier, toluene can penetratethrough barrier pinholes and can be adsorbed by the Low K film..

29

Interconnectivity

Source: Shamyrian, Maex, MRS2003

30

Young Modulus calculation

Acquisition of SE spectra

Analysis of SE spectra:Calculation of Thickness / Refractive index

0.0 0.2 0.4 0.6 0.8 1.00.393

0.394

0.395

0.396

0.397

0.398

0.399

0.400

0.401

Thic

knes

s, µ

m


Ads. Des.

P/Po=1

(P/Po) (P/Po)

time

Pres

sure

Fit of the curve with theYoung – Laplace equation:T =T0 – k.ln(P/P0)K=T0RT/V.E

V=Volume of the solvent molecule

31

Young Modulus calculation

Effect of nanoindentoron porous low K

32

Correlation to electrical K

Sample 5 Thickness (nm) Optical Index (633 nm) Porosity (%)Pore Radius (Ads/Des) (n

Low K 277.1 ± 0.8 n = 1.287 & k = 0 31.1 1.5Silicon n = 3.881 & k = 0.019







05

1015202530354045

2 2.2 2.4 2.6 2.8

K valuePo

rosi

ty (%

)Porosity (%)

33

0.0

0.1

0.1

0.2

0.2

0.3

0.3

0.4

0.4

0.5

0.5


dV/d

(lnR

)


0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.0 0.2 0.4 0.6 0.8 1.0


Solv

ent v

olum

e

Ads

Des

TOLUENE

Summary table

0.0 0.2 0.4 0.6 0.8 1.00.0

0.1

0.2

0.3

0.4

0.5

0.6

IPA

Volu

me


Ads. RO Des.

Micro porous

Meso porous

Bi modal

0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4


dV/d

(lnR

)


34

Conclusion - EP

1. EP gives quantitative, accurate and repeatable measurement for:• Porosity • Pore size distribution for meso, microporous and bi-

modal distribution• Film thickness and refractive index• Mapping of this parameters• Small spot for edge exclusion control

2. EP gives qualitative information for the pore sealing treatment of ULK layers.• Measurement of blanket wafers• Measurement of patterned wafers• ULK behavior in a process integration scheme

35

Conclusions - EP

"Low dielectric constant materials for microelectronics"K. Maex, M.R. Baklanov, D. Shamiryan and F. Iacopi, S.H. Brongersma, Z.S. YanovitskayaJ. Appl. Phys., Foc. Rev. 93, N11, 1 June 2003, pp 8793-8841

36

Bibliography"Ellipsometric Porosimetry of Porous Low-k Films with Quasi-Closed cavities"Mikhail R. Baklanov, Konstantin P. Mogilnikov, Jin-Heong YimMRS Spring Meeting, 12-16 April 2004, San Francisco, USA

"Nondestructive Characterization of a Series of Periodic Porous Silica Films by in situ Spectroscopic Ellipsometry in a Vapor Cell”

C. Negoro, N. Hata, K. Yamada, T. KikkawaJap. J. of Appl. Phys. Vol 43 No 4, 2004, pp 1327-1329

"Description of the porosity of inhomogeneous porous low-k films using solvent adsorption studied by spectroscopic ellipsometry in the visible range”

A. Bourgeois, A. Brunet Bruneau, V. Jousseaume, N. Rochat, S. Fisson, B. Demarets, J. RivoryThin Solid Films 455-456, 2004, pp 366-369

"Investigation of the microporous structure of porous layers using ellipsometric adsorption porometry”F.N. Dultsev, Thin Solid Films 458, 2004, pp 137-142

"Diffusion barrier integrity evaluation by ellipsometry porosimetry"D. Shamiryan, M.R. Baklanov, K. Maex, J. Vac. Sci. Technol. B 21(1), Jan-Feb 2003, pp 220-226

"Low dielectric constant materials for microelectronics"K. Maex, M.R. Baklanov, D. Shamiryan and F. Iacopi, S.H. Brongersma, Z.S. YanovitskayaJ. Appl. Phys., Foc. Rev. 93, N11, 1 June 2003, pp 8793-8841

"Porous Thin Film Metrology for Low-k Dielectric"Extrait de NIST Semiconductor Microelectronics and Nanoelectronics Programs, July 03, pp 82-86

"Determination of Porosity of TiO2 Films from reflection Spectra"T. Matsubara, T. Oishi and A. KatagiriJ. of the ECS, 149 (2), 2002, pp C89-C93

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CONTACTS

For more product information :www.sopra-sa.com

For any question please contact :Mr Laurent [email protected]

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