Chemical Mechanical Polishing

for Manufacturing of Smooth Nb Surfaces

George Calota1, Natalia Maximova2, Katherine Ziemer2 and Sinan Muftu1,3

Department of Mechanical Engineering

1

2
Department of Chemical Engineering
3
NSF-NSEC-Center for High-rate Nanomanufacturing

Northeastern University
Boston, MA 02115
s.muftu@neu.edu, (617) 373-4743

Acknowledgement:
• H.C. Starck, Inc, Newton, MA
• NSF-Center for High-rate Nanomanufacturing (Award # NSF-0425826)

Mechanical Engineering and Chemical Engineering

CMP in Semiconductor Manufacturing

Chemical Mechanical Polishing (CMP) is a

critical step in integrated circuit (IC)
manufacturing, typically used for
planarizing:
• Dielectric materials: SiO2
• Conductors: copper (Cu) and tungsten (W)
• Diffusion barrier: Tantalum (Ta)
In between processing steps.
Evans, D.R. “Metal Polishing Process,” in
Chemical-Mechanical Planarization of
Semiconductor Materials, ed. M.R. Oliver, Springer,
2003, p 41.

Mechanical Engineering and Chemical Engineering

Planarizing a SiO2 wafer using CMP

Experimental results:
Our polishing experiments on SiO2 show:
– Large wavelength roughness is reduced to 1 μm level
– Short wavelength roughness is reduced to 1 nm level.
– Sub nanometer roughness is typical for Si wafers

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Goal and Outline

The goal of this presentation is to demonstrate the potential of CMP as

an alternative method to manufacture very (nearly atomically)
smooth Niobium surfaces.

Outline
• Brief description of chemical mechanical polishing (CMP)
• Studies of Oxidation of Niobium
• Proposed two-step process for polishing of Niobium
• Initial results
• Summary and conclusions

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 CMP Process

Process description:
• A wafer is pushed against a polymeric polishing pad Carrier

• (Pa = 1-10 psi)

Polishing pad
Wafer
• Pad and wafer rotate independently (~60 rpm).
Rotating platen
• Slurry, containing oxidizing chemicals and abrasive particles is
supplied into the interface. Schematic of CMP operation

• Material removal occurs due to particle abrasion of the

chemically passivated wafer surface.
Wafer
Slurry
Designed to create (low-hardness) oxides.

Chemicals: Particles:
• Oxidizers • Material:
• Buffers Silica (SiO2), alumina (Al2O3, Ceria (CeO2)

• Surfactants • Size: 50-150 nm

• Shape: Spherical

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Contact at wafer-pad interface

Polishing pad (IC1000) Polyurethane Pad wafer interfacial contact

wafer

pad particles

wafer

Direct
contact Chemically
passivated
The mechanical component of material removal is primarily pad Particle layer
contact
dominated by particle-wafer contact. Abrasion of the particle

But, particle-to-wafer contact forces depend on many variables:

• Applied pressure
• Particle size
• Particle concentration
• Pad elasticity
• Pad thickness
• Pad roughness

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Material removal rate

Material Removal:
• Material removal is governed by an abrasive removal process:
F .Lsliding k: removal rate constant
V k
(')
Archard’s Law
H F Normal force
LS: Sliding distance
H: Hardness (material property)
V(‘): Worn volume

In CMP literature material removal rate (MRR) is used:

dV k: removal rate constant
MRR   kPV
c
Preston’s Law Pc: Applied push down pressure
dt
V: Sliding speed

Removal rate constant k represents the effects of:

• Abrasive particle size, concentration, hardness, morphology
• Wafer hardness, surface roughness
• Slurry chemistry
• Pad roughness, elasticity
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XPS Studies on Niobium oxidation

In general a passivated metal-oxide is softer and easier to remove mechanically.

CMP strives to find a delicate balance between oxide formation and mechanical
abrasion
The first step of our investigation was to understand oxidation of Niobium for
conditions relevant to CMP
Characterization using X-ray Photoelectron Spectroscopy (XPS) under various
processing conditions carried out
1. Characteristics of Niobium Oxide
2. Effect of base and acid on oxidation
3. Effect of buffered chemical polish (BCP) on Niobium
4. Hardness test on Niobium oxide underway.

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XPS Studies on Niobium oxidation-I

XPS Analysis Reveals Nb-O Bonding

Nb oxide
3d 5/2
Oxide Thickness
Oxides formed by Nb: ~4.5 nm

Nb oxide
Conditions 3d 3/2

Arbitrary Units
Nb metal
• Exposed to air, as received Nb metal 3d 5/2
3d 3/2

• After CMP using Cu and SiO2 slurry

(small amount of material removal)

Results 213 208 203 198

Binding Energy (eV)
The XPS study shows that Δ eV is
Characteristic
Sampling Depth: ~ 7 nm Δ eV ~ 5 eV of Nb2O5
• The oxide thickness is ~ 4.5 nm
• The majority of the oxide is Nb2O5
• The oxide layer thickness self limiting type
(long term exposure to ambient or to an oxidizer doesn’t change oxide depth)

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XPS Studies on Niobium oxidation-II

Effect of Base (H2O2) and Acid (HF)

Conditions Nb 3d
• Acid = 5 ml HF, 17 ml Nitric, 51 ml Methanol
Metal Peaks
• Base = 5 ml ammonium hydroxide, Active
10 ml H2O2, 50 ml DI water Oxidizer: H O 2 2

Results
The XPS study shows that
Cannot remove all
Active Etchant:
• Base (H2O2) forms oxide HF
of the oxide –
oxidizes in air and
seems limited to
• Acid (HF) removes oxide ~4.5 nm

214 209 204 199

Binding Energy (eV)

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XPS Studies on Niobium oxidation-III

Material Removal (g) PV (um)

0.4 14

Surface roughness, PV (um)

Buffered Chemical Polish (BCP)
0.35 12

Material Removal (g)

0.3
10

BCP Formula: 0.25

8
• 10 mL HF (49%), 0.2
6
• 10 mL HNO3 (65%), 0.15

• 20 mL H3PO4 (85%) 0.1

4

0.05 2

0 0
Results -5 0 5 10 15 20
BCP treatment time (min)
• 18 min of BCP removed up to 200 um
Nb 3d
• Surface roughness changed from 8 um-10 um (PV)
The XPS study shows that 6-minute
BCP dip
• BCP treatment exposes a highly ordered Nb

as-received

214 209 204 199

Binding Energy (eV)
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Niobium CMP using SiO2 slurry

PV RMS Ra
Expon. (PV) Expon. (RMS) Expon. (Ra)

10
Roughness (microns)

0.1
0 5 10 15 20
Polishing Time (min)

Surface roughness vs polishing time

Pad and wafer rotational speeds: 60 rpm

Supply pressure : 500 g/cm2
Carrier head linear oscillations : on
Slurry : Microplanar CMP 1150 by EKC Technology, Inc.
Polishing Pad : IC1000 A2, by Rohm and Haas Electronic Materials
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XPS Studies on Niobium oxidation - Conclusion

Characterization of Niobium oxide formation under various processing conditions:

1. Nb2O5, a stable oxide, is the dominant form when Nb is exposed to oxidants

2. This oxide is ~4.5 nm thick and its thickness is self-limiting.
3. a. It does not appear that passivation, in the CMP sense, will be helpful in
polishing a relatively rough surface.
b. Passivation may be useful in planarazing a smooth Niobium surface.

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Two step polishing process

Two step process :

Step-1: Use large, hard abrasive particles to remove large PV roughness
• Slurry-1: 0.5 um Alumina (Al2O3) 11 weight percent, dispersed in H20
(calcinated)
• Slurry-2: 1.0 um Alumina (Al2O3) 11 weight percent, dispersed in H20
(polycrystalline)
Pace Technologies, Tucson, AZ.
Step-2: Use CMP approach to planarize the surface using available slurries
Pourbaix diagrams give guidance in the selection.
• W-slurry
• Cu-slurry
• SiO2 (particle size O(50 - 100 nm))

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Abrasive wear

Two body abrasive mode: arises when a

hard rough surface slides against a softer
surface, digs into it and plows a series of
grooves.

Three body abrasive mode: arises when

abrasive particles are introduced between
sliding surfaces.
3-body wear produces lower wear rates,
and more randomized wear marks.
Stachowiak, G.W., Batchelor A.W. Engineering Tribology, 2nd edition, BH
Publishing, 2001.

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Two step process

PV RMS Ra
5 per. Mov. Avg. (PV) 5 per. Mov. Avg. (RMS) 5 per. Mov. Avg. (Ra)
10
Surface Roughness (microns)

0.1
Diluted 0.5 0.5 micron
micron alumina alumina
polish 0.5 micron 1 micron polish
alumina polish alumina polish
SiO2 Slurry
0.01
0 10 20 30 40 50 60 70
Polishing Time (min)

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Evolution of a smooth Nb surface by 2-Step Process

t = 0, PV=7.2 um t = 17 min, PV = 4.6 um t = 28 min, PV = 3.3 um

t = 42 min, PV=1.8 um t = 52 min, PV = 1.5 um t = 58 min, PV = 0.4 um

t = 60 min, PV = 0.5 um t = 67 min, PV = 0.3 um t = 71 min, PV =0.2 um

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Summary and conclusions

Chemical mechanical polishing of Niobium is investigated

• Niobium forms a stable Ni2O5 oxide, ~ 4.5 nm thick, and self limiting.
• BCP treatment exposes ordered Niobium metal, but prolonged treatment does not
improve surface roughness.

A two step procedure is proposed to first polish and then to planarize.

• Preliminary experiments show substantial improvements in surface finish.
• Peak-to-Valley roughness reduced from ~7 um to 0.2 um

Process parameters need to be optimized

• These include pressure, particle size and polishing time, final CMP slurry type

Implementation inside the cavities are not considered in this short term
investigation
Considering the potential surface quality obtainable implementation of
this approach inside cavities should be explored further

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 Backup Slides

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 Model predictions of material removal

Uniformity of material removal depends primarily on local contact pressure,

but also affected by slurry-chemistry, abrasive size, wafer speed, pad properties/roughness

Wafer scale
Polishing uniformity is important at three scales:
• Wafer (affects wafer bow)
• Die (affects die-scale bow)
• Feature (affects nano-wire flatness)

Modeling used to uncover fundamentals of the mechanisms

enabling macro- and nano scale material removal. Die scale
Feature scale

Non-uniform contact pressure

on the wafer will cause
Slurry pressure

Contact pressure
non-uniform material removal
and wafer bow at wafer-scale

y y More material removal predicted on wafer’s edges

x x
Slurry pressure Contact pressure
distribution under wafer distribution on the wafer

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BCP treatment

Material Removal (g) PV (um)

1.4 16 Removed Material (mm) PV (um)
0.6 16

Surface roughness, PV (um)

1.2 14

Surface roughness, PV (um)

14
0.5
Material Removal (g)

12

Material Removal (g)

1 12
0.4
10 10
0.8
8 0.3 8
0.6
6 6
0.2
0.4 4
4
0.1
2
0.2 2
0 0
0 0 -10 0 10 20 30 40 50 60 70 80 90 100
-10 0 10 20 30 40 50 60 70 80 90 100 BCP treatment time (min)
BCP treatment time (min)

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 XPS Analysis Reveals Nb-O Bonding
Nb oxide
3d 5/2
Oxide Thickness
~4.5 nm

Nb oxide
3d 3/2
Arbitrary Units

Nb metal
Nb metal 3d 5/2
3d 3/2

213 208 203 198

Binding Energy (eV) Δ eV is

Characteristic
Sampling Depth: ~ 7 nm Δ eV ~ 5 eV of Nb2O5
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 Nb 3d

Metal Peaks
Active Oxidizer:
H2O2

Cannot remove all

Active Etchant:
of the oxide –
HF
oxidizes in air and
seems limited to
~4.5 nm

214 209 204 199

Binding Energy (eV)

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 BCP Dip Study; Step 1 of 2-Step Process

Buffered Chemical Polishing (BCP)

Formula:
10 mL HF (49%), 10 mL HNO3 (65%),
and 20 mL H3PO4 (85%)

Nb 3d
0.4
0.35
Mass Removal Rate
Grams removed

0.3
6-minute
0.25 BCP dip
0.2
0.15
0.1
as-received
0.05
0
0 5 10 15 20
214 209 204 199
Time in minutes Binding Energy (eV)
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 BCP Dip Study; Step 1 of 2-Step Process

Nb 3d
0.4
0.35
Mass Removal Rate
Grams removed

0.3
6-minute
0.25 BCP dip
0.2
0.15
0.1
as-received
0.05
0
0 5 10 15 20
214 209 204 199
Time in minutes Binding Energy (eV)
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 Impact of 1-minute BCP Dip
1 minute BCP produced significantly narrower linewidth (more ordered
matrix) with potentially more surface removal than Cu Slurry alone…..

Nb 3d

FWHM = 1.3 eV

1 minute BCP +
Cu Slurry CMP

FWHM = 1.7 eV
Cu Slurry CMP
213 208 203 198
Binding Energy (eV)
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 Pourbaix Diagram for Nb-H2O System

Asselin, E., Ahmed, T.M., and Alfantazi, A., “Corrosion of niobium in sulphuric and hydrochloric
acid solutions at 75 and 95 DegC” Corrosion Science, 49(2): p. 694-710, 2007.
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 Pourbaix Diagram for Nb-H2O System
Cu
Slurry
+
H2O2

Cu
Slurry

Si
Slurry

Asselin, E., Ahmed, T.M., and Alfantazi, A., “Corrosion of niobium in sulphuric and hydrochloric
acid solutions at 75 and 95 DegC” Corrosion Science, 49(2): p. 694-710, 2007.
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CMP using High-Pressure & Copper slurry

PV RMS Ra
Linear (PV) Linear (RMS) Linear (Ra)
10
Surface Roughness (microns)

0.1
0 2 4 6 8 10 12 14 16 18
Polishing Time (min)

Surface roughness vs polishing time

Pad and wafer rotational speeds: 60 rpm

Supply pressure : 1000 g/cm2
Carrier head linear oscillations : on
Slurry : Microplanar CMP 1150 by EKC Technology, Inc.
Polishing Pad : IC1000 A2, by Rohm and Haas Electronic Materials
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CMP using High-Pressure & Copper slurry on BCP treated Nb

PV RMS Ra
Linear (PV) Linear (RMS) Linear (Ra)
10
Surface Roughness (microns)

0.1
0 5 10 15 20
Polishing Time (min)

Surface roughness vs polishing time

Pad and wafer rotational speeds: 60 rpm

Supply pressure : 1000 g/cm2
Carrier head linear oscillations : on
Slurry : Microplanar CMP 1150 by EKC Technology, Inc.
Polishing Pad : IC1000 A2, by Rohm and Haas Electronic Materials
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CMP-Physics-I: Continuum effects
z
y
w
Liquid slurry lubrication: Reynolds eqn.  th
r hp


 


 1  h  
   
y x
 h  p .p  12   V1  V2 . hT   V1  V2 s   T 
3 z x x
pc, p
w
 2   t 
z

Multiasperity Contact: Greenwood et al. (1966, 1967) Holder

Soft-pad
Wafer y
  x pc , p y
4
pc  NE * Rs1 / 2   z  d    z dz
3/ 2

3 d

Pad deflections: Elasticity

1  2 p  x ', y ' dx ' dy '

w  x, y   
E   x  x '   y  y '
2 2
Williams, J.A. Engineering Tribology, Oxford, 2000.

Pad wafer clearance

hT  h  1   2  w

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CMP Physics-II: Force Balance

z
y
w

 th

Forces acting on the pad need to be in balance: r


 y x
hp

z x x
pc , p
w
• Slurry pressure, p z

• Normal and tangential contact tractions, µpc, pc Holder

Soft-pad
Wafer y
 x pc, p y

RFz  
Af
pdA   pc dA  Fzext  0
Ac

RM x     x th dA     pc x th dA   pxdA   p xdA  M
c
ext
x 0
Af Ac Af Ac

RM y     y th dA     pc  y th dA   pydA   pc ydA  M yext  0

Af Ac Af Ac

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CMP-Physics:-III

Material Removal:
• Material removal is governed by an abrasive removal process:
F .Lsliding k: removal rate constant
V k
(')
Archard’s Law
H F Normal force
LS: Sliding distance
H: Hardness (material property)
V(‘): Worn volume

In CMP literature material removal rate (MRR) is used:

dV k: removal rate constant
MRR   kPV
c
Preston’s Law Pc: Applied push down pressure
dt
V: Sliding speed

Removal rate constant k represents the effects of:

• Abrasive particle size, concentration, hardness, morphology
• Wafer hardness, surface roughness
• Slurry chemistry
• Pad roughness, elasticity
Mechanical Engineering and Chemical Engineering