Plasma Removal Process

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 Outline
• Introduction
• Models to understand the plasma process
• Chemistry
• Analyzing recipe parameters, and the
resultant etch profiles
• Endpoint

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 Sidewall Passivation
• Sidewall passivation can be used in an etch process to
control sidewall profile
• A film forms on the sidewalls, preventing the material
from being etched isotropically
• The film is actually a polymer formed from the process
gases and the photoresist layer on the substrate
• The polymers are basically combinations of carbon and
hydrogen. May contain oxygen and nitrogen and other
etch byproducts. Polymer chemistry depends on process
conditions.
• Specific gases can be added to the recipe to insure
passivation film formation
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 Etch Profile with Sidewall Passivation
Radicals: reactive etching
species

Reaction Products:
volatile etch products

Film formers: provide

sidewall passivation,
photoresist can be a large
contributor

Positive ions: provide

physical bombardment on
surface, breaking surface
film formers at bottom,
physically etching and
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drive chemical reactions
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 Sidewall Passivation
• Polymers coat the sidewalls and act as a
“pseudo-mask” for protection from chemical
attack
• Ions, for the most part, strike vertically and
remove polymer buildup at the bottom of the
etch
• The sidewall polymers are removed by using O 2
plasma at 500-750mT
– This exposure uses a lot of chemistry and little
bombardment

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 Outline
• Introduction
• Models to understand the plasma process
• Chemistry
• Analyzing recipe parameters, and the
resultant etch profiles
• Endpoint

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 Controlling the Etch Process by Balancing
Chemistry and Bombardment

• In dry etch processes choosing the correct chemistries

can greatly increase the etch rate
• Increasing MFP of the plasma (decreasing the pressure)
also increases the etch rate, this will aid uniformity
• Combining chemistry and bombardment will produce an
etch rate that is greater than either contributor alone
• Combining chemistry and bombardment allows the
profile to be “tuned” between isotropic and anisotropic
• The etch profile can also be enhanced with side wall
passivation

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 Example Sidewall Chemistries
Material Chemistry Volatile Etch Sidewall
Product Material
Oxide SiO2 + CF4 + CHF3 + Ar  SiF, SiOF, SiF4, Si, C, CHx, F 
Etch SiH4

Poly Si Si + HBr + Cl2  SiBrx  Si,Br,C,Cl 

Etch SiClx

Al Etch Al + BCl3 + Cl2 + N2  AlCl3  Al,B,C,N,Cl 

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 Some etching Gases
Formula Common Chemical Name Formula Chemical
Name Name

CF4 Freon 14 Tetrafluoro-methane SiCl4 Silicon

Tetrachloride

C2F6 Freon 116 Perfluoro-ethane BCl3 Boron-

trichloride

C3F8 Freon 218 Perfluoro-propane Cl2 Chlorine

CHF3 Freon 23 Trifluoro-methane HCl Hydrogen

Chloride

CF3Br Freon Bromo- HBr Hydrogen

13B1 trifluoro-methane Bromide

SF6 Sulfur Hexafluoride He Helium

NF3 Nitrogen N2 Nitrogen

Trifluoride

SiF4 Silicon O2 Oxygen

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 Some Materials and Selected Etchants
Material Chemistry Material Chemistry
PolySilicon Cl2 or BCl3/CCl4 WSi2,TiSi2,CoSi2 CCl2F3
HBr /CF4
/CHCl3
/CHF3

Aluminum Cl2 Single crystal Si Cl2 or BCl3 +

BCl3 + passivating passivating gases
gases
SiCl4
AlSi(1%)-Cu(0.5%) same as Al SiO2 (BPSG) CCl2F2,CF4,C2F6,

C3F8
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 Outline
• Introduction
• Models to understand the plasma process
• Chemistry
• Analyzing recipe parameters and the
resultant etch profiles
• Endpoint

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 The “Egg” Chart
• This analytical model is a graphical representation of various
process parameters. The Y axis represents bombardment
energy, the X axis represents chemical energy, and the “dog
leg” boundary represents polymer formation.
• For an ideal anisotropic etch, the required parameter zone
resembles an “egg” in the middle of the chart
• This chart shows the combined effects of chemistry,
bombardment, and polymerization (C*B+P) to predict sidewall
profiles
• There are also other factors that determine the etch profile
that are not included in this exercise. These parameters will
be discussed after this first iteration analysis.

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 The “Egg” Chart
• A chart like this can be found and/or
generated for any dry etchable material
• Due to its wide use in micro and
nanofabrication, we will analyze the egg
chart for SiO2
• Naturally this chart is not “exact”, but can
be used as a starting point for building a
etch recipe.

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 Oxide Egg Chart Considerations
• F/C Ratio- the ratio of fluorine to carbon etching
species
• Increasing DC bias, increases bombardment
• The addition of H2 to the chamber increases
polymerization
• The addition of O2 to the chamber increases free
fluorine
• Aspect Ratio- the ratio of depth to width for a
small gap, trench, or hole

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 Fluorine to Carbon Ratio (F/C) of Gas Phase Etching Species vs DC Bias Level

High C2F4 C4F10 C2F6 CF4

Etching
Bias Applied to Surface (Volts)
DC Bias

O2 Addition

Loading
Polymerization
H2 Addition

Low
0 1 2 3 4

F/C Ratio
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 Fluorine to Carbon Ratio (F/C) of Gas Phase Etching Species vs DC Bias Level

High C2F4 C4F10 C2F6 CF4

Etching
Bias Applied to Surface (Volts)

1
DC Bias

O2 Addition

Loading
Polymerization
H2 Addition

Low
0 1 2 3 4

F/C Ratio
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 The Ideal Profile
• To be “in the egg” is to achieve the ideal
anisotropic etch
– The ideal F/C ratio is approximately 2
– An equal mix of hydrogen and oxygen to
balance polymerization and etch
– DC bias level that provides just enough
bombardment

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 The Ideal Profile

W
D

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 Sidewall Profile Two
• Low DC bias – little/no bombardment
• No H2 - no polymerization
• A lot of O2 – can increase etching
• F/C ratio = 4, SiF4 is formed
• Aspect ratio < 1, an isotropic etch profile

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 Fluorine to Carbon Ratio (F/C) of Gas Phase Etching Species vs DC Bias Level

High C2F4 C4F10 C2F6 CF4

Etching
Bias Applied to Surface (Volts)
DC Bias

O2 Addition

Loading
Polymerization
H2 Addition
2
Low
0 1 2 3 4

F/C Ratio
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 Sidewall Profile Two

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 Sidewall Profile Three
• Low DC bias – no bombardment
• A lot of H2 - a lot of polymerization
• No O2 – no etch
• F/C = 1/3, SiF4 is not formed

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 Fluorine to Carbon Ratio (F/C) of Gas Phase Etching Species vs DC Bias Level

High C2F4 C4F10 C2F6 CF4

Etching
Bias Applied to Surface (Volts)
DC Bias

O2 Addition

Loading
Polymerization
H2 Addition
3
Low
0 1 2 3 4

F/C Ratio
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 Sidewall Profile Three

Polymer buildup

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 Sidewall Profile Four
• High DC bias – high bombardment
• No H2 – no polymerization
• A lot of O2 – high etch
• F/C ratio = 4, SiF4 is formed
• Aspect ratio >1, a dry etch profile

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 Fluorine to Carbon Ratio (F/C) of Gas Phase Etching Species vs DC Bias Level

High C2F4 C4F10 C2F6 CF4

Etching 4
Bias Applied to Surface (Volts)
DC Bias

O2 Addition

Loading
Polymerization
H2 Addition

Low
0 1 2 3 4

F/C Ratio
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 Sidewall Profile Four

3
6

Sharp angles due

to high bombardment
with no polymerization
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 Sidewall Profile Five
• High DC bias – high bombardment
• A lot of H2 – a lot of polymerization
• No O2 – no etch
• F/C ratio =1/5, SiF4 is not formed
• Aspect ratio > 1, Dry etch profile with
undesirable features

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 Fluorine to Carbon Ratio (F/C) of Gas Phase Etching Species vs DC Bias Level

High C2F4 C4F10 C2F6 CF4

5 Etching
Bias Applied to Surface (Volts)
DC Bias

O2 Addition

Loading
Polymerization
H2 Addition

Low
0 1 2 3 4

F/C Ratio
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 Sidewall Profile Five

Jagged features
due to
polymer buildup
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 Sidewall Profile Six
• Medium DC bias – medium bombardment
• No H2 – no polymerization
• A lot of O2 – high etch
• F/C = 4, SiF4 is formed
• Aspect ratio < 1, a wet etch profile

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 Fluorine to Carbon Ratio (F/C) of Gas Phase Etching Species vs DC Bias Level

High C2F4 C4F10 C2F6 CF4

Etching
Bias Applied to Surface (Volts)
DC Bias

O2 Addition 6
Loading
Polymerization
H2 Addition

Low
0 1 2 3 4

F/C Ratio
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 Sidewall Profile Six

Wider and deeper

than profile one
due to increased
bombardment Public Domain: Image Generated by CNEU Staff for free use

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 Sidewall Profile Seven
• Medium DC bias – medium bombardment
• A lot of H2 – a lot of polymerization
• No O2 – no etch
• F/C ratio = ¼, SiF4 is not formed
• Aspect ratio > 1, Dry etch profile with
undesirable features

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 Fluorine to Carbon Ratio (F/C) of Gas Phase Etching Species vs DC Bias Level

High C2F4 C4F10 C2F6 CF4

Etching
Bias Applied to Surface (Volts)

7
DC Bias

O2 Addition

Loading
Polymerization
H2 Addition

Low
0 1 2 3 4

F/C Ratio
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 Sidewall Profile Seven

Less bombardment than profile four

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 Considerations Beyond
the Egg Chart
• The “egg chart” is a useful first
approximation to define some process
parameters, but it does not cover some
important considerations.
• We will discuss 4 additional
considerations:
• Residence time
• Microloading
• Proximity effect
• Post etch evaluation
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 Residence Time
• The average time gas is present in the
chamber (seconds)
• The residence time is a balance of the
pressure, input gas flow, and the pump
efficiency
• Naturally the residence time will impact the
etch process, because etch chemistry and
byproducts are constantly being pumped
away at a certain rate

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 Microloading
• The change in local etch rate relative to
the whole area of material being etched
– A large area will load the etching process with
volatile etch products, slowing the etch down
in that area while a smaller etch area
proceeds at a faster rate
• Etch rates change according to pattern
and exposed area

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 Microloading
Photoresist on top of Wafer

Patterned holes in the PR where

etching of the wafer occurs

Larger area loading More etching

the process with removed gas relative to area-
material- less etching gas etches quicker
relative to area

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 Proximity Effect- Etch Rate
Based on Feature Size

SiF4 SiF4
F F

Si Si Si Si

“Crowded”- Easier to remove byproducts,

harder to remove byproducts, faster etch rate
slower etch rate

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 Etch Evaluation
• Process quality parameters:
– Etch rate, selectivity, uniformity
– Sidewall Profile
– Loss or gain of critical dimensions
– Corrosion (in metal etch)
– Reproducibility

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 Outline
• Introduction
• Models to understand the plasma process
• Chemistry
• Analyzing recipe parameters, and the
resultant etch profiles
• Endpoint

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 Endpoint Detection
• General term describing when an etch
process has finished
• Two common methods of detection
– Optical emission
– Mass spectroscopy

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 Optical Emission
• Each volatile etch product emits a specific
wavelength
• The wavelength intensity shows the
relative amounts of products being formed
• A decrease in intensity corresponds to a
decrease in etch products.

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 RIE With Optical
Endpoint Detector

Endpoint Detector

Oxford Instruments Plasmalab System 100

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 Optical Emission
(nm)
Material to be etched Etchant Gases Emitting Species

Silicon CF4/O2; SF F(product) 704

CF4/O2; SF SiF(product) 440, 777
Cl2 SiCl(product) 287

SiO2 CHF3 CO(product) 484

Si3N4 CF4/O2 N2(product) 337

CF4/O2 CN(product) 387
CF4/O2 N(product) 674
CF4/O2 F(etchant) 704

Al Cl2; BCl3 Al(product) 391, 394, 396

Cl2; BCl3 AlCl(product) 261

Resist O2 O(etchant) 777, 843

O2 CO(product) 484
O2 OH(product) 309
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 Example Graph of Optical
Endpoint Detection
Endpoint
detection
Etch Parameter

Normal etch Change in

etch rate -
detection
occurs here.

Endpoint signal
stops the etch.

Time

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 Mass Spectroscopy
• This method of endpoint detection measures
the mass/charge ratio of the etch products
• As the mass/charge ratio peak declines, the
products being generated by the etch decline
due to the material being etched away
• A residual gas analyzer is a mass
spectrometer

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 Mass Spectrometer Schematic
Detector

A
Steering magnets

Particle Accelerator

Ionizing electron stream

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 Example Mass Spectra:
Benzyl Alcohol

Benzyl Alcohol

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