The effect of 'reflux' (ions from etch products) in a

microwave source Ar/HBr silicon-etch process.

Dr. James Munro

Prof. Jonathan Tennyson,
Mr. Stephen Harrison

Dr. Song-Yun Kang

8th Technological Plasma Workshop

Thurs. 6th Jan. '11, 14:35
 Electron Chemistry

Data Data

Global Model Reactor Model

Informs Informs Validates Validates

Process and Tool Measurement,

Development Experimentation
 Modeling polyatomic electron-molecule interactions
What does Quantemol-N do?

 Elastic cross sections

 Electronic excitation cross sections
 Electron impact dissociation Recent Additions v3.8:
 Rates o Atomic cross-sections
 Resonance parameters o High energy excitation cross-sections
 Ionisation cross sections
 Dissociative electron attachment
 Differential cross sections
 Momentum transfer cross sections
 Vibrational excitation cross sections

Tennyson et. al., J. Phys. Conf. Ser. 86, 012001 (2007)‫‏‬

Methane
 How does Quantemol-N work?

The R-Matrix Method

• The sphere, of radius a, has
e- the centre of mass of the
molecule as its origin;
• the sphere contains the
electron cloud of the
molecule;
• equations of motion are
r solved in the body-fixed
frame (fixed nuclei
approximation)‫‏‬
Tennyson, Phys. Rep. 491 (2010) 29-76
 Progress...

CF2 C6H6 C5H12 SiH4

Cl2 C3H4 NO2 C2H6
O2 C2 NO C3H8
H2O C3H6 O3 HCN
H3+ CaF+ PH3 HNC
CH4 CaF BF3 SiO
C3N CF N2 CS
Cl2O CO2 CO F2
CONH3 BF3 H2 HBr
... and more.
CF2
 CF4/O2 CCP etch

0-D plasma simulation CCP etching chamber

SCCM
 Simulation
9.0E+11
8.0E+11
7.0E+11 CF
6.0E+11

CF (#/cm3)
5.0E+11 Original
4.0E+11 CF2*
3.0E+11
2.0E+11
1.0E+11
0.0E+00
0 500 1000 1500 2000
Power (W)
2.0E+12 1.4E+14
1.8E+12
1.2E+14
1.6E+12
1.4E+12
CF2 F
1.0E+14
CF2 (#/cm3)

1.2E+12 F (#/cm3)
Original 8.0E+13 Original
1.0E+12
CF2* CF2*
8.0E+11 6.0E+13
6.0E+11
4.0E+13
4.0E+11
2.0E+11 2.0E+13
0.0E+00 0.0E+00
0 500 1000 1500 2000 0 500 1000 1500 2000
Power (W) Power (W)
T. Mori, M.Sasaki, T Nishizuka and T. Nozawa, 55th AVS, PS-TuM10
T. Mori, M.Sasaki, T Nishizuka and T. Nozawa, 55th AVS, PS-TuM10
13
Reaction model
-Charged species: e-, Br-, Ar+, HBr+, Br+, Br2+, SiBr2+, and SiBr+
-Neutral species: Ar, Ar*, HBr, Br, Br2, H2, H, SiBr2, SiBr, and Si
-Electron impact reactions: Ionization, excitation, dissociation,
attachment, and recombination
-Ion – neutral reactions
-Ion – ion reactions
-Molecule – molecule reactions

SiBr2+, SiBr+, SiBr, and Si are omitted in case

without SiBrx reactions.
Ar/Cl2 = 90/10 sccm
500 W ICP
15mTorr

Re-flux of SiCl2+ was

important but was not
dominant at this lower
pressure.

Agarwal A. & Kushner M.

JVSTA 26 (2008) 498

14
 SiBr
49 Electrons

Bond length: 2.641 Ang.

15
 e + SiBr >
1000

Ionisation Elastic

Dissociative impact Dissociative Attachment

Cross - section (ang. sqrd.)

100

10

0.1
0 2 4 6 8 10 12 14 16 18 20

Energy (eV)
 SiBr2
84 Electrons

Bond length: 2.039 Ang.

Bond Angle: 122.8 Deg.
 e + SiBr2 >
10000
Elastic Dissociative impact
1000
Dissociative Attachment Ionisation
100
Cross-section (ang. sqrd.)

10

0.1

0.01

0.001

0.0001

1E-05

1E-06
0 2 4 6 8 10 12 14 16 18 20

Energy (eV)
 Surface reactions with Walls
19
H
H

H
Br
HBr
Br2 H2
Open
HBr
H
Br

Br

Br
 Surface reactions with wafer
20
   
ER /   si i  SiBr   SiBr2  Si  SiBr  SiBr2  Si  Si  SiBr  SiBr

SiH H  H2
H Br  HBr

Si H  HBr
Ion  SiBr2
Ion  SiBr

SiBr2 SiBr
Br2 Br
H  HBr
SiBr  SiBr2
Si  SiBr
SiBr2 SiBr
SiBr
Br
Br2  Br
21 Simulation model
• Comsol
• Incompressible Navier-Stokes (INSM)
• Convection and diffusion transport (CDTM)
• Convection and conduction heat transport (CCHT)
• Transverse electromagnetic wave propagation (TEM)

• Gas flow
• Electron temperature
• Charged particles
• Neutral particles

Same model for Si2H6 & NH3 PECVD:

Jozef Brcka, Song-Yun Kang,
Plasma Process. Polym. 2009, 6, S776–S783
 Microwave
22
Gas flow

Gases
inlet

Stage with rf bias

Pumping
Wafer out
 100 mTorr
Number is e- Br- SiBr2
23
maximum
[#/cm3]
With
1.6e13
SiBrx 5.0e11 1.9e13
reactions

Without
SiBrx 6.6e13
1.5e13 4.6e11
reactions

Electron distributions are localized near top, because microwave heat comes from top.
Br negative ion produced both inlet and near wafer because of attachment reaction of SiBrx.
SiBr2 in case with SiBrx reactions is localized near wafer because there are reactions of SiBr2.
 100 mTorr

24 SiBr2 SiBr Si
1.8e13
1.9e13 5.7e12

SiBr2+ SiBr+

2.3e11 4.7e11 Number is

maximum
[#/cm3]

SiBr and Si are produced from SiBr2 and SiBr respectively.

Ions produced from byproducts are localized near wafer which is dominant ions attack to
wafer.
 Ion fluxes on wafer 2.5E+16
25
2.0E+16

Flux (#/cm2 s)
40
1.5E+16
Without SiBrx 70
80
reactions 1.0E+16
100

5.0E+15

0.0E+00
Ar+ Br+ HBr+ SiBr+ Br2+ SiBr2+
5.0E+15

4.0E+15
Flux (#/cm2 s)

Including SiBrx 40
3.0E+15
70
reactions 80
2.0E+15
100

1.0E+15

0.0E+00
Ar+ Br+ HBr+ SiBr+ Br2+ SiBr2+
26
180

150

Average mass of ions

120 with SiBr2 reaction
90
without SiBr2
60 reactions

30

0
0 50 100 150
Pressure (mTorr)

o Ion mass gets heavier as pressure

increases
o Ion fluxes and energies will change
significantly with pressure in this
collisional sheath.
Specific conclusions:

o SiBr1,2 molecular data is critical in the correct understanding

of this etch process.
o SiBr1,2 ions are important in determining the etch profile and
have pressure dependant concentrations (and therefore
fluxes and energies).
o Cross-sections with SiBr4 and SiBr3 could be included.
o SiBr3,4 are not expected to be important etch products
o Ions of SiBr3,4 could be important however.

General conclusions:

o The availability of molecular data is critical to understanding

the gas-phase.
o ...and therefore what arrives at the surface.
o Cross-sections can and have been calculated on demand for
these applications.

27
 Thank you for listening
Brought to you by:

Dr. James Munro

Prof. Jonathan Tennyson,
Mr. Stephen Harrison

Dr. Song-Yun Kang

With thanks also to:

Dr. Josef Brcka & Dr. Song-Yun Kang (for 2D Comsol model)
T. Mori, M.Sasaki, T Nishizuka & T. Nozawa (for experiment)