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37th International Conference on Plasma Science

MINICOURSE Low Temperature Plasma Modeling & Simulation and Applications ~ June 25 (Fri) 14:00-17:00 ~
Yuki Sakiyama, Ph.D. (ysaki@berkely.edu) Research Associate Department of Chemical Engineering, University of California, Berkeley

University of California, Berkeley

Outline
1. Problem setting and goals 2. Fluid modeling of atmospheric pressure plasmas 3. Simulation of atmospheric pressure plasmas using COMSOL and MATLAB 4. Plasma chemistry in atmospheric pressure plasmas 5. Neutral gas dynamics in atmospheric pressure plasmas 6. Overview of available codes for simulating low-temperature non-equilibrium plasmas

1. Problem setting and goals-1


helium RF plasma needle discharge
visible emission
CCD image (cross sectional view)

(Images courtesy of Prof. John Goree)

Predicted emission distribution

Understanding the governing equations and boundary conditions COMSOL and MATLAB Plasma chemistry Gas flow and plasma interaction

dark

bright

1. Problem setting and goals-2


corona-mode (1 mW) glow-mode (100 mW)

Y. Sakiyama and D.B.Graves, J.Phys.D 39 3451 (2006) and J.Phys.D 39 3644 (2006)

2. Fluid modeling of atmospheric pressure plasmas


2.1 Introduction 2.2 Governing equations 2.3 Necessary parameters 2.4 Boundary conditions 2.5 Local field approximation (LFA)

2.1 Introduction
problem setting
species: electrons (e), positive heavy ions (i), neutrals (n) geometry: 1-D parallel plate, gap 2mm external voltage: RF(= 13.56 MHz) gas pressure: 1 atm (= 760 torr), static gas temperature: room temperature

e n

Which equations to be solved? What is the physical meaning of the governing equations? What is appropriate boundary conditions? How and where are the necessary parameters obtained?

2.2 Governing equation-1


species continuity equation:
n j t + j = R j ,l
l

( j = e, i, n)

(eq-1) (eq-2) (eq-3) (eq-4)

drift-diffusion approximation: j = n j j E D j n j ( j = e, i, n) electron energy equation: Poissons equation:


5 5 + e ne De = e E Qe-N t 3 3 0 E = q j n j ( j = e, i, n)
j

( ne )

from (eq-1)

qj
j

n j t

+ q j j = R j ,l = 0
j j l

(eq-1) (eq-4')

total mass needs to be conserved!

from (eq-4) 0

n j E = qj t t j

(eq-1) + (eq-4) 0 E + q j j = 0 E + q j j = 0 t t j j
total current continuity equation

(eq-5)

2.2 Governing equation-2


species continuity equation:
change in time

n j t

+ j = R j ,l
l

( j = e, i, n)
local creation/loss

(eq-1)

due to motion (convection/diffusion) across the control volume

Reaction term:
Rl = k r nl = k r nl nl = k r nl nl nl

( k [ s ]) ( k [ m s ]) ( k [ m s ])
r r r 1 3 1 6 1

n
( x ) t = n ( x ) ut ( x + x ) t = n ( x + x ) u t

x x x+x

2.2 Governing equation-3


drift-diffusion approximation: j = n j j E D j n j ( j = e, i, n)
drift term (motion induced by electric field)

(eq-2)

diffusion term (motion induced by density gradient)

Note: from momentum conservation equation to drift-diffusion approximation

mnu + (mnuu) = qnE p mnmu t


= nu = qnE p q kT = nE n mm mm mm mm

(eq-6)
(eq-7)

= nE Dn

10

2.2 Governing equation-4


electron energy equation (EEE):

( ne ) t

5 5 + e ne De = e E Qe-N 3 3
electron heating

(eq-3)

change in time electron energy flux

collisional energy loss

collisional energy loss with background neutral:

Qe-N =
l

Elth klr ni ni ni

me el kb k ne ng (Te Tg ) +3 mg e

(eq-8)

inelastic loss (reaction, vibrational excitation)

3 e = kbTe : electron temperature 2 elastic loss with background gas

G.J. M. Hagelaar et al., Plasma Sources Sci. Technol. 14, 722 (2005) R.E. Robson, et al., Rev. Mod. Phys. 77, 1303 (2005)

11

2.3 Necessary parameters-1

electron (e) mobility () [m2V1s1] f ()

ions (i) const. f (, T)

neutrals (n) 0

diffusion (D) [m2s1] elastic collision rate coefficient (kel) [m3s1] inelastic collision rate coefficient (kr) [s1, m3s1, m6s1]

f ()

f (T)

f ()

f ()

f () or f (T)

f () or f (T)

12

2.3 Necessary parameters-2: electrons


collision cross section (with helium)
10
-19 -20 -21 -22 -23

[m ]

10 10 10 10

10

-2

10

-1

10 10 10 10 electron energy [eV]

10

Elastic 3 2S 1 2S 3 2P 1 2P 3SPD 4SPD 5SPD Ionization

Boltzmann equation f e + u f E v f = R( f ) for electrons: t me


10
0

(eq-9)

EEDF

EEDF (electron energy distribution function)


If EEDF is Maxwellian

10 10 10

-2

Actual EEDF is non-Maxwellian !

-4

-6

10

20 30 40 energy [eV]

50

60

13

2.3 Necessary parameters-3: electrons


parameters for electron (in He, 1 atm, and 300 K)
0.5 0.4 1.0

10 10

-12

diffusion mobility

0.8

-14

e [m /sV]

0.3 0.2 0.1 0.0 0.1


2 4 6 8 2 4 6 8 2 4

0.6 0.4 0.2 0.0

[m /s]

elestic collision excitation stepwise ionization


2 4 6 8 2 4

De [m /s]

10 10 10

-16

k
-18

ionization
6 8 2 4

-20

1 10 mean electron energy [eV]

0.1

1 10 mean electron energy [eV]

fitting functions or numerical lookup tables

e = e ( ) , De = De ( )
k el = k el ( ) , k r = k r ( )

from electron energy equation

14

2.3 Necessary parameters-4: ion mobility


1. Experimental data from literature:
H.W. Ellis, et al, At. Data Nucl. Data Tables 17, 177 (1976 ) H.W. Ellis, et al., At. Data Nucl. Data Tables 22, 179 (1978) H.W. Ellis, et al., At. Data Nucl. Data Tables 31, 113 (1984) L.A. Viehland, et al., At. Data Nucl. Data Tables 60, 37 (1995)

2. Estimation from theory


i =
3.6 103 1 + mg / mi
3 p mg ( / a0 )

ion mobility in helium [103 m2/Vs]

[m2 /Vs]
Bohr radius

(eq-10)

He+ N+ N2+ N4+ O+ O2+ He2+

1.16 2.19 2.28 1.60 2.25 2.18 1.83

NO+ N2O+ NO2+ H+ H2+ OH+ H2O+

2.15 1.84 1.78 3.39 2.69 2.69 2.28

[atm] [g-mol]

polarizability

Yu.P. Raizer, Gas Discharge Physics, (Springer, Berlin,1997) page 25

15

2.3 Necessary parameters-5: diffusion of ions


GER (generalized Einstein relation)
H.W. Ellis, et al, At. Data Nucl. Data Tables 17, 177 (1976 )

mi + mg mg ( i E )2 kbTi kbTi Di = = i , Ti = Tg + mm qi 5mi + 3mg kb


from (eq-7)

(eq-11)

effective heating from electric field

effective ion temperature in He gas


100

Ti / Tg

10

N2

He
1 10
4 2 4 6 8

+
6 8

10 10 electric field [V/m]

6 8

10

16

2.3 Necessary parameters-6: diffusion of neutrals


classical gas kinetic theory
mn + mg 3/ Dn = 1.8583 103 Tg 2 mn mg
[atm]

1/ 2

Lennard-Jones radius []

1
2 p LJ LJ

(eq-12)
collision integral [-]

LJ []
H He N O H2O N2 2.313 2.576 2.937 2.663 2.591 3.0985

LJ [-] 0.7713 0.6257 0.7298 0.7367 0.888 0.7487 NO O2 H2O2 N2O NO2 O3

LJ []
3.099 3.017 3.017 3.202 3.038 3.338

LJ [-] 0.7487 0.7546 0.755 0.8092 0.7981 0.7898

R.B. Bird, et al., Transport Phenomena (Wiley, New York, 2002), page 526 R.J. Kee, et al., Sandia Report SAND86-8246 (1986)

17

2.4 Boundary condition-1


Boundary conditions for species continuity equations
electrons: e n = ne ions: neutrals:
1 4 8kbTe + s e ne E s i ( i n ) (eq-13) me i (eq-14) (eq-15)

8kbTi 1 i n = ni + s i ni E mi 4 8kbTn 1 n n = nn mn 4

switching function
s =
1 (E n 0) 0 (E n < 0) 1 (E n < 0) 0 (E n 0) (eq-16)

E
i e e n e n

E
i

s =

G.J.M. Hagelaara, et al., Phys. Rev. E 62, 14521454 (2000) Y.B. Golubovskii, et al, J. Phys. D 35, 751 (2002)

18

2.4 Boundary condition-2


secondary electron emission coefficient from ions and metastables E
i e e

E
i

~ 0.016 E th 2

(eq-17)

(semi-empirical formula) secondary electron emission coefficient ( = 5.0 eV)

work function

[eV]
Al Fe Ni W Pt 4.25 4.31 4.5 4.54 5.32 He* He+ He2* He2+ N+

0.16 0.23 0.13 0.20 0.15 O+ N2+ O2+ N4+ O4+

0.1 0.09 0.03 0.07 0.03

Yu.P. Raizer, Gas Discharge Physics, (Springer, Berlin,1997) pages 68-71

19

2.4 Boundary condition-3


Boundary conditions for electron energy equation (EEE)
option 1: = const. (0.5 or 1.0 eV) option 2: n = e n w s i ( i n )

5 3

inward flux

from secondary electrons (w~5 eV)

(eq-18)

1D RF discharge in helium ( = 320 V)


5

m ]

1.2 0.8 0.4 0.0 0.0

electron energy [eV]

-3

ne (BC-1)

ne (BC-2)

4 3 2 1 0 0.0

(BC-2)

[10

17

density

(BC-1)

0.5

1.0 x [mm]

1.5

2.0

0.5

1.0 x [mm]

1.5

2.0

20

2.4 Boundary condition-4


Boundary conditions for Poissons equation
option 1: = ext at a powered conducting electrode =0 at a grounded conducting electrode option 2: on a dielectric surface

0 E = 0 r Ed + e s d s
dt
from Gausss law

(eq-19) (eq-20)
interface (s, s) dielectric gas E x 0 ld

= q j j
j

for perfect dielectric:

Ed =

s 0 Ld

Ed

21

2.5 Local field approximation (LFA)-1


Two options to calculate mean electron energy
EEE: LFA:
( ne ) t 5 5 + e ne De = e E Qe-N 3 3 (eq-3)

EEDF (F0)

= 0 3 2 F0 d

= f (E)

a fitting function or lookup table Electron energy dependence of field


10

10

18

comparison between EEE and LFA

energy [eV]

[m ] density

Table Fitting

-3

1 0.1

10

17

10

16

ne EEE LFA

ni

nn

He, 1 atm, 300 K


0.01 10
2

10

10

10

10

10

10

15

0.0

0.5

electric field [V/m]

1.0 x [mm]

1.5

2.0

22

2.5 Local field approximation (LFA)-2


A problem of the LFA in atmospheric pressure plasmas
ne E

ne e E

Dene

e e x
( ne ) t

e E = ( ne e E Dene ) E < 0
heating rate

electrons are cooled by field!?

EEE:

5 5 + e ne De = e E Qe-N ~ 0 3 3

Not negligible
Y. Sakiyama et al., J. Appl. Phys. 101, 073306 (2007) V.R. Soloviev et al., J. Phys. D 42, 15208 (2009)

23

3. Simulation using COMSOL and MATLAB


3.1 Introduction 3.2 How to set up and run a model in COMSOL 3.3 COMSOL with a MATLAB script 3.4 Example: plasma needle simulation (updated!)

24

3.1 Introduction
Problem setting
n j t + j = R j ,l
l

( j = e, i, n)

(eq-1) (eq-2) (eq-3) (eq-4)

e n

j = n j j E D j n j ( j = e, i, n)

5 5 + e ne De = e E Qe-N 3 t 3 ( j = e, i, n) 0 E = q j n j
j

( ne )

How to set up and run a model in COMSOL? How to evaluate the simulation results? How to control the current/power, instead of voltage?

25

3.2 Setting up and running a model-1


General idea about COMSOL Multiphysics
A convenient and powerful platform to solve reactive plasma equations: usually sets of coupled, nonlinear PDEs (partial differential equations) with associated initial and boundary conditions Treat charged and neutral species as continuum fluids (fluid model) Use either predefined modules (e.g. convection and diffusion, Helmholtz equation, etc.) or general PDE form Matlab scripts offer more flexible control of COMSOL ( e.g. solving equations sequentially and iteratively)

26

3.2 Setting up and running a model-2


Before starting to build a model cross section 1. drift-diffusion approximation m >> RF1

solve Boltzmann equation

m: ~1011-1012 [s1] for electrons ~109-1010 [s1] for ions

reaction rate

e, D e

2. electron energy equation (~109) >> RF1

solve plasma equations

27

3.2 Setting up and running a model-3


Step 1: Input constant parameters and variables Step 2: Draw simulation domain and generate meshes
use of symmetry (3D 2D 1D)

Step 3: Add the governing equations and the boundary conditions


general PDE mode rather than predefined modules Lagrange quadratic element mostly works finer meshes at electrodes and coarser meshes at the center

Step 4: Select time dependent solver


UMFPACK (default linear solver), or PARDISO (memory efficient) Absolute tolerance: 0.0001, Relative tolerance : 0.001

28

3.2 Setting up and running a model-4


A few more tips before running the simulation
Initial conditions: continuity equation: low and uniform density (e.g. ~1012 m3) electron energy equation: low and uniform (e.g. ~1 eV) Poissons equation: linear potential profile between electrodes Periodic steady state: Running for 100-1000 RF cycles Recording transient data of all variables to see the convergence at a fixed point (e.g. at the center)

Run the simulation!

29

3.2 Setting up and running a model-5


Transient behavior of variables at the center of gap (= 1 mm)
2.0
1.4

Phase-averaged properties after 500 RF cycles


5

normalized variables
1.5

nn
1.2

ne

ni

m ]

electron energy [eV]

-3 17

1.0 0.8 0.6 0.4 0.2

1.0

ne
0.5

ni

density

[10

3 2

nn

1 0 2.0

0.0

100

200

300

400

500

0.0 0.0

0.5

number of RF cycles

1.0 x [mm]

1.5

30

3.2 Setting up and running a model-6


load of the model
number of meshes: ~250 number of DOF: ~4000 60 RF cycles per hour (~5 hours until a steady state) memory usage: ~ 600 MB

computational environment
CPU: dual AMD Opteron 250 memory: 12 GB OS: Linux (OpenSuse)

After running the simulation


total current continuity: jtotal = 0
E + q j j = const. t j hi E Di <~ 2 (eq-21) (eq-5)

grid Peclet number (for ions): Pgrd =

mesh size dependency: doubling (or halving) the mesh size

31

3.3 COMSOL with Matlab-1


Example: a fixed current density

solve for a single RF cycle

A sample Matlab script to control the COMSOL solver

calculate phase-averaged current density


J total = 1
RF

RF

E + q j j dt (eq-22) t j

adjust magnitude of the voltage


= + c0 J goal J total

(eq-23)

32

3.3 COMSOL with Matlab-2


V-I curve predicted by a fluid model

2.0

current density [mA/mm ]

1.5
current control

1.0 0.5 0.0


lost convergence voltage control

100

200

300

400

500

voltage amplitude [V]

33

3.4 Plasma needle-1


Images of plasma needle discharge with surface without surface

E. Stoffels et al., Plasma Phys. Control. Fusion 46, B167 (2004) Applications in biomedicine

power: <1W voltage: ~300Vpkpk frequency: 13.56MHz gas: helium


http://medicalphysicsweb.org/

34

3.4 Plasma needle-2

Mesh size: 3 140 m Number of mesh: 3,000 5,000 Shape function: Lagrange-quadratic Number of DOF: 70,000 90,000 1 mm

= 30 m
needle RF (13.56 MHz) 1 mm axis of symmetry

35

3.4 Plasma needle-3: discharge at 1 mW


[1017 m-3] 2 1.8 1.6 1.4 1.2 1 1015 1016 1017 0.8 0.6 0.4 0.2 0

36

3.4 Plasma needle-4: discharge at 1 mW


Phase-averaged particle density
10 10
20

Current properties
0.2 1.0

19

density [m ]

10 10 10 10

18

current [mA]

electron He* He+ He2* He2+ N2+

0.1

Idsp Ie Itotal

0.5

normalized voltage

-3

0.0

0.0

17

Iion
-0.1

16

Vext

-0.5

15

0.0

0.2

0.4

0.6

0.8

1.0

-0.2 0.0

0.2

0.4

0.6

0.8

-1.0 1.0

z [mm]

ft

37

3.4 Plasma needle-5: discharge at 1 mW


16 electron energy [eV] electric field [10 Vm ]

ionization rate on the symmetry axis

0 12 -20 8 -40 4 -60 0 0.00 0.10 0.20 z [mm] joule heating inelastic loss elastic loss 0.30

Sheath

-1

heating rate [10 Wm ]

-3 9

4 3 2 1 0 -1 0.00 0.10 0.20 z [mm] 0.30

[1025 m-3s-1] 0 2 4 6 8 10

38

3.4 Plasma needle-6: discharge at 100 mW


[1019 m-3] 2 1.8 1017 1.6 1.4 1.2 1 0.8 1018 1019 1018 1019 0.6 0.4 0.2 0

39

3.4 Plasma needle-7: discharge at 100 mW


Phase-averaged particle density
10 10
21

Current properties
1.5 1.0 1.0

20

10 10 10 10

19

current [mA]

density [m ]

-3

electron He* He+ He2* He2+ N2+

0.5 0.0 -0.5 -1.0 -1.5 0.0

Ie

0.5

normalized voltage

Idsp
0.0

18

Iion
-0.5

17

Itotal

Vext
0.4 0.6 0.8 -1.0 1.0

16

0.0

0.2

0.4 0.6 z [mm]

0.8

1.0

0.2

ft

40

3.4 Plasma needle-8: discharge at 100 mW


electron energy [eV]

ionization rate on the symmetry axis

20 15 10 5 0 0.00 0.7 heating rate [10 Wm ]


-3

100 50 0 -50 -100 0.05 0.10 0.9 0.15 0.8 z [mm] joule heating inelastic loss elastic loss -150 0.20 1.0

electric field [10 Vm ] electric field [10 Vm ]

Sheath

-1

4 3 2 1 0 -1 0.00 0.7

[1027 m-3s-1] 0 3 6 9 12 15

11

0.05 0.10 0.9 0.8 0.15 z [mm]

0.20 1.0

41

3.4 Plasma needle-9: from 2D to 1D


1.5 mm

Treated surface 1 mm

Needle

Needle tip 1 mm

2D axisymmetric Minimum mesh size Number of finite element relative computational cost 3 m 4,000 1

Treated surface

1D spherical 3 m 200 1/50

42

3.4 Plasma needle-10: 1D spherical model


< low power (1 mW) >
10
20

< high power (1000 mW) >


10
22

10

19

metastables
density [m ]
-3

10

21

density [m ]

metastables
10
18

-3

10

20

10

17

positive ions

10

19

positive ions
10
16

10

18

electrons
10
15

electrons
0.4 0.6 0.8 1.0 10
17

0.0

0.2

0.0

0.2

0.4

0.6

0.8

1.0

distance from inner electrode [mm]

distance from inner electrode [mm]

43

3.4 Plasma needle-11: 1D spherical model


< phase-averaged total ionization rate >
10 10 ionization rate [m s ]
-3 -1 28

1 mm He
1000 mW 300 mW 100 mW

27

10 10 10 10 10

26

25

24

23

He (He flow: 2 m/s)


0.2 0.4 0.6 0.8 1.0 distance from the inner electrode [mm]
Photo: collaborative work with Dr. E.Stoffles in Eindhoven University of Technology

22

0.0

44

3.4 Plasma needle-12: 2D and 1D

10

20

< low power condition >


10

21

< high power condition >


metastables

10 density [m ]
-3

19

metastables density [m ]
-3

10

20

10

18

positive ions

10

19

10

17

10 electrons

18

electrons

positive ions

10

16

0.0

0.2

0.4

0.6

0.8

1.0

10

17

0.0

0.2

0.4

0.6

0.8

1.0

distance from inner electrode [mm]

distance from inner electrode [mm]

45

3.4 Plasma needle-13: 2D and 1D


Power-voltage curve
2D axisymetric 1D spherical

Time-averaged density
electron He2* density [m ]
10 10 10 10 10
21 20 19 18 17
21 20 19 18 17

He* He2+

He+ N2+

20

-3

1D spherical

power [mW]

15 10

density [m ]

10 10 10 10 10

5 0

-3

2D axisymmetric (on the axis)

80

120

160

200

voltage amplitude [V]

0.0

0.2

0.4 0.6 z [mm]

0.8

1.0

46

4. Plasma chemistry at atmospheric pressure

4.1 Introduction 4.2 Chemical reactions in fluid model 4.3 Example-1: simplified chemistry model for helium with impurity 4.4 Example-2: plasma chemistry in air 4.5 Tips for simulation with detailed chemistry model (advanced)

47

4.1 Introduction

Mass spectrometry in helium plasma needle discharge

E. Stoffels, et al., Plasma Sources Sci. Technol. 15, 501 (2006)

E. Stoffels et al., IEEE Trans. Plasma Sci., 36, 1441 (2008)

48

4.2 Chemical reactions in fluid models-1


Maxwellian? Yes! classical gas kinetic theory transition state theory empirically
k r = c0T c1 exp( E th / kbT ) (eq-24)

No (= electrons) cross sections for various species and paths

solve Boltzmann equation


various electron impact reaction rate coefficients

(c1= 0: Arrhenius equation)

e, D e

reaction rate coefficients for neutrals/ions

solve plasma equations

49

4.2 Chemical reactions in fluid models-2


A + e A* + e A + e A+ + 2e A* + e A+ + 2e A2 + e A + A + 2e A* + A* A+ + A + e A* + B B+ + A + e A+ + e + M A + M A + e A A + B A + B + e A+ + B A + B+ A+ + B + M A + B + M A+B+MC+D+M f() f() f() f() f(Tg) f(Tg) f() f() f(Tg) f(Tg) f(Tg) f(Tg) electron impact excitation electron impact ionization stepwise ionization electron impact dissociation associative ionization Penning ionization electron recombination electron attachment electron detachment charge transfer ion recombination neutral-neutral reaction

f(): rate constant obtained by solving Boltzmann equation

50

4.2 Chemical reactions in fluid models-3


Resources for reaction rate coefficient and cross sections data set
Cross section data set by A.V. Phelps in JILA (http://jila.colorado.edu/~avp/) Cross sections available in BOLSIG+ GAPHYOR online database (http://gaphyor.lpgp.u-psud.fr/) M. Capitelli, et.al, Plasma kinetics in atmospheric gases (Springer, Berlin, 2000). L.M. Chanin, et al., Phys. Rev. 128, 219 (1962). T. D. Mark, et al., Phys. Rev. A 4, 1445 (1971). H.W. Ellis, et al., At. Data Nucl. Data Tables 22, 179 (1978). C.B. Collins, et al., J. Chem. Phys. 68, 1391 (1978). J.W. Parker, et.al, J. Chem. Phys. 75, 1804 (1981). J.M. Pouvesle, et.al, J. Chem. Phys. 77, 817 (1982). H. Bohringer, et al., Int. J. Mass Spectrom. Ion Phys. 52, 25 (1983). J.M. Pouvesle, J. Chem. Phys. 83, 2836 (1985). F. Emmert, et al., J. Phys. D 21, 667 (1988).

51

4.2 Chemical reactions in fluid models-4


H. Matzing, Adv. Chem. Phys. 80, 315 (1991). I.A. Kossyi, et.al, Plasma Sources Sci. Technol. 1, 207 (1992). M.J. Kushner, J. Appl. Phys. 74, 6538 (1993). P.C. Hill, et al., Phys. Rev. A 47, 4837 (1993). T.L. Williams, et al., Mon. Not. R. Astron. Soc. 282, 413 (1996). R. Atkinson, et al., J. Phys. Chem. Ref. Data 26, 1329 (1997). G.S. Voronov, At. Data Nucl. Data Tables 65, 1 (1997). O. Eichwald, et al., J. Appl. Phys. 82, 4781 (1997). H. Tawara, et al., NIFS DATA-51 (1999). V.G. Anicich, J. Phys. Chem. Ref. Data 22, 1469 (1999). S. Rauf, et al., J. Appl. Phys. 88, 3460 (1999). L.W. Sieck, et al., Plasma Chem. Plasma Process. 20, 235 (2000). J.T. Herron, et al., Plasma Chem. Plasma Process. 21, 459 (2001). I Stefanovic et al., Plasma Sources Sci. Technol. 10, 406416 (2001). F. Tochikubo, et al., Jpn. J. Appl. Phys. 41, 844852 (2002). R. Dorai, et al., J. Phys. D 36, 666 (2003). C.D. Pintassilgo et al., J. Phys. D 38, 417430 (2005). K.R. Stalder, et.al, J. Appl. Phys. 99, 093301 (2006). etc. etc. etc

52

4.3 Helium plasmas with impurity-1


He DBD for material processing OES in helium glow DBD

measured waveform

A. Ricard et al., Surf. Coat. Tech. 112, 1 (1999)

53

4.3 Helium plasmas with impurity-2


Index R1 R2 R3 R4 R5 R6 R7 R8 R9 R10 R11 R12 R13 Reaction He + e He* + e He + e He+ + 2e He* +e He+ + 2e He* + 2He He2* + He He+ + 2He He2+ + He He2 + M 2He + M 2He*
+ *

He R1

R2

He+ + R3

He* R7 R4 He2* R10 R11 N2+ + e R8 He2+ + e

He2 + e He* + He

2He2* He2+ + 2He + e He2 + e He* + N2 N2+ + He + e He2* + N2 N2+ + 2He + e He2+ + N2 N2+ + He2* N2+ + e N2

Y B. Golubovskii, et al.,J. Phys. D 36, 39 (2003) Y. Sakiyama et al., J. Appl. Phys. 101, 073306 (2007)

54

4.3 Helium plasmas with impurity-3


Particle density distributions with 0.5ppm N2 (helium RF) Volume-averaged particle density for different impurity level (helium DBD)

T. Martens et al., Appl. Phys. Lett. 92, 041504 (2008) X. Yuan, et al., IEEE Trans. Plasma Sci., 31, 495 (2003)

55

4.4 Plasma chemistry in air-1


48 species 11 negative particles: e, O, O2, O3, O4, H, OH, NO, N2O, NO2, NO3 16 positive particles: N+, N2+, N3+, N4+, O+, O2+, O4+, NO+, N2O+, NO2+, H+, H2+, H3+, OH+, H2O+, H3O+ 21 neutrals/radicals: N, N*, N2, N2*, N2**, O, O*, O2, O2*, O3, NO, N2O, NO2, NO3, N2O5, H, H2, OH, H2O, HO2, H2O2 630 reactions 21 electron impact excitation/ionization/dissociation 76 electron recombination/attachment 159 charge transfer 245 ion recombination 129 neutral-neutral reactions

56

4.4 Plasma chemistry in air-2


Various air DBD devices for biomedicine

Drexel, US

Berkeley, US

Max-Planck, DE

Model description
pulse-like plasmas 0D simulation (spatially uniform plasmas) pressure: 1 atm gas temperature: 300 K gas concentration: air with 30% humidity computational time: ~10 hours (Dual Opteron 250, 12GB Mem, comsol3.5a)

n j t

= R j ,l
l

on (100 ns)

E = 3106 V/m ne = 1017 m3

1 cycle (100 s)

57

4.4 Plasma chemistry in air-3

time development of species density (in periodic steady state)


10 10 10
0

-1 -2 -3 -4 -5 -6 -7 -8 -9

Ox NxOy

neutrals

positive ions

negative ions

density fraction

10 10 10 10 10 10 10

HxOy Nx
+ HxOy + Ox

Ox HxOy
-

NxOy

electron
-7 -5

10

-9

10 time [s]

-7

10

-5

10

-9

10 time [s]

-7

10

-5

10

-9

10 time [s]

10

58

4.4 plasma chemistry in air-4


phase-averaged species density (in periodic steady state)
10 10 10
0

-1 -2 -3 -4 -5

O3

density fraction

10 10 10 10 10 10

O2 H2 N O OH NO

H2O2 HO2

N2O NO2

N2O5

-6 -7 -8

NO3

(charged particle density < 10ppb)

59

4.4 plasma chemistry in air-5


Ozone reaction paths 3%: NO + O3 NO2 + O2 4%: O2* + O3 O + 2O2 6%: e + O3 O + O2 + e

74%
O + O2 + M O3 + M

6%: O3 + OH HO2 + O2

60

4.4 plasma chemistry in air-6


NO reaction paths 4%: N + OH NO + H

41%: NO + O3 NO2 + O2

5%: NO + HO2 NO2 + OH

8%: N* + O2 NO + O*

30%: O + NO2 NO + O2

61

4.4 plasma chemistry in air-7


NO2 reaction paths 4%: NO + HO2 NO2 + OH 7%: O + NO2 + M NO3 + M 8%: NO2 + NO3 + M N2O5 + M 29%: O + NO2 NO + O2

40%: NO + O3 NO2 + O2

62

4.4 plasma chemistry in air-8


O2 O e, O2* O3 OH N HO2 NO2 O NO3 N2O5 NO N*

63

4.5 Tips for complex chemistry model-1


Before starting simulation with hundreds of reactions
n1 1 + 1 = R1 + R12 + K + R1Nr t n2 N 1 2 + 2 = R2 + R2 + K + R2 r t M nNs N 2 + Ns = R1 s + RNs + K + RN r N s t

Ns

highly nonlinear problems (stiff problem)

heavy computation

Nr For example 40 species/700 reactions (air) one-dimensional, RF excitation 12 GB, Dual Opteron 250

wait for a few months until reaching steady state?

64

4.5 Tips for complex chemistry model-2


To reduce the computational time
1. Sensitivity analysis
dn j dt + j = R (klr , t ) = klr nl nl (eq-1 ) (eq-25)

d n R R R t = = + dt klr klr klr t klr dS jl R R S jl = 0 = r + dt kl n j


(steady state assumption)

R R n j = r + r kl n j kl (eq-26)

S jl =

n klr
sensitivity coefficient

R S jl = n j (jl) matrix

R klr

(eq-27)

(l1) matrix

low computational load perturbation around equilibrium state sensitivity dominant reaction path
H. Rabitz et al, Ann. Rev. Phys. Chem. 34, 419 (1983)

65

4.5 Tips for complex chemistry model-3


To reduce the computational time
2. Reference calculation solve ODEs in several typical conditions (e.g. given ne, )
dn j dt + j = R(klr , t ) = klr nl nl (eq-1 )

calculate contribution matrix (normalized reaction rates for each species)


species

R11 L R1Ns O M lj = M R N r 1 L R Ns N r
normalized

reaction

(eq-28)

medium computational load directly evaluating reaction rate need of finding typical conditions

eliminate unimportant reaction paths (e.g. 1% threshold)

66

5. Neutral gas dynamics


5.1 Introduction 5.2 Interaction between neutral gas flow and plasmas 5.3 Example-1: Plasma jet and flow (one-way coupling) 5.4 Example-2: RF plasma needle and flow (two-way coupling)

67

5.1 Introduction
Loughborough, UK

gas: rare gas, air, hydrocarbon power: DC, RF, Microwave


Greifswald, GE Eindhoven, NL Old Dominion, US

application: etching, thin film deposition, biomedicine

air feed gas plasmas

68

5.2 Plasma-flow interaction-1


Assumption: laminar flow, no thermal radiation
Re = ud

< Rec (~ 2000 : inside a tube)

Governing equations for neutral gas flow:


total mass conservation:

( u ) = 0 T + ucpT = Q ( air u Dair ) = 0 p = RT

(eq-29) (eq-30) (eq-31) (eq-32) (eq-33)

total momentum conservation: ( uui ) = p ( 0 ) g total energy conservation: mass conservation of air: perfect gas law:

(need compressible N-S equation !)


R.B. Bird, et al., Transport Phenomena (Wiley, New York, 2002)

69

5.2 Plasma-flow interaction-2

neutral gas heat and mass transfer model gas temperature gas velocity gas component

momentum transfer energy transfer

plasma fluid model

background gas density mobility and diffusion coefficients for electrons/ions diffusion coefficients for neutrals reaction rate coefficients (including elastic energy loss) flux of species

70

5.2 Plasma-flow interaction-3


Momentum transfer from plasmas to neutral gas flow
body force (ion wind): f pls ~ qi ni E
from ions

(eq-34)
E N N i N N

mnu + (mnuu) = qnE p mnmu t f pls = mn jm, j u j


j =i , e

(eq-6)

m j n j u j q j n j E p j (m j n j u j u j ) t j =i , e

Under typical conditions: qi ni E > qe ne E, kb(neTe ) > others


J.P. Boeuf et al., J. Appl. Phys. 97, 103307 (2005) C.C. Leiby, Phys. Fluids 10, 1992 (1967) J-S Chang, IEEE Trans. Diel. Electr. Insul. 1, 871 (1994)

71

5.2 Plasma-flow interaction-4


Energy transfer from plasmas to neutral
heating source: Qpls ~ Qe-N + qi i E + QN-N
electrons (eq-8) ions

(eq-35)

chemical reactions

Energy transfer between electrons, ions, and neutrals

external electrical power P = qe e E + qi i E (=Joule heating) source terms for EEE source terms for IEE

Se = qe e E Qe-N Qe-i
elastic collision

Si = qi i E + Qe-i Qi-N Qi-N ~ qi i E + Qe-i

(~ 0)

Qpls = Qe-N + Qi-N + QN-N = Qe-N + qi i E + Qe-i + QN-N


from plasmas to neutral

72

5.2 Plasma-flow interaction-5


Assumption: heat/mass transfer from neutral ( < ~103 s) >> RF (external electric field oscillation)

solve time dependent plasma equations for one RF cycle

f pls =

RF

RF

qi ni Edt ,

Qpls =

RF

RF

qi ni E dt

solve steady state neutral gas flow equations

73

5.3 Plasma jet-1: introduction

X.Liu and M.Larousi, J. Appl. Phys. 100, 063302 (2006).

Observed ring-shaped emission pattern

M. Teschke et al, IEEE Trans. Plasma Sci. 33, 310 (2005)

N. Merciam-Bourdet et al, J. Phys. D 42, 055207 (2009)

74

5.3 Plasma jet-2: one way coupling


He: 7 slpm 7 kV pulse excitation 8 kHz repetition
r N2 He

2D steady state neutral gas flow N2 density distribution

N2 density
c

1D plasma dynamics in cylindrical coordinates (cross sectional view)

75

5.3 Plasma jet-3: neutral gas flow


0.4

mole fraction of N 2

0.3 0.2 0.1 0.0 0.0

Compressible N-S equation


( u ) = 0

: total mass continuity

N2 u DN2 = 0 : continuity for N2 ( uui ) = p


0.5 1.0 r [mm] 1.5 2.0

: total momentum continuity

Mole fraction of air


20 r [mm] z

N2 rich

10

He channel

0 -20

-10

10

20

30

40

50

He rich

76

5.3 Plasma jet-4: plasma dynamics


N2
species: e, He*, He2*, He+, He2+, N2*, N2+

nN2 rate coefficients: from local Boltzmann equation


(local field and N2 concentration)

He channel 0

pressure: 1 atm

temperature: 300 K solver: COMSOL and Matlab

Fluid model with local field approximation

ni 1 (ri ) + = Si t r r

(mass continuity)

ni i = sgn(qi ) ni i Er Di (drift-diffusion) r 1 (rEr ) = qi ni (Poissons eq. in r-direction) 0 r r i

77

5.3 Plasma jet-5: given electric field

nN2

Ez
0

Given electric field (not self-consistent!) Ez = 3105 V/m 400 ns 0 125 s (8 kHz)
reaction rate:

E=

Er + Ez

Poissons eq.

given

k = f (E)

78

5.3 Plasma jet-6: time evolution of bullet

given electric field

particle density distribution in radial direction

79

5.3 Plasma jet-6: time evolution of bullet

80

5.3 Plasma jet-7: Penning ionization is a key


Ez [10 V/m]
4 3 2 1 0
5

200

400

time [ns]

600

800

1000

10 10

29

early stage (200 ns)


excitation direct ionization Penning ionization

10 10

29

late stage (400 ns)


excitation direct ionization Penning stepwise associative

28

28

reaction rate [m s ]

10 10 10 10 10

27

reaction rate [m s ]

-3 -1

-3 -1

10 10 10 10 10

27

26

e He* He He2* N2+

N2 e

26

25

25

24

24

23

23

0.0

0.5

1.0 r [mm]

1.5

2.0

0.0

0.5

1.0 r [mm]

1.5

2.0

81

5.3 Plasma jet-8: for comparison with simulation


Time resolution: 1 ns Spatial resolution: ~50 m

inner diameter: 3 mm

amplitude : 7 kV pulse width : 2 s repetition rate : 8 kHz Helium flow: 7 slpm

82

5.3 Plasma jet-9: ionization = emission?


6000 5000

+ + B2 u X 2 g
OH N2 N2
+

3 S , P, D 2 S , P
He He

He O

intensity

4000 3000 2000 1000 0

N2

N2

He
500 600 700

He
800

300

400

wavelength [nm]

N2+(B) He*, He2* (40%) kPen He2+ (75%) kchg Emission rate = kem ~ kPen+ kchg (kem >> kPen, kchg) kem N2+(X) kex kem

3SPD

2P 2S

Emission rate = kem ~ kex (kem >> kex) ~ kiz (kiz ~ kex)

Effective emission rate = kiz + kPen+ kchg

83

5.3 Plasma jet-10: ring shaped pattern


Y. Sakyiama et al, Appl. Phys. Lett. 96 (2010) 041501

r z 0
1.0

20 mm

40 mm

integration time for OES: 100 ms (800 bullets)

OES
0.8

Model

normalized intensity

0.6 0.4 0.2 0.0 -2

-1

0 r [mm]

84

5.4 Plasma needle-1: introduction


RF(13.56 MHz)-excited gas: He gap distance: 2.5 ~ 4 mm light intensity

0.3 m/s

1.0 m/s

4 radial position

4 radial position

5 mm Killing pattern
J.Goree, et al, J. Phys. D. 39, 3479 (2006) and IEEE Trans.Plasma Sci. 34, 1317 (2006) (Images courtesy of Prof. John Goree)

85

5.4 Plasma needle-2: two-way coupling


Neutral Gas flow He flow
( u ) = 0, ( air u Dair ) = 0 ( uui ) = p + qi ni E T + ucpT = + qi i E + Qel

(mass conservation) (energy conservation)

(momentum conservation)

air (diffusion) Plasma dynamics


ni + i = Si t i = sgn(qi ) ni i E Di ni + ni u ( ne )

(mass conservation) (drift-diffusion)

5 5 + e ne De = e E Q (electron energy) 3 t 3 (Poissons equation) 0 E = qi ni


Y. Sakyiama et al, Plasma Sources Sci. Technol. 18, 025022 (2009).

86

5.4 Plasma needle-3: neutral gas flow


He (1.5 m/s) 1 mm needle N2 (1atm) 2.5 mm z r 5 mm insulator

N2 (1atm)

Unknown variables He/N2 concentration gas pressure

glass plate 5 mm

gas flow velocity (r and z) gas/needle temperature

87

5.4 Plasma needle-4: plasma dynamics

needle 0.85 mm insulator 1.5 mm

1 mm

Unknown variables density: electron, He*, He+,


glass plate 2 mm

He2*, He2+, N2+ electron energy electrical potential

88

5.4 Plasma needle-5: gas flow field


Mole fraction of air (log scale) Gas temperature

89

5.4 Plasma needle-6: particle density


0.5 0 z [mm]

electrons

1019

He*

-0.5

1018 1017

1018 1016 1018

1017

1016

-1 0.5 0 z [mm]

He2+ 1018

N2+

-0.5

1017 1016
1017 1.5 2 0 0.5 1 r [mm] 1.5 1016 2

-1

0.5

1 r [mm]

90

5.4 Plasma needle-7: ring-shaped emission!


Predicted emission intensity
0.5

Experimental results by J. Goree et al


insulator needle

e He* He He2* N2+

N2 e He gap: 3 mm

0 z [mm]

He

-0.5

-1 0

0.5

1 r [mm]

1.5 [1023

2 m-3s-1] 1

4 mm

0.2

0.4

0.6

0.8

91

5.4 Plasma needle-8: one-way coupling (again)


humid air concentration: 2D neutral flow simulation (N-S equation, convection-diffusion) 1D fluid model with detailed chemistry in spherical coordinates on-axis on-axis
(1mm gap) Humid air concentration needle Insulator tube

off-axis
nair/nHe>10-3 S. mutans

off-axis
(2mm gap)

nair/nHe<10-5 S. mutans

Which is the major species hitting the surface?

92

5.4 Plasma needle-9: charged particle density


on-axis (1mm gap)
10 10
21

off-axis (2mm gap)


10
21

20

He2+ O+

N+,N2+
density [m ]
-3

10 10 10 10 10

20

He2+ N+,N2+ NO+ O+,O2+

density [m ]

-3

10 10 10 10

19

H2O+,H+,OH+

19

18

18

17

NO+

17

16

16

0.0

0.2

0.4

0.6

0.8

1.0

0.0

0.5

1.0

1.5

2.0

r [mm]

r [mm]

93

5.4 Plasma needle-10: neutral density


on-axis (1mm gap)
10 10
21

off-axis (2mm gap)


10
21

20

N,N*,N2*

He*,He2* O,O*,O2*
density [m ]
-3

10 10 10 10 10

20

He*,He2* O,O*,O2* N,N*,N2*

density [m ]

-3

10 10 10 10

19

19

18

H,OH,H2

18

NO H,OH,H2

17

17

16

16

0.0

0.2

0.4

0.6

0.8

1.0

0.0

0.5

1.0

1.5

2.0

r [mm]

r [mm]

94

5.4 Plasma needle-11: reaction kinetics


On-axis (1mm gap) Off-axis (2mm gap)
He* He* N2+ He2* e He2+ N2+ O2+ N2** N2* O O* N* N O2* H2O+ O2+

OH

NO

95

5.4 Plasma needle-12: flux to a surface


12

flux [10 m s ]

-2 -1

10 8 6 4 2 0

On-axis (1mm gap)


S. mutans
e He2
+

19

N2

O2

12

flux [10 m s ]

-2 -1

10 8 6 4 2 0

Off-axis (2mm gap)


S. mutans

19

e H N OH H2O N + 2 NO
+

O2

O2

96

6. Available codes for plasma simulation-1


1. Bolsig+: Boltzmann solver for electrons freeware developed and managed by Dr. Hagelaar in LAPLACE ( G.J. M. Hagelaar et al., Plasma Sources Sci. Technol. 14, 722 (2005)) 2. ELENDIF: Boltzmann solver Kinema Research & Software (http://www.kinema.com/)

3. HPEM: solver for low pressure plasma processing reactors (ICP, RIE, ECR, etc) developed and managed by CPSEG in U. Michigan (http://uigelz.eecs.umich.edu/)

97

6. Available codes for plasma simulation-2


4. CFD-ACE+: general PDE solver plasma physics module available ESI Group (http://www.esi-group.com/)

5. ANSYS Fluent: general fluid dynamics solver applicable to low pressure CVD simulation ANSYS Inc. (http://www.ansys.com/)

6. COMSOL Multiphysics: FE (finite element) solver ~20 pre-defined application modules from fluid dynamics to mechanics plasma module included in the latest version 4.1 Comsol, Inc. (http://www.comsol.com/)

98

6. Available codes for plasma simulation-3


7. SIGLO and SIPDP series: plasma fluid solver in 1-D and 2-D from AC to RF Kinema Research & Software (http://www.kinema.com/)

8. XPDP1, XPDP2, XPDS1: particle-in-cell (PIC) solver freeware developed and managed by PTSG group in UC Berkeley (http://ptsg.eecs.berkeley.edu/) 9. VORPAL, OOPIC Pro: PIC solver Tech-X corp. (http://www.txcorp.com/)

10. LSP Suite: 2-D and 3-D PIC solver Alliant Techsystems Inc. (http://www.mrcwdc.com/LSP/)

99

Notation
cp: specific heat [J kg1 K1] R: S: t: T: reaction rate [m3s1] sensitivity coefficient time [s] temperature [K]

D : diffusion coefficient [m2s1] e: electron charge (=1.601019) [C] Eth: ionization/excitation energy [eV] fpls: body force from plasmas [kg m s2] g: J: h: gravity (= 9.81) [m s2] current density [A m2] grid size [m]

kinel: reaction rate coefficient [s1, m3s1, m6s1 ] kel: elastic collision rate coefficient [m3 s1] kb: m: n: p: Boltzmann constant (=1.381023) [J K1] mass [kg] density [m3] pressure [Pa]

Qpls: heating from plasmas [W m3] Qe-N: collisional energy loss [W m3] Q: viscous heat dissipation [W m3]

100

Notation-2
: mean electron energy [eV] 0 : vacuum permittivity (=8.851012)
[CV1m1] E: electric field [V m1] : flux [m2s1] n: unit surface vector [-] : stress tensor [Pa] u: neutral gas velocity [m s1]

r : dielectric constant : electrical potential [V]


: secondary electron emission coefficient [-]

: work function [eV]


: thermal conductivity [W m1 K1]

RF: RF period [s] : mobility [m2 V 1 s1]

: neutral gas density [m3] s: surface charge [Cm2]

Subscripts e : electron i : heavy positive ions n: neutrals g: background gas

m: momentum transfer collision frequency [s1] : electron energy relaxation frequency [s1]

air:mass fraction of air