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Lecture 11.

Etching
Etching
Patterned
Material Selectivity is Important!!
Un-patterned
x

Etching
y
Dry Etch Wet Etch=Dissolution
Isotropic
An-isotropic dy/dt:dx/dt:1.2
dy/dt:dx/dt:6 Si Etch
Gas Phase Reaction Strong HF
SiO2 Etch
with volatile products Strong NH4OH not NaOH (Na
Frequent use of very ion is bad)
Si3N4 Etch
reactive species in a Phosphoric Acid
Plasma Metal Etch
Si Etch Acid Solution (HNO3)
SiO2 Etch Photoresist
Solvent
Metal Etch H2SO4 Solution
Etching
Wet
and Dry Etch have very different
chemical reactions!

Wetand Dry Etch have similar rate


determining steps
Mass Transfer Limiting
Surface Reaction Limiting
Similar mathematics
Wet Etch Chemistries
Layer Etchant
Photoresist H2SO4, H2O2
SiO2 HF, NH4F-HCl-NH4F
Si3N4 ?, HNO3
Si HF
Dissolution of Layer-Wet Etch
BL-Mass Transfer
A(l)+b B(s) ABb(l)
A=
Acid for metal (B) dissolution
redox reaction
Base for SiO2 (B) dissolution
Solvent for photoresist (B) dissolution
Etch Reactions
Boundary Layer Mass Transfer
Surface Chemical Reaction
Like Catalytic reaction
Product diffusion away from surface
Product Reactant
Concentration Concentration
Profile Profile
Rate Determining Steps

X
Global Dissolution Rate/Time
Depends on
Mass Transfer
Diffusion Coefficient
Velocity along wafer surface
Size of wafer
Solubility
Density of film being etched
Wet Etch Reaction

Wafers in Carriage
Placed in Etch
Solution
How Long??
Boundary Layer MT is
Rate Determining
Flow over a leading
edge for MT
Derivation & Mathcad Also a C for the
solution
Concentration profile
Local Dissolution Rate/Time
Depends on
Mass Transfer
Diffusion Coefficient
Velocity along wafer surface
Size of wafer
Solubility
Density of film being etched
Position on the wafer
see photoresist dissolution example
Dry Etch
Physical Evaporation
Not typically used
Heating chip diffuses dopants out of
position
Sputteringfrom a target
Plasma reactor with volatile reaction
product
RF Plasma Sputtering for
Deposition and for Etching

RF + DC field
Removal Rate
Sputtering Yield, S
S=(E1/2-Eth1/2) 5.2 Zt Zx
2/3

Z Z
U ( Z t2 / 3 Z x2 / 3 )3 / 4
t x

U surface binding energy


Z i atomic numbers of (t) target and (x) gas

Deposition Rate
Ion current into Target *Sputtering Yield
Fundamental Charge
Plasma
Free Electrons accelerated by a strong
electric field
Collide with gas molecules and eject e-
Collision creates more free electrons
Free electrons combine with ions to form free
radicals
Gas Ions/Free Radicals are very reactive with
materials at the wafer surface
Ions non-selective removal
Free Radicals
Plasma Conditions
Reduced Pressure ~100 mtorr
Flow of gases in and out
DC or AC (rf) electric field
Parallel plate electrodes
Other geometries
Dry Etch Chemistries
Gas Surface Etched
O2 Pre-clean
95%CF4-5% O2 Si
50%CF4-25%HBr-25%O2 Poly Si
75%Cl2-25%HBr Metal etch

CF2layer on side walls prevents wall


etching
Plasma
Temperature of Gas molecules, Tgas PVm/Rg
Temperature of Electrons,
Te =e2E2Mg/(6me2 m2 kB)
Accelerated by E field between collisions with gas molecules
m= momentum collision frequency=N g vel m(v)
Te E/Ng ERgTg/Ptot >> Tgas

kBTe > Gas Ionization Energy


kBTe > Molecular Dissociation Energy
Plasma Gas Chemistries
Reactant Gases
Physical Etch = Sputtering from chip target
Ar
Chemical Etch
O2
CF4
HBr
Cl2
CHF3
C 2F6
Mixtures
CF2 deposition (like a teflon polymer layer) prevents side
wall etch
Gaseous (Volatile) Products
SiO(g), SiF4(v), SiCl4(v), SiBr4(v)
MFx(v), MClx(v), MBrx(v),
1st Ionization Energies
O 13.618 eV
Br 11.814 eV
Cl 12.967 eV
F 17.422 eV
H 13.598 eV
Ar 15.759 eV
Plasma Etch Mechanism
PreClean Metal (M) Etch
O2+ eO2+ + 2e Cl2 + e 2Cl + e
Cl2 Cl2+ + e
O2+ e2O + e
O + e O-
Cl + s Cl-s
O2+ + e 2O x Cl-M(s) MClx(g)
O + s O-s Simultaneously
O + Si(s) s-SiO e + CF4 CF3+ +F+ 2e
e + CF3+ CF2 + F
SiO-s SiO(g)
CF3+ + CF2 (CF2)n+F
Polymer on wall of etch
Neutrals are main reactive species!!
Degree of Ionization,
= Ni/No= Qi N D
N = neutral number density
N = Ni+No
D = Characteristic Diffusion length
(mean free path)
Qi= ionization collision cross section
Qi= 0.283 x 10-16(cm2) Pi(E)
Pi(E)= ionization probability
Plasma Transport Equations
Flux, J dnn
J n Dn for neutrals
dx
dni
J i Di i ni E for ions
dx
dne
J e De e ne E for electrons
dx
i ion mobility
e electron mobility
Etch Reactions
Boundary Layer Mass Transfer
Surface Chemical Reaction
Like Catalytic reaction
Product diffusion away from surface
Product Reactant
Concentration Concentration
Profile Profile
Etch Reaction
A(g)+bB(s) ABb(g)
-(1/A) dNB/dt= -(1/A)(/MwB)dVB/dt= -(/MwB) dy/dt = - JB
JB= b JA =b Kg(CAg-CAs) BL-MT of A
JB= b JA= b ks Cag Surface Reaction
may be catalytic
JB= b JABb = Kg(CABb-s-CABb-g) BL-MT of Abb

JB= b q/Hrxn
q = h (Ts Tg) BL-HT
q = k dT/dy Conduction in wafer
Rate Determining Steps

X
Plasma Etch Rate of Polymers
Residue Build-up
Plasma Etch Rate of Polymers
Clean developed Photoresist off of wafer

Wet-chemical stripping agents


(solvents)
Incomplete wetting at small scale
Supercritical CO2.-new technology
Zero surface tension
Complete wettability
Good for small line widths

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