Lecture 11.

0

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 .

H2O2  SiO2 HF.Wet Etch Chemistries  Layer Etchant  Photoresist H2SO4. HNO3  Si HF . NH4F-HCl-NH4F  Si3N4 ?.

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=α(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 .

• 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  Temperature of Gas molecules. Tgas PVm/Rg  Temperature of Electrons.

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 .

MClx(v). SiBr4(v) – MFx(v). SiF4(v). SiCl4(v).Gaseous (Volatile) Products – SiO(g). . MBrx(v).

759 eV .422 eV H 13.1st Ionization Energies O 13.814 eV  Cl 12.967 eV F 17.598 eV  Ar 15.618 eV  Br 11.

Plasma Etch Mechanism  PreClean  Metal (M) Etch • O2+ eO2+ + 2e • Cl2 + e  2Cl + e • Cl2  Cl2+ + e • O2+ e2O + 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!! .

α α = Ni/No= Qi N λD – N = neutral number density • N = Ni+No – λD = Characteristic Diffusion length (mean free path) – Qi= ionization collision cross section • Qi= 0.Degree of Ionization.283 x 10-16(cm2) Pi(E) – Pi(E)= ionization probability .

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 μ i  ion mobility μ e  electron mobility .Plasma Transport Equations  Flux.

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 .

-new technology – Zero surface tension • Complete wettability • Good for small line widths .Clean developed Photoresist off of wafer  Wet-chemical stripping agents (solvents) – Incomplete wetting at small scale  Supercritical CO2.