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Oxidation Oxidation

Oxidation Oxidation
Introduction
Applications Applications
Mechanism
P Process
System
RTO
Introduction Introduction
Siliconreactswithoxygen
Stable oxide compound Stableoxidecompound
WidelyusedinICmanufacturing
Si+O
2
SiO
2
Oxidation
OriginalSiliconSurface
SiliconDioxide
Silicon
O
O
2
O
2
O
2
O
2
O
2
O
2
O
2
O
2
O
2
O
2
O
2
O
2
O
2
O
2
O
2
45% 55%
SomeFactsAboutSilicon
Name Silicon Name Silicon
Symbol Si
Atomic number 14
Atomic weight 28.0855
Discoverer J ns J acob Berzelius Discoverer J ns J acob Berzelius
Discovered at Sweden
Discovery date 1824
Origin of name From the Latin word "silicis" meaning "flint"
Bond length in singlecrystal Si 2 352 Bond length in single crystal Si 2.352
Density of solid 2.33 g/cm
3
Molar volume 12.06 cm
3
Velocity of sound 2200 m/sec
Hardness 6 5 Hardness 6.5
Electrical resistivity
100,000 cm
Reflectivity 28%
Melting point
1414 C
B ili i t
2900 C
Boiling point
2900 C
Thermal conductivity 150 W m
-1
K
-1
Coefficient of linear thermal
expansion
2.610
-6
K
-1
Etchants (wet) HNO
4
and HF, KOH, etc.
Etchants (dry) HBr, Cl
2
, NF
3
, etc.
CVD Precursor SiH
4
, SiH
2
Cl
2
, SiHCl
3
, and SiCl
4
FactAboutOxygen
Name Oxygen
Symbol O
Atomic number 8
Atomic weight 15.9994
Discoverer J oseph Priestley, Carl Scheele
Discovered at England, Sweden
Discoverydate 1774 Discovery date 1774
Origin of name From the Greek words "oxy genes" meaning
"acid" (sharp) and "forming" (acid former)
Molar volume 17.36 cm
3
Velocity of sound 317.5 m/sec
Refractivity 1.000271
Melting point
54.8 K =-218.35 C
Boilingpoint
902K 18295C
Boiling point
90.2 K =-182.95 C
Thermal conductivity 0.02658 W m
-1
K
-1
Applications Thermal oxidation, oxide CVD, reactive
sputtering and photoresist stripping
Main sources O
2
, H
2
O, N
2
O, O
3
Application of Oxidation ApplicationofOxidation
DiffusionMaskingLayer
Surface Passivation SurfacePassivation
Screenoxide,padoxide,barrieroxide
Isolation Isolation
FieldoxideandLOCOS
Gateoxide
Diffusion Barrier DiffusionBarrier
MuchlowerBandPdiffusionratesinSiO
2
than
thatinSi
SiO
2
canbeusedasdiffusionmask
Dopant
SiO
2
SiO
2
Si
SiO
2
SiO
2
Application, Surface Passivation Application,SurfacePassivation
PadOxide ScreenOxide
Sacrificial Oxide Barrier Oxide
SiO
2
SacrificialOxide BarrierOxide
Si
Normallythinoxidelayer(~150)toprotectsilicon
defects from contamination and over stress defectsfromcontaminationandoverstress.
ScreenOxide
Dopant Ions
Photoresist Photoresist
DopantIons
Si Substrate SiSubstrate
ScreenOxide
PadandBarrierOxidesinSTIProcess
PadOxide
Nitride
Silicon
TrenchEtch
USG
l
PadOxide
Nitride
Silicon
USG
BarrierOxide
TrenchFill
Silicon
USGCMP;USGAnneal;NitrideandPadOxideStrip
Application, Pad Oxide Application,PadOxide
Relievestrongtensilestressofthenitride
Preventstressinducedsilicondefects
l d
PadOxide
Siliconnitride
SiliconSubstrate
Application, Device Isolation Application,DeviceIsolation
Electronicisolationofneighboringdevices
Blanketfieldoxide
Local oxidation of silicon (LOCOS) Localoxidationofsilicon(LOCOS)
Thickoxide,usually3,000to10,000
BlanketFieldOxideIsolation
Silicon
WaferClean
Silicon
SiliconDioxide
Fi ld O id
FieldOxidation
ActivationArea
Silicon
FieldOxide
OxideEtch
LOCOSProcess
Siliconnitride
P t b t t
PadOxide
Ptypesubstrate
Padoxidation,nitridedepositionandpatterning
b
Siliconnitride
SiO
2
Ptypesubstrate p
+
p
+
p
+
IsolationDoping
LOCOSoxidation
BirdsBeak
Ptypesubstrate p
+
p
+
p
+
IsolationDoping
SiO
2
Nitrideandpadoxidestrip
LOCOS LOCOS
C ith bl k t fi ld id Comparewithblanketfieldoxide
Betterisolation
Lowerstepheight
Lesssteepsidewall
Disadvantage
roughsurfacetopography
Birdsbeak
Replacingbyshallowtrenchisolation(STI) p g y ( )
Application, Sacrificial Oxide Application,SacrificialOxide
Defectsremovalfromsiliconsurface
STI
USG
SacrificialOxide
NWell
PWell
STI
USG
SacrificialOxidation
NWell
PWell
STI
USG
StripSacrificialOxide
Gate Oxide
NWell
PWell
STI
USG
G t O id ti
GateOxide
GateOxidation
Application, Device Dielectric Application,DeviceDielectric
Gate oxide: thinnest and most critical layer Gateoxide:thinnestandmostcriticallayer
Capacitordielectric
Poly Si
V
D
>0 V
G
n
+
Gate
Thinoxide
Si
n
+
Si Substrate
Source Drain
pSi
Electrons
Oxide and Applications OxideandApplications
NameoftheOxide Thickness Application Timeinapplication
Native 15 20 undesirable
Screen ~200 Implantation Mid70stopresent
Masking ~5000 Diffusion 1960stomid1970s
FieldandLOCOS 3000 5000 Isolation 1960sto1990s
Pad 100 200 Nitridestressbuffer 1960stopresent
Sacrificial <1000 Defectremoval 1970stopresent
Gate 30 120 Gatedielectric 1960stopresent
Barrier 100 200 STI 1980stopresent
Silicon Dioxide Grown on Improperly SiliconDioxideGrownonImproperly
CleanedSiliconSurface
PreoxidationWaferClean
Particulates
Organicresidues
Inorganicresidues g
Nativeoxidelayers
RCA Clean RCAClean
Developed by Kern and Puotinen in 1960 at RCA DevelopedbyKernandPuotinenin1960atRCA
MostcommonlyusedcleanprocessesinICfabs
SC O O O i h 2 i SC1 NH
4
OH:H
2
O
2
:H
2
Owith1:1:5to1:2:7ratio
at70to80Ctoremoveorganiccontaminants.
SC2 HCl:H
2
O
2
:H
2
Owith1:1:6to1:2:8ratioat70
to80Ctoremoveinorganiccontaminates.
DIwaterrinse
HF dip or HF vapor etch to remove native oxide HFdiporHFvaporetchtoremovenativeoxide.
PreoxidationWaferClean
ParticulateRemoval
Highpuritydeionized(DI)wateror
f ll d b i H
2
SO
4
:H
2
O
2
followedbyDIH
2
Orinse.
Highpressurescruborimmersioninheated
dunktankfollowedbyrinse,spindry
and/ordrybake(100to125C).
PreoxidationWaferClean
OrganicRemoval
Strongoxidantsremoveorganicresidues.
H
2
SO
4
:H
2
O
2
orNH
3
OH:H
2
O
2
followedbyDI
H
2
Orinse.
Highpressurescruborimmersioninheated
dunktankfollowedbyrinse,spindry y , p y
and/ordrybake(100to125C).
PreoxidationWaferClean
InorganicRemoval
HCl:H
2
O.
Immersionindunktankfollowedbyrinse,
spindryand/ordrybake(100to125C).
PreoxidationWaferClean
NativeOxideRemoval
HF:H
2
O.
Immersionindunktankorsinglewafer
vaporetcherfollowedbyrinse,spindry
and/ordrybake(100to125C).
Oxidation Mechanism OxidationMechanism
Si+O
2
SiO
2
Oxygen comes from gas Oxygencomesfromgas
Siliconcomesfromsubstrate
O diff i i ili Oxygendiffusecrossexistingsilicon
dioxidelayerandreactwithsilicon
Thethickerofthefilm,thelowerof
thegrowthrate
Oxide Growth Rate Regime OxideGrowthRateRegime
LinearGrowthRegime
B
n
e
s
s
A
X=t
O
x
i
d
e

T
h
i
c
k
n
DiffusionlimitedRegime
X= Bt
O
OxidationTime
<100> Silicon Dry Oxidation <100>SiliconDryOxidation
1 2
1.0
1.2
1200C
<100>SiliconDryOxidation
0.6
0.8
s
s

(
m
i
c
r
o
n
)
1150C
1100C
0 2
0.4
d
e

T
h
i
c
k
n
e
s
1050C
1000C
950C
2 4 6 8 10 12 14 16 18 20
0.2
0
O
x
i
d
900C
OxidationTime(hours)
Wet (Steam) Oxidation Wet(Steam)Oxidation
Si + 2H
2
O SiO
2
+ 2H
2
Si+2H
2
O SiO
2
+2H
2
AthightemperatureH
2
OisdissociatedtoH
and H O andHO
HOdiffusesfasterinSiO
2
thanO
2
Wetoxidationhashighergrowthratethandry
oxidation.
<100>SiliconWetOxidationRate
3.0
1150C
1100 C
<100>SiliconWetOxidation
2 0
2.5
n
)
1100 C
1050C
1000C
1.5
2.0
e
s
s

(
m
i
c
r
o
n
950C
900C
0.5
1.0
x
i
d
e

T
h
i
c
k
n
2 4 6 8 10 12 14 16 18 20 0
Oxidation Time (hours)
O
x
OxidationTime(hours)
Oxidation Rate OxidationRate
Temperature
Chemistry wet or dry oxidation Chemistry,wetordryoxidation
Thickness
P Pressure
Waferorientation(<100>vs.<111>)
Silicondopant
OxidationRate
Oxidation rate is very sensitive (exponentially
Temperature
Oxidationrateisverysensitive(exponentially
related)totemperature
Higher temperature will have much higher Highertemperaturewillhavemuchhigher
oxidationrate.
The higher of temperature is, the higher of the Thehigheroftemperatureis,thehigherofthe
chemicalreactionratebetweenoxygenand
siliconisandthehigherdiffusionrateof
oxygeninsilicondioxideis.
OxidationRate
WaferOrientation
<111>surfacehashigheroxidationrate
h f than<100>surface.
Moresiliconatomsonthesurface.
WetOxidationRate
1.6
1.8
<111>Orientation
1200C
1.2
1.4
m
i
c
r
o
n
)
95CWater
1100C
0.8
0.6
1.0
h
i
c
k
n
e
s
s

(
m
1000C
0.4
0.2
0.6
O
x
i
d
e

T
h
920C
1 2 3 4 0
Oxidation Time (hours) OxidationTime(hours)
OxidationRate
D t C t ti DopantConcentration
Dopantelementsandconcentration
Highlyphosphorusdopedsiliconhashigher
growthrate,lessdensefilmandetchfaster.
Generallyhighlydopedregionhashigher y g y p g g
growratethanlightlydopedregion.
More pronounced in the linear stage (thin Morepronouncedinthelinearstage(thin
oxides)ofoxidation.
Oxidation: Dopants Oxidation:Dopants
PileupandDepletionEffects
Ntypedopants(P,As,Sb)havehigher
solubilityinSithaninSiO
2
,whenSiO
2
growtheymoveintosilicon,itiscall
pileuporsnowploweffect.
BorontendstogotoSiO
2
,itiscalled
depletioneffect.
DepletionandPileupEffects p p
OriginalSiSurface OriginalSiSurface
SiSiO
2
interface SiSiO
2
interface
O i i l Di ib i
t
r
a
t
i
o
n
t
r
a
t
i
o
n
OriginalDistribution
SiO
n
t

C
o
n
c
e
n
t
SiO
n
t

C
o
n
c
e
n
t
SiO
2
D
o
p
a
Si
SiO
2
D
o
p
a
Si
PtypeDopantDepletion NtypedopantPileup
OxidationRate
D d id i (HCl) Dopedoxidation(HCl)
HClisusedtoreducemobileioncontamination.
Widelyusedforgateoxidationprocess.
Growth rate can increase from 1 to 5 percent. Growthratecanincreasefrom1to5percent.
Oxidation Rate OxidationRate
DifferentialOxidation
Thethickeroftheoxidefilmis,theslowerof
theoxidationrateis.
Oxygenneedmoretimetodiffusecrossthe yg
existingoxidelayertoreactwithsubstrate
silicon.
Preoxidation Clean Pre oxidationClean
ThermallygrownSiO
2
isamorphous.
Tends to crosslink to form a crystal Tendstocross linktoformacrystal
Innature,SiO
2
existsasquartzandsand
D f d i l b h l i Defectsandparticlescanbethenucleation
sites
CrystallizedSiO
2
withpoorbarriercapability.
Needcleansiliconsurfacebeforeoxidation.
Oxidation Process OxidationProcess
Dry Oxidation thin oxide DryOxidation,thinoxide
Gateoxide
Pad oxide screen oxide sacrificial oxide etc Padoxide,screenoxide,sacrificialoxide,etc.
WetOxidation,thickoxide
Fieldoxide
Diffusionmaskingoxide
DryOxidationSystem
MFC
To
Process
Tube
MFC
MFC
MFC
ControlValves
Regulator

N
2
N
2
P
r
o
c
e
s
s
P
u
r
g
e

N
O
2
H
C
l
Dry Oxidation DryOxidation
DryO
2
asthemainprocessgas
HCl is used to remove mobile ions for HClisusedtoremovemobileionsfor
gateoxidation
High purity N as process purge gas HighpurityN
2
asprocesspurgegas
LowergradeN
2
asidlepurgegas
Gate Oxidation Steps GateOxidationSteps
IdlewithpurgeN
2
flow
IdlewithprocessN
2
flow
WaferboatspushinwithprocessN
2
flow
TemperaturerampupwithprocessN
2
flow
Temperature stabilization with process N flow TemperaturestabilizationwithprocessN
2
flow
OxidationwithO
2
,HCl,stopN
2
flow
Dangling Bonds and Interface Charge DanglingBondsandInterfaceCharge

Interface State Charge (Positive)
SiO
2
Dangling
Bond
+ + + + +
Si SiO
Si
Si-SiO
2
Interface
Gate Oxidation Steps, Continue GateOxidationSteps,Continue
Oxideannealing,stopO
2
,startprocessflowN
2
Temperature cooldown with process N
2
flow Temperaturecool downwithprocessN
2
flow
WaferboatspulloutwithprocessN
2
flow
Idl i h N fl IdlewithprocessN
2
flow
Nextboatsandrepeatprocess
IdlewithpurgeN
2
flow
Wet Oxidation Process WetOxidationProcess
Faster,higherthroughput
Thick oxide such as LOCOS Thickoxide,suchasLOCOS
Dryoxidehasbetterquality
Process Temperature FilmThickness OxidationTime
Dry oxidation
1000

C
1000 ~ 2 hours Dryoxidation
1000 C
1000 2hours
Wetoxidation
1000

C
1000 ~12minutes
Water Vapor Sources WaterVaporSources
Boiler
Bubbler
Flush Flush
Pyrogenic
Boiler System
Heated Gas line Heated Fore line
BoilerSystem
Process
HeatedGasline HeatedForeline
MFC
Process
Tube
Exhaust
VaporBubbles
Water
Heater Heater
BubblerSystem y
MFC
Process
Tube
N
2
N
2
+H
2
O
Tube
HeatedGasLine
Exhaust
N
2
Bubbles
Water
Heater Heater
FlushSystem
Water
HotPlate
MFC
Process
Tube
N
2
Tube
Heate
r
PyrogenicSteamSystem
HydrogenFlame,2H
2
+O
2
2H
2
O
H
O
2
ToExhaust
H
2
Process Tube
Wafer Boat
ThermalCouple
ProcessTube
WaferBoat
Paddle
Pyrogenic System PyrogenicSystem
Advantage
Allgassystem g y
Preciselycontrolofflowrate
Disadvantage Disadvantage
Introducingofflammable,explosivehydrogen
TypicalH
2
:O
2
ratioisbetween1.8:1to1.9:1.
Pyrogenic Wet Oxidation System PyrogenicWetOxidationSystem
MFC
MFC
Process Tube
MFC
MFC
MFC
Wafers
Burn Box
Control Valves
Regulator
o
c
e
s
s

N
2
u
r
g
e

N
2
O
2
H
2
Scrubbier
P
r
o
P
u
Exhaust
Wet Oxidation Process Steps WetOxidationProcessSteps
IdlewithpurgeN
2
flow
IdlewithprocessN
2
flow
RampO
2
withprocessN
2
flow
WaferboatpushinwithprocessN
2
andO
2
flows
TemperaturerampupwithprocessN
2
andO
2
flows
TemperaturestabilizationwithprocessN
2
andO
2
flows
Ramp O turn off N flow RampO
2
,turnoffN
2
flow
StabilizetheO
2
flow
Wet Oxidation Process Steps WetOxidationProcessSteps
TurnonH
2
flow,ignitionandH
2
flowstabilization
2
, g
2
SteamoxidationwithO
2
andH
2
flow
Hydrogentermination,turnoffH
2
whilekeepingO
2
flow
Oxygentermination,turnoffO
2
startprocessN
2
flow
TemperaturerampdownwithprocessN
2
flow
WaferboatpulloutwithprocessN
2
flow
IdlewithprocessN
2
flow
Next boats and repeat process Nextboatsandrepeatprocess
IdlewithpurgeN
2
flow
RapidThermalOxidation
Forgateoxidationofdeepsubmicrondevice
Verythinoxidefilm,<30
Needverygoodcontroloftemperature
uniformity,WIWandWTW.
RTOwillbeusedtoachievethedevice
requirement.
RTPProcessDiagram
Ramp
up1&2
Cool
down
RTA Load
wafer
Unload
wafer
RTO
O
2
flow
Temperatur
e
HClflow
N
2
flow
Time
HighPressureOxidation
Faster growth rate Fastergrowthrate
Reducingoxidation
temperature: temperature:
1amt.=30C
Higherdielectricstrength
High Pressure Oxidation HighPressureOxidation
StainlessSteelJacket
HighPressure
InertGas
HighPressure
OxidantGas
QuartzProcessChamber
High Pressure Oxidation HighPressureOxidation
Oxidationtimetogrow10,000wetoxide
Temperature Pressure Time
1atmosphere 5hours 1 atmosphere 5 hours
1000 C
5 atmosphere 1 hour
25 t h 12 i t 25 atmosphere 12 minutes
High Pressure Oxidation HighPressureOxidation
Oxidationtemperaturetogrow10,000wetoxidein5hours
Time Pressure Temperature
1atmosphere
1000C
1 atmosphere
1000 C
5 hours
10 atmosphere
700 C
HighPressureOxidation
Complex system Complexsystem
Safetyissues
NotwidelyusedinICproduction
Oxide Measurement OxideMeasurement
Thickness
Uniformity
Gateoxide
Break down Uniformity
C l h
Breakdown
voltage
C V
Colorchart
Ellipsometry
CV
characteristics
Reflectometry
Ellipsometry
EllipticallyPolarized
Reflected Light
Ellipsometry
LinearlyPolarizedIncidentLight
ReflectedLight
s
p
n
1
,k
1
, t
1
n
2
,k
2
Reflectometry
Humaneyeor
Reflectometry
1
Incidentlight
y
photodetector
2
1
g
t
Dielectric film n(

)
Substrate
Dielectricfilm,n(

)
Substrate
CV Test Configuration C VTestConfiguration
Capacitor
Meter
LargeResistor
Aluminum
Oxide
MetalPlatform
Silicon
Heater Heater
Summary of Oxidation SummaryofOxidation
Oxidationofsilicon
Highstabilityandrelativelyeasytoget.
Application Application
Isolation,masking,pad,barrier,gate,andetc.
W t d D WetandDry
MoredryprocessesforadvancedICchips
Rapidthermaloxidationandannealingfor
ultrathingateoxide