PatternTransfer:AdditivetechniquesPhysical

VaporDepositionandChemicalVapor
Deposition
Dr.MarcMadou,Fall2012
UCIClass9

Content

Physicalvapordeposition
(PVD)
Thermalevaporation
Sputtering
Evaporationandsputtering
compared
MBE
Lasersputtering
IonPlating
ClusterBeam

Chemicalvapordeposition
(CVD)
Reactionmechanisms
Stepcoverage
CVDoverview
Epitaxy
ElectrochemicalDeposition

Physicalvapordeposition(PVD)

Thephysicalvapordepositiontechniqueisbasedontheformationofvaporof
thematerialtobedepositedasathinfilm.Thematerialinsolidformiseither
heateduntilevaporation(thermalevaporation)orsputteredbyions
(sputtering).Inthelastcase,ionsaregeneratedbyaplasmadischargeusually
withinaninertgas(argon).Itisalsopossibletobombardthesamplewithan
ionbeamfromanexternalionsource.Thisallowstovarytheenergyand
intensityofionsreachingthetargetsurface.

Physicalvapordeposition(PVD):
thermalevaporation
N=No exp

Thenumberofmolecules
leavingaunitareaofevaporant
persecond

HeatS ources
Resistance
ebeam
RF
Laser

Advantages
Noradiation
Lowcontamination
Noradiation
Noradiation,low
contamination

Dis advantages
Contamination
Radiation
Contamination
Expensive

Physicalvapordeposition(PVD):thermal
evaporation
N(molecules/unitarea/unittime)=
3. 513. 10 22 Pv (T)/(MT) 1/2

d
Resist
Si

Thisistherelationbetweenvaporpressureof
theevaporantandtheevaporationrate.Ifahigh
vacuumisestablished,mostmolecules/atomswillreach
thesubstratewithoutinterveningcollisions.Atomsand
moleculesflowthroughtheorificeinasinglestraight
track,orwehavefreemolecularflow:
Kn=

Thefractionofparticlesscatteredbycollisions
withatomsofresidualgasisproportionalto:
Thesourcetowaferdistancemustbesmalerthanthemeanfreepath(e.g,25to70cm)

Thecosinelaw
A~cos

Physicalvapordeposition(PVD):thermal
evaporation
Fromkinetictheorythemeanfreepathrelates
tothetotalpressureas:

tSurfacefeature

Substrate
Shadow
Source
12

=(RT/2M) 1/2/PT

Sincethethicknessofthedepositedfilm,t,isproportional
tothecos,theratioofthefilmthicknessshowninthe
figureontherightwith=0isgivenas:

t1/t2=cos

t1
cos1
=
3
t2
cos2

Physicalvapordeposition(PVD):sputtering
W=kVi
PTd

Momentumtransfer

Vworkingvoltage
idischargecurrent
d,anodecathodedistance
PT,gaspressure
kproportionalityconstant

Rate
Choiceofmaterials
Purity

Evaporation
and
sputtering:
comparison

S ubs trateheating
S urfacedamage
Insitucleaning
Alloycompos itions ,
s tochiometry
X raydamage
Changesinsource
material
Decompos itionof
material
S calingup
U niformity
CapitalEquipment
N umberof
depos itions
Thicknes scontrol
Adhes ion
S hadow ingeffect
Filmproperties (e. g.
grainsizeands tep
coverage)

Evaporation

Sputtering

Thousandatomiclayerspersecond
(e.g.0.5m/minforAl)
Limited

Oneatomiclayerpersecond
Almostunlimited

Better(nogasinclusions,veryhigh Possibilityofincorporating
vacuum)
impurities(lowmediumvacuum
range)
Verylow
Unlessmagnetronisusedsubstrate
heatingcanbesubstantial
Verylow,withebeamxray
Ionicbombardmentdamage
damageispossible
Notanoption
Easilydonewithasputteretch
Littleornocontrol
Alloycompositioncanbetightly
controlled
Onlywithebeamevaporation
Radiationandparticledamageis
possible
Easy
Expensive
High

Low

Difficult
Difficult
Lowcost
Onlyonedepositionpercharge

Good
Easyoverlargeareas
Moreexpensive
Manydepositionscanbecarried
outpertarget
Severalcontrolspossible
Excellent
Small
Controlbybias,pressure,
substrateheat

Noteasytocontrol
Oftenpoor
Large
Difficulttocontrol

Physicalvapordeposition(PVD):MBE,
LaserAblation

MBE
Epitaxy:homoepitaxy
heteroepitaxy
Veryslow:1m/hr
Verylowpressure:1011
Torr
Lasersputterdeposition
Complexcompounds(e.g.
HTSC,biocompatible
ceramics)

Physicalvapordeposition(PVD):Ioncluster
plating

Ionizedcluster:itispossibleto
ionizeatomclustersthatarebeing
evaporatedleadingtoahigher
energyandafilmwithbetter
properties(adherence,density,etc.).
From100mbar(heatercell)to
105to107mbar(vacuum)
suddencooling
Depositsnanoparticles
Combinesevaporationwitha
plasma
fasterthansputtering
complexcompositions
goodadhesion

Physicalvapordeposition(PVD):Ion
clusterplatingandionplating

Gas cluster ions consist of many atoms or

molecules weakly bound to each other and
sharing a common electrical charge. As in the
case of monomer ions, beams of cluster ions
can propagate under vacuum and the energies
of the ions can be controlled using acceleration
voltages. A cluster ion has much larger mass
and momentum with lower energy per atom
than a monomer ion carrying the same total
energy. Upon impact on solid surfaces, cluster
ions depart all their energy to an extremely
shallow region of the surface. Cluster plating
material is forced sideways and produces highly
smooth surfaces.
Also individual atoms can be ionized and lead
to ion plating (see figure on the right, example
coating : very hard TiN)

Masstransportofthereactantin
thebulk
Gasphasereactions
(homogeneous)
Masstransporttothesurface
Adsorptiononthesurface
Surfacereactions
(heterogeneous)
Surfacemigration
Incorporationoffilm
constituents,islandformation
Desorptionofbyproducts
Masstransportofbyproduccts
inbulk

CVD:Diffusiveconvectivetransportof
depositingspeciestoasubstratewith
manyintermolecularcollisions
drivenbyaconcentrationgradient

Chemicalvapordeposition(CVD):reaction
SiH
SiH4
mechanisms

Si

Chemicalvapordeposition(CVD):
reactionmechanisms

Energysourcesfordeposition:

Thermal
Plasma
Laser
Photons
Depositionrateorfilmgrowthrate

Fl = D

Laminarflow

(U)
(x)

(Ficksfirstlaw)
1
2

?x ?
(x) = ? ?
?U ?

dx

(Boundarylayerthickness)

(gasviscosity,gasdensity,gasstreamvelocityU)
1

L
2
1
2 ? ?
?
(x)dX = L ?
L0
3 ?UL ?

Fl = D

(DimensionlessReynoldsnumber)
Re L

= 2L
3 ReL

(bysubstitutioninFicksfirstlawandx=)

Chemicalvapordeposition(CVD)
:reactionmechanisms

Massflowcontrolledregime
(squarerootofgasvelocity)
(e.g.APCVD~10010kPa):
Fl = D

FASTER
Thermallyactivatedregime:
ratelimitingstepissurface
reaction(e.g.LPCVD~100
PaDisverylarge):
Ea
SLOWER
R=Ro ekT

Chemicalvapordeposition(CVD):
stepcoverage

Stepcoverage,twofactorsare
important
Meanfreepathandsurface
migrationi.e.PandT
Meanfreepath:

Ea
R=Ro ekT

Fl = D

2 P T

Fld

kT
1
2

arctan

w
z

isangleofarrival

Chemicalvapordeposition(CVD):
overview

CVD(thermal)
APCVD(atmospheric)
LPCVD(<10Pa)
VLPCVD(<1.3Pa)
PECVD(plasmaenhanced)
PhotonassistedCVD
LaserassistedCVD
MOCVD

Compressive
Deposited
Tensile
stress
filmstress
causescauses
concave
convex
bending
bendingof
ofaathin
thinsubstrate
substate

Chemicalvapordeposition(CVD):LCVD

TheLCVDmethodisabletofabricate
continuousthinrodsandfibresbypullingthe
substrateawayfromthestationarylaserfocusat
thelineargrowthspeedofthematerialwhile
keepingthelaserfocusontherodtip,asshown
intheFigure.LCVDwasfirstdemonstratedfor
carbonandsiliconrods.However,fiberswere
grownfromothersubstratesincludingsilicon,
carbon,boron,oxides,nitrides,carbides,borides,
andmetalssuchasaluminium.TheLCVD
processcanoperateatlowandhighchamber
pressures.Thegrowthrateisnormallylessthan
100m/satlowchamberpressure(<<1bar).At
highchamberpressure(>1bar),highgrowth
rate(>1.1mm/s)hasbeenachievedforsmall
diameter(<20m)amorphousboronfibers.

Epitaxy

VPE:
MBE(PVD)(seeabove)
MOCVD(CVD)i.e.organometallic
CVD(e.g.trimethylaluminumto
depositAl)(seeabove)
Liquidphaseepitaxy
Solidepitaxy:recrystallizationof
amorphousmaterial(e.g.polySi)

Liquidphaseepitaxy

Epitaxy

Selectiveepitaxy
Epilayerthickness:
IR
Capacitance,Voltage
Profilometry
Taperedgroove
Anglelapandstain
Weighing

Selectiveepitaxy

Electrochemicaldeposition:electroless

Electrolessmetaldisplacement
Electrolesssustainableoxidationofa
reductant
Metalsalt(e.g.NiCl2)
Reductant(e.g.hypophosphite)
Stabilizer:bathis
thermodynamicallyunstableneeds
catalyticpoison(e.g.thiourea)
Complexingagent:preventtoo
muchfreemetal
Buffer:keepthepHrangenarrow
Accelerators:increasedeposition
ratewithoutcausingbath
instability(e.g.pyridine)

Depositiononinsulators(e.g.plastics):seed
surfacewithSnCl2/HCl

1.Zn(s)+Cu2+(aq)>Zn2+(aq)+Cu(s)

Cu
2.Reduction(cathodereaction):
Ni+2+2e>Ni
Oxidation(anodereaction):
H2PO2+H2O>H2PO3+2H++2e

Ni+2+H2PO2+H2O>Ni+H2PO3+2H+

e.g.electrolessCu:40mhr1

Electrochemicaldeposition:electroless

Evansdiagram:electrolessdepositionis
thecombinedresultoftwoindependent
electrodereactions(anodicandcathodic
partialreactions)
Mixedpotential(EM):reactionsbelongto
differentsystems
ideposition=ia=icandI=Axideposition
Totalamountdeposited:mmax=ItM/Fz(t
isdepositiontime,Molecularweight,Fis
theFaradayconstant,zisthechargeonthe
ion)
CMOScompatible:noleadsrequired

+ Evansdiagram

F=96,500coulombs=1,61019(electroncharge)x6.021023(Avogadrosnumber)

Electrochemicaldeposition:electrodeposition
thermodynamics

Electrolyticcell
Aucathode(inertsurfaceforNi
deposition)
Graphiteanode(notattackedbyCl2)

Twoelectrodecells(anode,cathode,
workingandreferenceorcounterelectrode)
e.g.forpotentiometricmeasurements
(voltagemeasurements)
Threeelectrodecells(working,reference
andcounterelectrode)e.g.for
amperometricmeasurements(current
measurements)

Electrochemicaldeposition
:electrodepositionthermodynamics(E)
1.Freeenergychangeforioninthesolutiontoatominthemetal(cathodicreaction):

G = G (freeenergypuremetal) G (freeenergyofionintheelectrolyte) oralso

m

G=G0RTlnaMz+=G 0RTlnCMz+ (1)

2.Theelectricalwork,w,performedinelectrodeposition
atconstantpressureandconstanttemperature: G = w + PV andsinceV=0

G=EzF (2)

3.SubstitutingEquation(2)in(1)onegets
E

(Nernstequation)

4.Repeat(1)and(2)foranodicreaction:

G=G2G1

or G=(E2E1)zF=EcellzF
E2>E1:battery
E2<E1:+Eext>Ecelltoafforddeposition

Electrochemicaldeposition
:electrodepositionthermodynamics()

Athermodynamicpossiblereaction
maynotoccurifthekineticsare
notfavorable
Kineticsexpressthemselves
throughalltypesofoverpotentials
EEo=anodicandis
cathodic)

Electrochemicaldeposition
:electrodepositionkineticsactivationcontrol

kc

(withoutfield)
G*=G #+

(withfield)

Understandingofpolarization
curves:considerapositiveion
transportedfromsolutiontothe
electrode
Successfulionjumpfrequencyis
givenbytheBoltzmann
distributiontheory(hisPlanck
constant):

Electrochemicaldeposition
:electrodepositionkineticsactivationcontrol

Atequilibriumtheexchangecurrent
densityisgivenby:

i e

Thereactionpolarizationisthengiven
by:
e

Themeasurablecurrentdensityisthen
givenby:

Forlargeenoughoverpotential:


i (ButlerVolmer)

a + blog(i)

(Tafellaw)

Electrochemicaldeposition
:electrodepositionkineticsdiffusioncontrol

Fromactivationcontroltodiffusion
control:

dC

dX

Concentrationdifferenceleadsto
anotheroverpotentiali.e.concentration
polarization:
c =

C
RT
ln x=0
nF
C 0

UsingFaradayslawwemaywrite
also:

i

C x=0

AtacertainpotentialCx=0=0andthen:

I l

weget:

Electrochemicaldeposition
:electrodepositionnonlineardiffusioneffects

Nonlineardiffusionandtheadvantagesofusingmicro
electrodes:

I l

Anelectrodewithasizecomparabletothethicknessof
thediffusionlayer

1
( D0 t ) 2

TheCottrellequationisthecurrentvs.timeonan
electrodeafterapotentialstep:
Il

Formicroelectrodesitneedscorrection:

Il

Electrochemicaldeposition
:electrodepositionnonlineardiffusioneffects

Thediffusionlimitedcurrentsfor
somedifferentelectrodeshapesare
givenas(atlongertimesafterbias
applicationandforsmall
electrodes):
I l,m

Iftheelectrodesarerecessed
anothercorrectiontermmustbe
introduced:
I l,m

Homework

Homework:demonstrateequalityof=(RT/2M)1/2/PTand=kT/21/2a2PT
(whereaisthemoleculardiameter)
Whatisthemeanfreepath(MFP)?HowcanyouincreasetheMFPinavacuum
chamber?Formetaldepositioninanevaporationsystem,comparethedistance
betweentargetandevaporationsourcewithworkingMFP.Whichonehasthe
smallerdimension?1atmospherepressure=____mmHg=___torr.Whatarethe
physicaldimensionsofimpingementrate?
Whyissputterdepositionsomuchslowerthanevaporationdeposition?Makea
detailedcomparisonofthetwodepositionmethods.
DeveloptheprincipalequationforthematerialfluxtoasubstrateinaCVDprocess,
andindicatehowonemovesfromamasstransportlimitedtoreactionratelimited
regime.Explainwhyinonecasewaferscanbestackedcloseandverticallywhilein
theotherahorizontalstackingispreferred.
DescribestepcoveragewithCVDprocesses.Explainhowgaspressureandsurface
temperaturemayinfluencethesedifferentprofiles.