A.A.

Chernov
chernov2@llnl.gov
Lawrence Livermore National Laboratory, P. O. Box 808, Livermore, CA 94551
ThisworkperformedundertheauspicesoftheU.S.DepartmentofEnergyby
LawrenceLivermoreNationalLaboratoryunderContractDEAC5207NA27344
Crystal Growth and
Crystal Growing
Santander Spain, July 20-24, 2009
Lawrence Livermore National Laboratory
SurfacePhenomenaandParameters
ofCrystalGrowth:SimpleBasics
ISSCG14,DailanChina,August172010
LLNL-PRES-445231
Outline
Interface:
SmoothversusRoughState
Nucleation
GrowthKinetics:
SmoothInterface
RoughInterface
Growthmodesandasgrown
defects
Bibliography
Monographs
A.A.Chernov.CrystallizationProcesses.ModernCrystallographyIII.
SpringerSer.SolidState,vol36,1984(basicmolecularandmacroscopic
phenomena)
F.Rozenberger.FundamentalsofCrystalGrowth.Springer,1976(phase
diagrams,transport,convection)
A.Pimpinelli,J.Villain.PhysicsofCrystalGrowth.CambridgeUnivPress,
1998(generalphysicalapproach)
K.A.Jackson.KineticProcesses.CrystalGrowth,Diffusion,andPhaseTransition
inMaterials.WileyVCH,Weinheim,2004
J.W.Mullin.Crystallization.Butterworths,2001(4dedition)(growthfrom
solution,industrialcrystallization)
D.Kashciev.Nucleation.BasicTheoryWithApplications.
Butterworth/Heinemann,2000
I.Gutzov,J.Schmelzer.TheVitreousState.Thermodynamics,Structure,
Rheology,andCrystallization.Springer,1995
I.Markov.CrystalGrowthforBeginners.WorldScientific,1996
J.A.Venables.SurfaceandThinFilmProcesses.CambridgeUnivPress,2000

J.N.Israelachvili.Intermolecularandsurfaceforces.Academicpress,1992
A.Zangwill.PhysicsatSurfaces.CambridgeUnivPress.1988
MonograpicReviewes
CurrentTopicsidMaterialsScience.Ed.E.Kaldis.NorthHolland,Vols110,
19761982.
Crystals.Growth.Properties.Applications.Ed.H.C.Freihardt.Springer,Vols
113,19781991.
HandbookofCrystalGrowth.EdD.T.J.Hurle,vols1A,B,2A,B,3A,B.North
Holland,199394
SolidsFarFromEquilibrium.EdC.Godreche.CambridgeUnivpress,1992
BulkCrystalGrowthofElectronic,OpticalandOptoelectronicMaterials.
Ed.P.Capper.J.Wiley&Sons,2005
InternationalSummerSchoolsonCrystalGrowth
Crystal Growth AnIntroduction.EdP.Hartman.NorthHolland
1973
CrystalgrowthandCharacterization.Ed.R.Ueda,J.B.Mullin.North
Holland.1974
CrystalgrowthofElectronicMaterials.Ed.E.Kaldis.NorthHolland,
1985
ScienceandTechnologyofCrystalGrowth.Ed.J.P.vanderEerden,
O.S.L.Bruinsma.Kluwer1995
TheoreticalandTechnologicalAspectsofCrystalGrowth.Ed.
R.Fornari,C.Paorichi.TransTechPublications1998
AdvancesinCrystalGrowthResearch.Ed.K.Sato,Y.Furukawa,
K.Nakajima.Elsevier,2001
CrystalGrowth FromFundamentalstoTechnology.Ed.G.Muller,
J.J.Metois,P.Rudolf.Elsevier2004
Smooth and Rough Interface
cubicle approximation
H.J .Leamy,G.Gilmer, K.A.J ackson. In: Surfaces of Materials vol 1 p.121 (1975)
c/2kT
Non-Kossel crystal
w
i
i = 3
3
1
2
w

w
+
b
c
w
-
Kossel Crystal
Kink
positions of
a molecule
InterfaceGeometry.KinkPosition.
Smooth interface
b
c
w

w
+
w
-
A
M

S
=(u
M
+Pe
M
Ts
M
) (u
S
+Pe
S
Ts
S
) =0.
u
S
u
M
+P(e
S
- e
M
) =- T(s
M
s
S
) =- Ah =- 3c.
c/2 dangling bond energy
Ah ~ 3c
Accuracy estimate :
Melting:
Si Ah =8.3.10
-13
erg (T
m
=1678K, As =3.6k =1.38.10-16 erg/K) ,
Fe Ah =2.3.10
-13
erg (T
m
=1811K, As =0.91k).
PAe =P(e
M
- e
S
) <~ 0.1.3.10-23cm3. 10
6
erg/cm
3
~ 2.10
-18
erg
Sublimation:
Si Ah ~ 7.7.10
-12
erg, PAe ~ kT ~ 1.4.10
-13
erg at T =1000K
Kink energy
S.Toshev,inCrystalgrowth AnIntoduction,EdP.Hartman,NH,1973p.1
o
m
=N
A
e
2/3
molarsurfacefreeenergy
cal/gatom
Enthalpyofmelting,AH, cal/gatom
Slope=0.3 0.5
Fromhomogeneousnucleationinmelts(D.Turnbull):
Interfaceenergy:
SL
~ c/2e
2/3
~Ah/6e
2/3
~ 0.17Ah/e
2/3
LV L S LV S L SV
e e
3 / 2 3 / 2
) / ( 13 . 1 ) / ( 13 . 1 = =
Empirical rule for the crystal melt surface energy
SurfaceReconstruction,Si(001)
Surface energy, Si, crystal vacuum: ~ c/2e
2/3
~ 2,600 erg/cm
2
, saturation of
two bonds releases ~ 1,000 erg/cm
2
(40%) , thus ~ 1,600 erg/cm
2
.
Experiment, computations: 1,490 1,623 erg/cm
2
.
M.Lagally et al
Typically, no reconstruction in condensed surrounding or in adsorbing gases.
Chemically Complex Solutions: both Ah < 0 and Ah > 0.
Melting and evaporation always require heat supply.
Dissolution:
Na
2
SO
4
in water generates Ah = 0.28kcal/mol (= 1.9.10
-14
erg per molecule)
Na
2
SO
4
.10H
2
O requires Ah = 18.7kcal/mol.
Mn(NO
3
)
2
generates Ah = 12.7kcal/mol,
Mn(NO
3
)
2
.7H
2
O requires Ah = 6.1kcal/mol.
MgI
2
, K
2
CO
3
, CaBr
2
generates 50.2, 6.9, 26.3kcal/mol
The reason hydration (solvation) of ions.
Hydration enthalpy, ~(ion-dipole electrostatic attraction) x (N of H
2
O molecules) ~
Experiment: Na
+
101 kcal/mol, Ca
2+
386 kcal/mol,
SO
4
2-
265 kcal/mol, NO
3
74 kcal/mol
+
= ~ Na for 115 5 . 9 . 22 5 .
) .(
2
mol
kcal
mol
kcal
r
el Ze
T T
m

u
L
u
S
s
L
s
S
Melt
Solid
T

u
L
u
S
Liquid,C
2
>C
1
C
1
C
2
T
2
T
1
Liquid,C
2
>C
1
C
1
C
2
u
L1
u
L2
u
S
T
T
1
T
2

Solutions retrograde solubility

Regular melting
Regular solubility
Retrograde solubility
c/2kT ~ -0.272 lnC
e
(mol/m
3
) + 2.82.
Step meandering fluctuations by attachments -detachments
2
( )
Roughening transition: G
step
= U
step
TS
step
= 0
kT
w
e q
Roughening transition viewed by Monte Carlo simulation
meandering rises as c/2kT decreases
H.J .Leamy,G.Gilmer, K.A.J ackson in Surfaces of Materials vol 1 p.121 (1975)
c/2kT =
4
He Crystal in its melt
1.4K
1K
0.4K
0.1K
S.Balibar, H.Alles, A.Ya. Parshin.
Rev Mod. Phys. 77(2005)317-370
KH2PO4, KDP CaCO3, Calcite Lysozyme
Step fluctuation viewed by AFM: meandering
increases together with solubility and decreasing step energy
J .J .DeYoreo, L.N.Rashkovich, R Friddle
Nucleation:
3Dimensional,
2Dimensional
Criticalradius:coG/cr=0:r
c
=2e/A
oG
c
=(16t/3)e
2

3
/A
2
3Dimensions,sphere
Nucleationissolids elasticstress :
oG= (4tr
3
/3e)[A 9(1v)e(AP)
2
/16E ]+4tr
2

Ifelasticstress issignificanttheequilibriumshapeisaflatdisc
orablade
Nucleation rate: J (1/cm
3
s) = Bexp(- oG
c
/kT)
Nucleation work is minimal for equilibrium shape. Sphere:
oG = - (4tr
3
/3e)A + 4tr
2

s
r

f
3D Homogeneous Nucleation

M
-
S
A = kTlnC/C
e
- solution
A = ASAT = AH(AT/T) - melt
oG
r
c
=2e/A
oG
c
Classical
Quantum

Pre-exponent, B
Homogeneous nucleation:B = 4tr
c
2
an
2
vexp(E/kT)Z= 4tr
c
2
|n
2
Z,
Zeldovich factor: , = - (1/n
c
)(c
2
oG(n)/cn
2
)
nc
,
Z = (,/2tkT)
1/2
= (1/n
c
)(oG
c
/3tkT)
1/2
~ 10
-2
Heterogeneous nucleation.
Equilibrium shape on a substrate is a part of the free equilibrium shape
because of the Gibbs-Thomson law:
Estimated B:
vapor B ~ 10
28
1/cm
3
s; melt B ~10
35
10
38
1/cm
3
s, solution B ~ 10
27
1/cm
3
s
oG
het
= oG
c
A/
h
L
h/L = A/2
h
c
= 2eA/A
A +
s
-
i

i
Non steady state nucleation - time lag
oG = - nA + bn
2/3

n
c
= (32/3)e2o3/(A)3
n
oG
c
Number of nuclei
time
0
n
0 1 2 3 .
N = (Nucleation rate J ).Volume.t
Diffusion along the n-axis:
D* = v
+
+ v
-
Time to reach maximum of the
nucleation barrier:
t ~ n
c
2
/D*
(Nucleation Rate J ).Volume
oG
r
c
= eo/A
r
oG
c
2D Nucleation
oG = - (tr
2
h/e)A + 2trh
r
c
= eo/A
oG
c
= the
2
/A
New atomic layer, one atomic size or lattice
spacing high, h:
Homogeneous 2D nucleation rate:
J (1/cm
2
s) = 2tr
c
anvexp(-E/kT)nZexp(-oG
c
/kT) = 2tr
c
|n
2
exp(-oG
c
/kT)
Heterogeneous 2D nucleation rate: n
2
nn*, oG
c
oG
c
*
r
c
+a
r
c
Growth Kinetics
Smooth Interface Layer-byLayer Growth
Generation of steps:
3D nucleation
Screw dislocation
Nucleation rate, J (nuclei/cm
2
s = 1/cm
2
s)
Step expansion rate, v cm/s
Low nucleation rate, small face of the area S: R = J Sh
High nucleation rate, large area S: R = h(tv
2
J /3)
1/3
h
R rate of the face propagation
S
Active
nucleation site
v
2 Dimensional nucleation
M = 14,000 Da, effective
molecular diameter ~ 2.5nm
2D nucleation on lysozyme
Step Sources: Screw Dislocations
D
R = pv=hv/
h/=p
Face growth rate R:
(0001) SiC
P.G.Vekilov et al
Step Propagation
High Kink Density.
Ferritin, M = 450,000 Da, spheres 13nm,
FCC lattice.
Supply of species to steps and incorporation
into kinks.
1. Surface/at-surface diffusion: vapor, MBE,CVD, etc
2. Bulk diffusion: solution
steps
kinks
(111)
Incorporation into a kink
,
i
u
kT
i
p Ae

=
1, sum over medium or solid, except top of the barrier,
i
u
kT
i
i
Ae u E

= =

, ln ) (ln ln ln
T
u
A k
kT
u
A Ae k p p k p k s
i
kT
u
i i i
i
+ = = > < =

. , ln
kT
Ts u
e A u A kT Ts

= + =
kT
E
kT
u
i
kT
u Ts u
i
e e p e p
i i

= = =

pressure, constant at or, ,
:
Activated complex includes:
The still hydrated molecule/ion to be incorporated, the hydrated kink and their
surrounding,
or
The molecule/atom/ion to be incorporated still bound within the species that have
carried it to the kink and the kink occupied by other species, if any.
Probability of having the activated complex at the energy level u
i
:
Kinetic coefficient
kT
E u
k
e k
kT kT
E
kT
E
kT
E
M
S M S S M
e a
C C e e a e e a w w a

= = = =
v |
e | v v

), ( ) 1 ( ) ( ) ( v
k
M e S
u C kT + = e ln
a C w
C
C C
e
w
w
e k
e
e
kT
/ flux exchange the and e |

= =

A

+
Attachment and detachment frequencies of species to a kink:
kT
E
kT
E
S M
e w e w

+
= =

v v ,
kT
u E
k st e st st
M
e a C C

= =

2
) / ( ), ( v v | e |
Kink velocity:
Step velocity:
Face velocity:
) ( v
st e st
C C p p R = = e |
J.Q.Broughton,A.Bonisent,F.F.Abraham.J.ChemPhys74(1981)4029
Delocalizedinterface
J.Q.Broughton,A.Bonisnt,F.F.Abraham.J.ChemPhys74(1981)4029
Meltnearsoidwall densitywaves
Severalatomicplanesare
beingpacked
simultaneously
Mikheev,Chernov,JCG112(1991)591
Normalgrowthrate:
V=bAT=A(kT/m)
1/2
(AT/T),
A~ 1;b=A(k/mT)
1/2
Lead:
m=207.1.67.1024g,
T=600K,
(kT/m)
1/2
=155m/s
b=26cm/Sk
Experiment:
b=28 8cm/sK
Rodway,HuntJCG112(1991)554
Growth modes and
as grown defects
See K.F.Hulme, J .B.Mullin. Phil Mag 22(1959)1286
K = 0.5
K = 4
Sectoriality and Striation
Vicinal Sectoriality
Bottom Lines
Crystal interface may be either smooth or rough
at high or low energy, respectively.
Surface energy may be estimated from phase transformation
enthalpy for vapor and melt and from solubility for solution.
Growth of a smooth interface is impossible without kinks at
steps and is thus slower than growth of the rough interface full
of kinks or is fully disordered
Growth rate of a smooth interface is controlled by step
generation by 2D nucleation or by screw dislocations and by
incorporation of growth units at kinks.
Growth mode controls crystal perfection