byeong-joo lee calphad computational thermodynamics byeong-joo lee computational materials science...
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Byeong-Joo Lee www.postech.ac.kr/~calphad
Computational Computational ThermodynamicsThermodynamics
Byeong-Joo Lee Byeong-Joo Lee
Computational Materials Science & Engineering Lab.Computational Materials Science & Engineering Lab.Pohang University of Science & TechnologyPohang University of Science & Technology
Byeong-Joo Lee www.postech.ac.kr/~calphad
R&D in Materials Science and EngineeringR&D in Materials Science and Engineering
Structure Structure EvolutionEvolution
Process Process ConditionCondition
Materials Materials PropertyProperty
Research Type I : experiments first, then thinkingResearch Type II: think first, then do experiments
Byeong-Joo Lee www.postech.ac.kr/~calphad
Lattice StabilityLattice Stability
VPSTHG
Byeong-Joo Lee www.postech.ac.kr/~calphad
BABABBAA
Bo
BAo
Am
LxxxxxxRT
GxGxG
,)lnln(
ABABBBBBAAAABA EWEWEWE
221
AAA NzxW 221
BBB NzxW
BAAB xNzxW
])2[(2 BBAAABBABBBAAABA EEExxExExNz
E
Regular Solution vs. Quasi-Chemical ModelRegular Solution vs. Quasi-Chemical Model
Byeong-Joo Lee www.postech.ac.kr/~calphad
Thermodynamic Assessment Thermodynamic Assessment – Cr-Ni Binary System– Cr-Ni Binary System
NiCrNiCrNiNiCrCrNio
NiCro
Crm LyyyyyyRTGyGyG ,)lnln(
B.-J. Lee, 1992B.-J. Lee, 1992
LLfccfccCr,Ni Cr,Ni = 8030 – 12.8801·T + (33080 – 16.0362·T)(1-2X = 8030 – 12.8801·T + (33080 – 16.0362·T)(1-2XNiNi))
LLbccbccCr,NiCr,Ni = 17170 – 11.8199·T + (34418 – 11.8577·T)(1-2X = 17170 – 11.8199·T + (34418 – 11.8577·T)(1-2XNiNi))
LLliqliqCr,NiCr,Ni = 318 – 7.3318·T + (16941 – 6.3696·T)(1-2X = 318 – 7.3318·T + (16941 – 6.3696·T)(1-2XNiNi))
Byeong-Joo Lee www.postech.ac.kr/~calphad
Thermodynamic Calculation – Fe-Cr-Ni Ternary SystemThermodynamic Calculation – Fe-Cr-Ni Ternary System
Byeong-Joo Lee www.postech.ac.kr/~calphad
Thermodynamic Parameters (Fe,Cr,Mo)(Va,B,C,N)Thermodynamic Parameters (Fe,Cr,Mo)(Va,B,C,N)
VaMoo
VaMoVaCro
VaCrVaFeo
VaFem GyyGyyGyyG ::: BMoo
BMoBCro
BCrBFeo
BFe GyyGyyGyy :::
CMoo
CMoCCro
CCrCFeo
CFe GyyGyyGyy ::: NMoo
NMoNCro
NCrNFeo
NFe GyyGyyGyy :::
)lnlnln( MoMoCrCrFeFe yyyyyyaRT )lnlnlnln( NNCCBBVaVa yyyyyyyycRT
xsmo GG
VaMoCrVaMoCrVaMoFeVaMoFeVaCrFeVaCrFexs LyyyLyyyLyyyG :,:,:, BVaMoBVaMoBVaCrBVaCrBVaFeBVaFe LyyyLyyyLyyy ,:,:,:
CVaMoCVaMoCVaCrCVaCrCVaFeCVaFe LyyyLyyyLyyy ,:,:,: NVaMoCVaMoNVaCrCVaCrNVaFeNVaFe LyyyLyyyLyyy ,:,:,:
BMoCrBMoCrBMoFeBMoFeBCrFeBCrFe LyyyLyyyLyyy :,:,:, CMoCrCMoCrCMoFeCMoFeCCrFeCCrFe LyyyLyyyLyyy :,:,:,
NMoCrCMoCrNMoFeCMoFeNCrFeNCrFe LyyyLyyyLyyy :,:,:, CBMoCBMoCBCrCBCrCBFeCBFe LyyyLyyyLyyy ,:,:,:
NBMoNBMoNBCrCBCrNBFeNBFe LyyyLyyyLyyy ,:,:,: NCMoNCMoNCCrNCCrNCFeNCFe LyyyLyyyLyyy ,:,:,:
VaMoCrFeVaMoCrFe Lyyyy :,,
Byeong-Joo Lee www.postech.ac.kr/~calphad
Thermodynamic Calculation – Practical SteelsThermodynamic Calculation – Practical Steels
Byeong-Joo Lee www.postech.ac.kr/~calphad
Thermodynamic Calculation – Application to Alloy DesignThermodynamic Calculation – Application to Alloy Design
Computational Thermodynamics 의 적용 분야 Structural Materials (Steel, Solder, Al-, Ti-, Ni-, Mg-alloys), Semiconducting Materials, Ceramic Materials, Hydrogen Storage Materials, CVD process 등 열역학이 지배하는 모든 물질계
Byeong-Joo Lee www.postech.ac.kr/~calphad
AB1: 0.1C-5MN-7Al AB2: 0.2C-4Mn-6.6Al AB3: 0.3C-3.5Mn-6Al AB4: 0.4C-3.5Mn-5.8Al
AB5: 0.5C-3Mn-4.9Al AB6: 0.3C-4Mn-7.3Al-0.05Ti
Thermodynamic Calculation – Application to Alloy/Process DesignThermodynamic Calculation – Application to Alloy/Process Design
Byeong-Joo Lee www.postech.ac.kr/~calphad
Thermodynamics Assessment - Na-Al-H system
Byeong-Joo Lee www.postech.ac.kr/~calphad
Assessment of thermodynamic properties in the Li-Al-H ternary systemAssessment of thermodynamic properties in the Li-Al-H ternary system
Byeong-Joo Lee www.postech.ac.kr/~calphad
※ Example: Deposition of Silicon SiH4 + 2Cl2 = Si + 4HCl
Driving force of CVD Deposition Driving force of CVD Deposition
Byeong-Joo Lee www.postech.ac.kr/~calphad
Interfacial ReactionsInterfacial Reactions
Byeong-Joo Lee www.postech.ac.kr/~calphad
Interfacial Reaction between Cu and Various Solder
-Experimental Observation
▶ Cu/Sn : Cu6Sn5 ▶ Cu/Sn-Pb eutectic : Cu6Sn5 ▶ Cu/Sn-Ag eutectic : Cu6Sn5 ▶ Cu/Sn-Zn eutectic : CuZn_γ ▶ Cu/Sn-In eutectic : Cu2(Sn,In) or Cu2In3Sn
Byeong-Joo Lee www.postech.ac.kr/~calphad
Application to Solder/Substrate Interfacial Reactions Application to Solder/Substrate Interfacial Reactions – Cu/Sn – Cu/Sn ReactionReaction
Byeong-Joo Lee www.postech.ac.kr/~calphad
Application to Solder/Substrate Interfacial Reactions Application to Solder/Substrate Interfacial Reactions – Cu/Sn – Cu/Sn ReactionReaction
Byeong-Joo Lee www.postech.ac.kr/~calphad
Application to Thin Film Reactions Application to Thin Film Reactions – Metal/Si Reaction– Metal/Si Reaction
Byeong-Joo Lee www.postech.ac.kr/~calphad
Application to Thin Film Reactions Application to Thin Film Reactions – Metal/Si Reaction– Metal/Si ReactionSi Sample Preparation Heat Treatment Measurement Amorphous First Silicide ref.
crystal(111)
triode d.c. sputteringbilayer (Ti: 95,400nm)
isothermal(30min at 500oC)
XRD/TEM - Ti5Si3 & TiSi 50
crystal(111)
electron-gun depositionbilayer (Ti: 300nm)
isothermal120min at 500oC
RBS - aTiSi & TiSi251
polycrystal magnetron S-gun sputteringbilayer (Ti: 100nm)
isothermal(40min at 600oC)
XRD - TiSi & TiSi252
crystal<100>
evaporationbilayer (Ti:100nm)
isothermal(30min at 750oC)
RBS/XRD - TiSi & TiSi253
amorphousor <100>
electron-gun depositionbilayer (Ti: 90nm)
isothermal(20min at 450oC)
BackscatteringSpectroscopy
- TiSi 54
crystal(111)
electron-beam evaporationbilayer (Ti: 3nm)
isothermal(30min at 600oC)
TEM - TiSi & TiSi255
crystal(100)
conventional HV sputteringbilayer (Ti: 30nm)
isothermal(60min at 650oC)
RBS/TEM - TiSi2 (C49) 56
crystal<100>
electron-gun evaporationbilayer (Ti: 140nm)
isothermal(120min at 550oC)
RBS/XRD/TEM - bTiSi257
amorphous electron-beam evaporationtrilayer (Ti: 10~100nm)
isothermal(~300s at 560oC)
TEM yesSSA Ti5Si3
45
amorphousor <100>
sputter-depositiona-Si/Ti/Si trilayer (Ti: 23nm)
isothermal(60min at 500oC)
TEM/RBS yesSSA TiSi2 (C49) 58
crystal(100)
sputter depositionbilayer (Ti: 25~35nm)
isothermal(30min at 460oC)
HRTEM/EDS yesSSA TiSi2 (C49) 59
crystal(111)
UHV e-beam evaporationa-Si/Ti/Si trilayer (Ti: 30nm)
isothermal(30min at 450oC)
in-situ RHEED/HRTEM
yesSSA
cTi5Si360
poly Si rf sputteringbilayer (Ti: 55nm)
heating (10oC/m)to 510oC
XTEM/STEM yesSSA TiSi2 (C49) 61
crystal(100)
magnetron sputteringbilayer (Ti: 32,51nm)
heating (15oC/min)to approx. 800oC
IR-abs spect.XRD/resistivity
yesSSA TiSi2 (C49) 62
crystal(100)
magnetron sputteringbilayer (Ti: 32,46nm)
heating (3,20oC/s)to approx. 800oC
in-situ XRD - Ti5Si3/Ti5Si463
Byeong-Joo Lee www.postech.ac.kr/~calphad
Application to Thin Film Reactions Application to Thin Film Reactions – Metal/Si Reaction– Metal/Si Reaction
Byeong-Joo Lee www.postech.ac.kr/~calphad
Application to Thin Film Reactions Application to Thin Film Reactions – Metal/Si Reaction– Metal/Si Reaction
Byeong-Joo Lee www.postech.ac.kr/~calphad
Application to Interfacial Reactions Application to Interfacial Reactions – Metal/Si Reaction– Metal/Si Reaction
Byeong-Joo Lee www.postech.ac.kr/~calphad
Application to Metal/Ceramics Interfacial Reactions Application to Metal/Ceramics Interfacial Reactions – Ti/Al– Ti/Al22OO33
ReactionReaction
Byeong-Joo Lee www.postech.ac.kr/~calphad
Application to Metal/Ceramics Interfacial Reactions Application to Metal/Ceramics Interfacial Reactions – Ti/Al– Ti/Al22OO33
ReactionReaction
Byeong-Joo Lee www.postech.ac.kr/~calphad
Computational Materials Science & Engineering Lab.Computational Materials Science & Engineering Lab.Pohang University of Science & Technology, KoreaPohang University of Science & Technology, Korea
Eunha KimEunha Kim
Inyoung SaInyoung Sa
Byeong-Moon LeeByeong-Moon Lee
andand
Byeong-Joo Lee Byeong-Joo Lee
Thermodynamics Nano MaterialsThermodynamics Nano Materials
Byeong-Joo Lee www.postech.ac.kr/~calphad
Size Effect on the Melting Point Size Effect on the Melting Point for Au nano particles & wiresfor Au nano particles & wires
Byeong-Joo Lee www.postech.ac.kr/~calphad
VLS Growth of Nanowires VLS Growth of Nanowires - GeSi Nanowires - GeSi Nanowires
Byeong-Joo Lee www.postech.ac.kr/~calphad
②
①
① Vapor-Liquid
② Liquid-Solid
SiH4 + GeH4 + H2
0.0 0.2 0.4 0.6 0.8 1.00
50
100
150
200
250
Act
ivit
y o
f S
i
X(Si)
Au-Si liquid solution, T=673K, P=200Torr
(a)
Reactions during the VLS Process
Byeong-Joo Lee www.postech.ac.kr/~calphad
②
①
① Vapor-Liquid
② Liquid-Solid
①
②
SiH4 + GeH4 + H2
0.0 0.2 0.4 0.6 0.8 1.00
50
100
150
200
250
Act
ivit
y o
f S
i
X(Si)
Au-Si liquid solution, T=673K, P=200Torr
(a)
Reactions during the VLS Process
200 torr
400 oC
Byeong-Joo Lee www.postech.ac.kr/~calphad
Size dependence of SiGe nanowire compositionSize dependence of SiGe nanowire composition
0.00 0.25 0.50 0.75 1.000.00
0.25
0.50
0.75
1.000.00
0.25
0.50
0.75
1.00
Liquid (Bulk) Solid (Bulk) Liquid (D=10nm) Solid (D=10nm)
FCC+LDIAMOND+L
SiAu
Ge
0.0 0.2 0.4 0.6 0.8 1.0
Gib
bs
Ener
gy
of Form
atio
n
Bulk liquid
XSi or XGe
Nanosized liquid
Capillarity Effect
Si or Ge
0.0 0.2 0.4 0.6 0.8 1.0-10
0
10
20
30
Au-Ge liquid
Gib
bs
En
erg
y o
f F
orm
ati
on
,k
J/g
ram
ato
m
XSi or XGe
Au-Si liquid
Byeong-Joo Lee www.postech.ac.kr/~calphad
Size dependence of SiGe nanowire compositionSize dependence of SiGe nanowire composition
0 30 60 90 120 15065
70
75
80
85
XAu=0.20, XSi=0.20, XGe=0.60
XAu=0.40, XSi=0.15, XGe=0.45
XAu=0.60. XSi=0.10, XGe=0.30
Ge
con
ten
t, a
t%
Diameter, nm
0 30 60 90 120 15035
40
45
50
55
XAu
=0.20, XSi=0.40, XGe
=0.40
XAu
=0.40, XSi=0.30, XGe
=0.30
XAu
=0.60, XSi=0.20, XGe
=0.20
Ge
con
ten
t, a
t%
Diameter, nm
0 30 60 90 120 1505
10
15
20
25
XAu=0.20, XSi=0.60, XGe=0.20
XAu=0.40, XSi=0.45, XGe=0.15
XAu=0.60, XSi=0.10, XGe=0.30
Ge
con
ten
t, a
t%
Diameter, nm
CALPHAD (2008)CALPHAD (2008)
Byeong-Joo Lee www.postech.ac.kr/~calphad
SummarySummary
Computational Thermodynamics
• Calculation of Multi-component Phase DiagramsCalculation of Multi-component Phase Diagrams • Interfacial Reactions Interfacial Reactions – – Metal/Liquid Solder, Metal/CeramicsMetal/Liquid Solder, Metal/Ceramics• Thin Films ReactionsThin Films Reactions – – Metal/SiliconMetal/Silicon• Thermodynamics of Nano MaterialsThermodynamics of Nano Materials – – Capillarity Effect Capillarity Effect