Brno contribution to the COST 531 Brno contribution to the COST 531 LLead-ead-FFree Solders thermodynamic database ree Solders thermodynamic database

Aleš Kroupa1, Jan Vřešťál2, Jiří Vízdal1,3, Adéla Zemanová1

2Institute of Theoretical and Physical Chemistry Faculty of Science, Masaryk University, Czech Republic

1Institute of Physics of MaterialsAcademy of Sciences of Czech Republic

3Institut fur Anorganische Chemie –

Materialchemie, Universität Wien, Währinger Strasse, Austria

11st st step – Brno solder database step – Brno solder database ((year 2003year 2003))

Unary data:Based on SGTE (4.4)

Covered the following 8 elements:Ag, Bi, Cu, In, Sb, Sn, Pd, Zn

Contained data for 22 binary systems from the literature: Ag-Bi, Ag-In, Ag-Pd, Ag-Sb, Ag-Sn, Ag-Zn, Bi-In, Bi-Sb,Bi-Sn, Bi-Zn, Cu-Ag, Cu-Bi, Cu-Sb, Cu-Sn, In-Sb, In-Sn,In-Zn, Pd-In, Pd-Sn, Sb-Sn, Sb-Zn, Sn-Zn

22st st step – Unification step – Unification and development of COST and development of COST database database ((year 2004-2007year 2004-2007)) + A. DINSDALE, A. + A. DINSDALE, A.

WATSONWATSON

MethodologyMethodology

Choose unary data– SGTE unary database v4.4

Search for binary data– SGTE/NPL solders database– Brno solders database– Literature– Data generated by COST 531

Test for consistency/compatibility– MTDATA– ThermoCalc– Pandat

Creation of consistent TDCreation of consistent TD

The Gibbs energy descriptions included in the database should be unique, based on the same assumptions, conditions and models.

A reliable thermodynamic database has to be consistent with respect to:

1. models used for the expression of Gibbs energy functions in the system

2. models and names used for the description of phases, included in the system

3. thermodynamic data used for the same elements and compounds in different systems, starting with unary data for stable and unstable crystallographic structures for all elements, included in the database.

33rd rd step – Actual state of the step – Actual state of the COST database COST database ((year 2007year 2007))version 2.2 + A. DINSDALE, A. WATSONversion 2.2 + A. DINSDALE, A. WATSON

Scope of the database - Ag, Au, Bi, Cu, In, Ni, Pb, Pd, Sb, Sn, Zn

Assessed Binary Systems– Ag-Au, Ag-Bi, Ag-Cu, Ag-In,

Ag-Ni, Ag-Pb, Ag-Pd, Ag-Sb, Ag-Sn, Ag-Zn,

– Au-Bi, Au-Cu, Au-In, Au-Ni, Au-Pb, Au-Pd, Au-Sb, Au-Sn, Au-Zn,

– Bi-Cu, Bi-In, Bi-Ni, Bi-Pb, Bi-Pd, Bi-Sb, Bi-Sn, Bi-Zn,

– Cu-In, Cu-Ni, Cu-Pb, Cu-Pd, Cu-Sb, Cu-Sn, Cu-Zn,

– In-Ni, In-Pb, In-Pd, In-Sb, In-Sn, In-Zn,

– Ni-Pb, Ni-Pd, Ni-Sn, Ni-Zn, – Pb-Pd, Pb-Sb, Pb-Sn, Pb-Zn, – Pd-Sn, Pd-Zn, – Sb-Sn, Sb-Zn, – Sn-Zn

Assessed Ternary Systems– Ag-Au-Cu, Ag-Au-Sb, Ag-Bi-

Sn, Ag-Cu-Ni, Ag-Cu-Pb, Ag-Cu-Sn, Ag-In-Sn, Ag-Ni-Sn

– Au-In-Sb, Au-Ni-Sn– Bi-In-Sn, Bi-Sn-Zn– Cu-In-Sn, Cu-Ni-Pb, Cu-Ni-Sn – In-Sn-Zn

The “Atlas of lead free solders phase Diagrams” is under construction, to bepublished in fall 2007

The reassessment of the Sb-Sn system - reassessment and new experimental data

Calculated according to Oh utilizing unary data from

SGTE version 1.0 (original paper) and version 4.4

13000-8*T + GHSERSBG(BCT_A5,SB;0) 1000 + GHSERSB

Calculated according to our reassessment utilizing unary data from SGTE version 4.4

Sources of experimental data

[Vass] Vassiliev, V., Feutelais, Y., Sghaier, M., Legendre, B.: J. Alloys Comp. 314, pp. 198-205, 2001.[Pre] Predel, B., Schwermann, W.: J. Inst. Met. 99, pp. 169-173, 1971.[Iwa] Iwasé, K., Aoki, N., Osava, A.: Sci. Rep. Res. Inst. 20, Tôhoku Univ., pp. 353-368, 1931.[Han] Hanson, D., Pell-Wallpole, W. T.: J. Inst. Met. 58, pp. 299-310, 1936.

The reassessment of the Sb-Sn system - reassessment and new experimental data

Prediction of Phase Equilibria in the System Ag-In-Pd – partial new assessment using COST experimental

data, cooperation with other labs

In cooperation with Olga Semenova , Karthik Chandrasekaran, Klaus W.Richter, Herbert Ipser, Universitat Wien

Ag-In-Pd Isothermal Cross Section at 500 °CAg-In-Pd Isothermal Cross Section at 500 °C

With ternary corrections Experiment

A g In

Pd

L

L + In 7Pd 3

L+ In 7Pd 3+ In 3Pd 2

H C P+ InPd+ In 3Pd 2

L+ In 3Pd 2L+H C P+ In 3Pd 2

H C P+In 3Pd 2H C P+InPd

FC C +H C P+ InPd

FC C

F C C +

InP d

InPd

InPd+ InPd 2+T 1

InPd+ InPd 2

InPd 3+ InPd 2+T 1

InPd 3+ InPd 2

FC C + InPd 3InPd 3+ FC C +T 1

InPd+ FC C +T 1

FC C +T 1

A g In

Pd

L

L + In 7Pd 3

L+ In 7Pd 3+ In 3Pd 2

H C P+ InPd+ In 3Pd 2

L+ In 3Pd 2L+H C P+ In 3Pd 2

H C P+In 3Pd 2H C P+InPd

FC C +H C P+ InPd

FC C

F C C +

InP d

InPd

InPd+ InPd 2+T 1

InPd+ InPd 2

InPd 3+ InPd 2+T 1

InPd 3+ InPd 2

FC C + InPd 3InPd 3+ FC C +T 1

InPd+ FC C +T 1

FC C +T 1

, single phase , two-phase, three-phase

With ternary corrections Experiment

A g In

P d

FC C

L

L + In 3P d 2

L + In 3P d 2+ InP d

InP d

L + InP dF C C +

InP d

FC C + L + InP d

FC C + InP d 3

InP d 3+ InP d 2

InP d+ InP d 2

InP d 3+ InP d 2+ T 1

InP d+ InP d 2+ T 1

InP d 3+ FC C + T 1

InP d+ FC C + T 1

FC C

A g In

P d

FC C

L

L + In 3P d 2

L + In 3P d 2+ InP d

InP d

L + InP dF C C +

InP d

FC C + L + InP d

FC C + InP d 3

InP d 3+ InP d 2

InP d+ InP d 2

InP d 3+ InP d 2+ T 1

InP d+ InP d 2+ T 1

InP d 3+ FC C + T 1

InP d+ FC C + T 1

FC C

, single phase , two-phase, three-phase

Ag-In-Pd Isothermal Cross Section at 700 °CAg-In-Pd Isothermal Cross Section at 700 °C

Prediction of Phase Equilibria in the System In-Pd-Sn – partial new assessment using COST experimental data, cooperation with other labs

In cooperation with Ch. Luef, H. Flandorfer and Herbert Ipser, Universitat Wien

With ternary corrections Experiment

In-Pd-Sn In-Pd-Sn Isothermal Cross Section at Isothermal Cross Section at 700 °C700 °C

In Sn

Pd

L

FCC

InPd Pd20Sn13

PdSn

Pd2Sn

Prediction of Phase Equilibria in the System Ag-Ni-Sn – partial new assessment using COST experimental data, cooperation with other labs

In cooperation with U. Saeed, H. Flandorfer and Herbert Ipser, Universitat Wien

Ag-Ni-Sn Isothermal Cross Section 1050 °C

L + Ni3Sn2 + Ni3Sn

L + FCC + Ni3Sn

L + FCC

L + Ni3Sn2L + L

Ni

AgSn

THERMODYNAMIC REASSESSMENT OF THE Cu-Ni-Sn SYSTEM

-in cooperation with H. Flandorfer, C. Schmetterer and H. Ipser

Will be presented by A. Zemanova

THERMODYNAMIC ASSESSMENT OF THE Cu-In-Sn SYSTEM

-in cooperation with J. Drapala et al.,

Presented by J. Drapala

Complete new experimental and theoretical assessments systems

Systems studied:

Bi-Pd - MU, IPM, Univ. Leeds

Bi-Sn - IPM, Univ. of Porto, Univ. of Minho, Univ. of Wien

Pd-Zn - IPM

Bi-Sn-Zn - IPM, Univ of Porto, Univ. of Minho, Univ. of Wien

Pd-Sn-Zn - IPM, Univ of Wien

In-Sb- Sn - MU, IPM, University of Beograd – Faculty in Bor

Bi-Sb- Sn - MU, IPM, University of Beograd – Faculty in Bor

The X-Sn-Zn systems will be presented by J. Vizdal and H. Braga

THERMODYNAMIC ASSESSMENT OF THE Bi-Pd SYSTEM

-in cooperation with A. Watson, A. Scott and J. Pavlu,

The combination of experimental work, CALPHAD modelling and ab-initio calculation – avoiding general lack of experimental measurements

The total energies for intermetallic phases at 0 K were calculated and used in the CALPHAD to model Gibbs energyof formation of relevant phase

THERMODYNAMIC ASSESSMENT OF THE In-Sb-Sn SYSTEM

-in cooperation with D. Manasijevic, D. Zivkovic et al.,

THERMODYNAMIC ASSESSMENT OF THE Bi-Sb-Sn SYSTEM

-in cooperation with D. Manasijevic, D. Zivkovic et al.,

New COST MP0602New COST MP0602

Advanced Solder Materials for High Temperature Application – their nature, design, process and control in a multiscale domain - HISOLD

COST MP0602

‣ how ?Truly multidisciplinary and multiscale approach

On a meso-scale:

The establishment of materials property databases for Pb-free alloy systems suitable for high-temperature solder applications. The aim is to compile a set of databases (e.g. through application of thermodynamics and kinetics studies) containing compilations of information on:

phase diagrams, thermodynamic properties,materials properties (structural, physical, electrical, mechanical …)process related properties of the solder and joint materials.

Advanced Solder Materials for High Temperature Application – their nature, design, process and control in a multiscale domain - HISOLD

COST MP0602

‣ how ?

On a macro-scale: The creation of a phenomenological description and models for the prediction of corrosion behaviour, deformation processes, failure modes etc. occurring in the soldered structure during fabrication and service at high temperatures. Development of processing-structure-property relations, an understanding of thermo-mechanical fatigue, scale and constraining effects of the thermo-mechanical response, the durability of interfaces and intermetallics and to identify optimum process conditions.

Truly multidisciplinary and multilevel approach

On a micro- (nano-) scale: Reactive phase formation study. Formation of intermetallic compounds at solder/substrate interfaces The development of texture of the reaction products in concentration gradients and the development of defect structures in the vicinity of the reaction interface. the study of the role of competitive nucleation and growth of intermediate phases on the interface of solder/substrate system.

Advanced Solder Materials for High Temperature Application – their nature, design, process and control in a multiscale domain - HISOLD

COSt MP0602

‣ how ?

Lead free high-temperature solders – Ag-Bi-…, Zn-Sn-…, Zn-Al-(Mg,Ge,Ga,Bi,Sn), Sb-Sn-…

Meso- Macro- Micro(nano)-

Corrosion prop. ...Fabrication Interface reactionMaterial prop.Phase diagram

assess.

WG1-database of MP WG2-properties of solder joints

WG3-interface properties

Optimal solder system – fundamental prop., processing and reliability issues,…

Advanced Solder Materials for High Temperature Application – their nature, design, process and control in a multiscale domain - HISOLD

OC-2006-1-0599

Management committee “kick-off” meeting

MC Chair A. KroupaVicechair A. WatsonGrant holder ?(STSM officer)

WG1 coordinator G. BorzoneWG2 coordinator J. VillainWG3 coordinator N. Moelans (A. Kodentsov)TP Database A. DinsdaleMP Database J. CugnoniP&M Database ?

Austria, Belgium, Bulgaria, Czech Rep., Finland, France, Germany, Italy, Netherlands, Poland, Serbia, Slovakia, Slovenia, Switzerland, UK - signedPortugal, Sweden – intention to sign

Advanced Solder Materials for High Temperature Application – their nature, design, process and control in a multiscale domain - HISOLD

OC-2006-1-0599

Workgroup “kick-off” meeting

Held in BRNOeither end of August or September

Participants – anybody involved

Program:

•Plenary lectures from “experts”•Round robin discussions – WG separately, the overall discussion at the end of the

session •Presentation of ideas and plans by WG and database coordinators•Presentation of Group project (by the leaders) both prepared and planned – actualized with respect to previous discussion results.

Aim: Plan and coordinate the work on systems and methodology as much as possible, preparation of much detailed working plans for WGs

This work was supported by the COST projects This work was supported by the COST projects Nos. OC 531.001 and OC 531.002 of Ministry of Nos. OC 531.001 and OC 531.002 of Ministry of

Education of Czech Republic.Education of Czech Republic.

Thank you for attentionThank you for attention

With ternary corrections Experiment

In-Pd-Sn In-Pd-Sn Isothermal Cross Section at Isothermal Cross Section at 500 °C500 °C

Pd

In SnL

FCC

Pd2Sn

Pd20Sn13

PdSn

PdSn2

InPd

AgSn

L + Ni3Sn4

FCC#1+FCC#2+Ni3Sn

FCC + Ni3Sn2 + Ni3Sn

L + Ni3Sn4 + Ag3Sn

Ag-Ni-Sn Isothermal Cross Section 450 °C

Ni

AgSn

L + Ni3Sn4

FCC#1+FCC#2+Ni3Sn

FCC + Ni3Sn2 + Ni3Sn

L + Ni3Sn4 + Ag3Sn

HCP + Ni3Sn4 + Ni3Sn2

Advanced Solder Materials for High Temperature Application – their nature, design, process and control in a multiscale domain - HISOLD

COST MP0602

‣ … and the benefits ?

At the end of the COST Action, a wide set of data will be available for different solder alloys.

Number of environmentally friendly lead-free solder systems for high-temperature applications that exhibit properties suitable for industrial use and which can be taken into further consideration as replacements for the existing high-lead solders.

The present Action will also provide the opportunity for Academic Institutions to coordinate their research efforts on a European level with industry - SME and large companies are involved either directly (Cookson Electronic, Next Experience B.V., Mat-Tech, B.V.) or through cooperating partners (PHILIPS, etc.)

It will contribute to the strong position of the Universities and Research Institutions involved in the field of materials science. This will make these academic institutions more attractive for industrial (commercial) partners oriented towards sustainable technologies and maintain the education standard of European students at a high level

Institute of Physics of Materials, AS CR, Brno, Czech Republic

0 0.2 0.4 0.6 0.8 1

x S n

200

400

600

800

1000

1200

1400

1600

1800

2000

Tem

per

atu

re /

K

P d S n

L I Q U IDF C C

Pd

3Sn

Pd

2S

n

P

d3S

n2

Pd

Sn

Pd

Sn

2

Pd

Sn

3

Pd

Sn

4

P

d2S

n

Pd

20S

n13

xSn

Calculated according to Ghosh Calculated according to „COST531“before optimisation of FCC_A1parameter

Comparison between calculated phase diagram Pd-Sn and experimental data - reassessment of original data only

Calculated according to „COST531“with optimised L(FCC_A1) parameter

Comparison between calculated phase diagram Pd-Sn and experimental data - reassessment of original data only

Differences between SGTE 4.4 and Differences between SGTE 4.4 and SGTE 1.0SGTE 1.0

GG ppaarraammeetteerr SSoollddeerrss SSGGTTEE ((44..44))G(TETRAGONAL_A6,BI;0) 5575.382 + GHSERBI 4184.07 + GHSERBI

G(BCT_A5,IN;0) 2092 +GHSERIN 5040.87-3.33969*T + GHSERIN

G(FCC_A1,IN;0) 123-.1988*T+GHSERIN 162.061+ GHSERIN

G(BCT_A5,SB;0) 1000 +GHSERSB 13000-8*T + GHSERSB

G(FCC_A1,SN;0) 4150-5.2*T+GHSERSN 5510-8.46*T + GHSERSN

G(HCP_A3,SN;0) 2400-3.1*T+GHSERSN 3900-7.646*T + GHSERSN

G(TETRAGONAL_A6,SN;0) 5015.5-7.5*T+GHSERSN 5387-8.26212*T + GHSERSN

G(BCT_A5,ZN;0) 4184. + GHSERZN 2886.96-2.5104*T + GHSERZN

G(HCP_A3,ZN;0) GHSERZN 2969.82-1.56968*T+ GHSERZN

Gref - the reference level of the molar Gibbs energy of the phase, Gid - the contribution of the ideal mixing, Gex - excess Gibbs energy, which describes the influence of non-ideal

behaviour on the thermodynamic properties of the phaseOther terms can be added related to contributions from e.g. the interface energy, energy of plastic deformation, magnetism, pressure etc.

Excess Gibbs energy – Redlich-Kister-Muggianu polynomial

,... fP

fmag

fE

fid

fref

fm GGGGGG

The temperature and concentration dependency of Gibbs energy of studied phase:

n

k

kji

kji )xL(xxxG

0

E

Creation of consistent TD – cond. 1Creation of consistent TD – cond. 1

Selection of models for the description of a particular phase and allocation of a name to it.

Cu6Sn5 and CuIn - phases

in the ternary Cu-In-Sn system - complete solubility was found experimentally between the phases, which were not deemed to be identical from the crystallographic point of view when the theoretical assessments of relevant binary systems were prepared by various authors.

The same systems were often modelled several times by various authors – identification of models used in these assessments, number of sublattices, sublattice ratios, etc.

Creation of consistent TD – cond. 2Creation of consistent TD – cond. 2

Consistency of the assessment of the Gibbs energy for an element or compound in a given crystallographic structure (specie) in various subsystems in the database, containing this specie.

Especially the Gibbs energy assessment for the metastable crystallographic structures may differ significantly

the parameters are either estimated (in the past) modelled during the assessment of higher order system, where such structure

exists the energy difference of such hypothetical phase at 0K with respect to stable

phases is calculated by ab-initio methods.

Differences between SGTE unary database version 4.4 and version 1.0Differences between SGTE unary database version 4.4 and version 1.0

GG ppaarraammeetteerr SSGGTTEE 11..00 SSGGTTEE 44..44 G(TETRAGONAL_A6,BI;0) 5575.382 + GHSERBI 4184.07 + GHSERBI

G(BCT_A5,IN;0) 2092 +GHSERIN 5040.87-3.33969*T + GHSERIN

G(FCC_A1,IN;0) 123-.1988*T+GHSERIN 162.061+ GHSERIN

G(BCT_A5,SB;0) 1000 +GHSERSB 13000-8*T + GHSERSB

G(FCC_A1,SN;0) 4150-5.2*T+GHSERSN 5510-8.46*T + GHSERSN

G(HCP_A3,SN;0) 2400-3.1*T+GHSERSN 3900-7.646*T + GHSERSN

G(TETRAGONAL_A6,SN;0) 5015.5-7.5*T+GHSERSN 5387-8.26212*T + GHSERSN

G(BCT_A5,ZN;0) 4184. + GHSERZN 2886.96-2.5104*T + GHSERZN

G(HCP_A3,ZN;0) GHSERZN 2969.82-1.56968*T+ GHSERZN

Creation of consistent TD - cond. 3Creation of consistent TD - cond. 3

Solid Phases…….(Solid Phases…….(some of them!some of them!))

Phase NameNumber ofsublattices

Stoichiometry Constituents

AUZN_GAMMA 4 0.15385 0.15385 0.23077 0.46153 Au, Zn Au Au, Zn Zn

CUIN_GAMMA 3 0.654 0.115 0.231Ag,Cu

Ag,CuIn

In, Sn

BETA_INPD2 2 0.34 0.66 In Pd

INNI_CHI 3 1 1 1 Ni, Va Ni In, Ni

IN3PD2 2 0.6 0.4 In Ag,Pd

LAVES_C15 2 2 1Cu, Zn

Cu,Zn

NI3SN2 3 0.5 0.25 0.25 Ni, Sn Au,Ni Au,Ni

PDZN_GAMMA 2 2 9 Pd, Zn Pd,Zn

SBSN 2 1 1Bi,Pb,Sb,Sn

Sb,Sn

ZETA_AGZN 2 1 2 Zn Ag, Zn

AgIn

Pd

FCCFCC+InPd3

InPd3+InPd2+T1

InPd+InPd2+T1

InPd+T1

InPdIn3Pd2+InPd+HCP

Ag2In+In7Pd3+In3Pd2

L+In7Pd3

L + In 7P d 3 + H C P

Ag2In + HCP + In7Pd3H C P + A g 2In + I n 3P d 2

HCP + In3Pd2F C C + H CP + InP d

FCC+

InPdFCC

FCC+T1

InPd+FCC+ T1

InPd3+FCC+T1

AgIn

Pd

FCCFCC+InPd3

InPd3+InPd2+T1

InPd+InPd2+T1

InPd+T1

InPdIn3Pd2+InPd+HCP

Ag2In+In7Pd3+In3Pd2

L+In7Pd3

L + In 7P d 3 + H C P

Ag2In + HCP + In7Pd3H C P + A g 2In + I n 3P d 2

HCP + In3Pd2F C C + H CP + InP d

FCC+

InPdFCC

FCC+T1

InPd+FCC+ T1

InPd3+FCC+T1

AgIn

Pd

FCCFCC+InPd3

InPd3+InPd2+T1

InPd+InPd2+T1

InPd+T1

InPdIn3Pd2+InPd+HCP

Ag2In+In7Pd3+In3Pd2

L+In7Pd3

L + In 7P d 3 + H C P

Ag2In + HCP + In7Pd3H C P + A g 2In + I n 3P d 2

HCP + In3Pd2F C C + H CP + InP d

FCC+

InPdFCC

FCC+T1

InPd+FCC+ T1

InPd3+FCC+T1

AgIn

Pd

FCCFCC+InPd3

InPd3+InPd2+T1

InPd+InPd2+T1

InPd+T1

InPdIn3Pd2+InPd+HCP

Ag2In+In7Pd3+In3Pd2

L+In7Pd3

L + In 7P d 3 + H C P

Ag2In + HCP + In7Pd3H C P + A g 2In + I n 3P d 2

HCP + In3Pd2F C C + H CP + InP d

FCC+

InPdFCC

FCC+T1

InPd+FCC+ T1

InPd3+FCC+T1

, single phase , two-phase, three-phase

Ag-In-Pd Isothermal Cross Section at 200 °CAg-In-Pd Isothermal Cross Section at 200 °C