Brno contribution to the COST 531 Lead- Free Solders thermodynamic database Aleš Kroupa 1, Jan Vřešťál 2, Jiří Vízdal 1,3, Adéla Zemanová 1 2 Institute of Theoretical and Physical Chemistry Faculty of Science, Masaryk University, Czech Republic 1 Institute of Physics of Materials Academy of Sciences of Czech Republic 3 Institut fur Anorganische Chemie – Materialchemie, Universität Wien, W ä hringer Strasse, Austria

1 st step – Brno solder database (year 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

2 st step – Unification and development of COST database (year ) + A. DINSDALE, A. WATSON Methodology 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 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.

3 rd step – Actual state of the COST database (year 2007) version 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 be published 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 *T + GHSERSB G(BCT_A5,SB;0) 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 , [Pre]Predel, B., Schwermann, W.: J. Inst. Met. 99, pp , [Iwa]Iwasé, K., Aoki, N., Osava, A.: Sci. Rep. Res. Inst. 20, Tôhoku Univ., pp , [Han]Hanson, D., Pell-Wallpole, W. T.: J. Inst. Met. 58, pp , 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 °C With ternary correctionsExperiment  , single phase , two-phase , three-phase

With ternary correctionsExperiment , single phase , two-phase , three-phase Ag-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 Isothermal Cross Section at 700 °C In Sn Pd L FCC InPdPd 20 Sn 13 PdSn Pd 2 Sn

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 + Ni 3 Sn 2 + Ni 3 Sn L + FCC + Ni 3 Sn L + FCC L + Ni 3 Sn 2 L + L Ni Ag Sn

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 energy of 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 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....FabricationInterface 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 Management committee “kick-off” meeting MC ChairA. Kroupa VicechairA. Watson Grant holder? (STSM officer) WG1 coordinatorG. Borzone WG2 coordinatorJ. Villain WG3 coordinatorN. Moelans (A. Kodentsov) TP Database A. Dinsdale MP DatabaseJ. Cugnoni P&M Database? Austria, Belgium, Bulgaria, Czech Rep., Finland, France, Germany, Italy, Netherlands, Poland, Serbia, Slovakia, Slovenia, Switzerland, UK - signed Portugal, Sweden – intention to sign

Advanced Solder Materials for High Temperature Application – their nature, design, process and control in a multiscale domain - HISOLD OC Workgroup “kick-off” meeting Held in BRNO either 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 Nos. OC and OC of Ministry of Education of Czech Republic. Thank you for attention

With ternary corrections Experiment In-Pd-Sn Isothermal Cross Section at 500 °C Pd In Sn L FCC Pd 2 Sn Pd 20 Sn 13 PdSn PdSn 2 InPd

Ag Sn L + Ni 3 Sn 4 FCC#1+FCC#2+Ni 3 Sn FCC + Ni 3 Sn 2 + Ni 3 Sn L + Ni 3 Sn 4 + Ag 3 Sn Ag-Ni-Sn Isothermal Cross Section 450 °C Ni Ag Sn L + Ni 3 Sn 4 FCC#1+FCC#2+Ni 3 Sn FCC + Ni 3 Sn 2 + Ni 3 Sn L + Ni 3 Sn 4 + Ag 3 Sn HCP + Ni 3 Sn 4 + Ni 3 Sn 2

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

x Sn 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 SGTE 1.0

G ref - the reference level of the molar Gibbs energy of the phase, G id - the contribution of the ideal mixing, G ex - excess Gibbs energy, which describes the influence of non-ideal behaviour on the thermodynamic properties of the phase Other 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 The temperature and concentration dependency of Gibbs energy of studied phase: Creation of consistent TD – cond. 1

Selection of models for the description of a particular phase and allocation of a name to it.  Cu 6 Sn 5 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. 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 1.0 Creation of consistent TD - cond. 3

Solid Phases…….(some of them!) Phase Name Number of sublattices StoichiometryConstituents AUZN_GAMMA Au, ZnAuAu, Zn Zn CUIN_GAMMA Ag, Cu Ag,Cu In In, Sn BETA_INPD InPd INNI_CHI3111Ni, VaNiIn, Ni IN3PD InAg,Pd LAVES_C15221 Cu, Zn Cu,Zn NI3SN Ni, SnAu,Ni PDZN_GAMMA229Pd, Zn SBSN211 Bi,Pb, Sb,Sn ZETA_AGZN212ZnAg, Zn

, single phase , two-phase , three-phase Ag-In-Pd Isothermal Cross Section at 200 °C