.. .. Electronic,

, Double roadmap for further miniaturization of electronic system

]. .. , 5 1.4 Schematic diagram showing two approaches, (a) System on chip (SOC), vol.9

. , Ball and wedge wire bonding

. , 9 1.10 (a) Schematic for flip chip bonding (b) cross-section view of flip chip bonding, Schematic for showing different components of flip chip bonding

. , Schematic diagram for (a) UBM and (b) solder deposition on for C4 bumping

]. .. ,

. .. Thermocompression, Flip chip bonding with (a) Mass reflow, (b), p.12

, SEM image for different levels of packaging included WLP, p.14

. .. , 14 1.17 Misalignment due to CTE mismatch between wafers (a) schematic diagram and (b) SEM micrograph [39], Difference in geometries for solder bump and microbump

, SEM micrograph of interconnect failure due to CTE mismatch, p.16

, Schematic diagram showing problem with bonding due to warpage, p.17

. , 20 1.22 10 µm pitch assembly, (a) schematic diagram for the assembly, (b) electrical resistance graph for formed interconnect (c) SEM image showing the interconnect after bonding at 240°C [53], vol.23, p.164

. Chapter, LIST OF FIGURES

]. .. , 25 (a) SEM images for Cu pillar at 10 µm pitch, (b) schematic diagram showing mechanical key and (c) SEM image for assembly [58, p.23

, SEM image of assembly at 10 µm pitch with Cu/Sn interconnect, p.24

. , 25 1.28 Schematics showing different mechanism for diffusion. J D is diffusional flux due to volume diffusion and J GB is diffusion flux due to grain boundary diffusion, Equilibrium Phase Diagrams for binary system (a) Ag-Ni [64] (b)Sn-Ag [65] and (c) Sn-Ni [66]

, Sn interface after (a) 150°C for 600 hrs (granular, non continuous IMC) (b) 200°C for 1200 hrs (continuous scalloped shape IMC) with traditional diffusion couples, SEM micrographs showing IMC formed at Ni, p.28

]. .. , 29 1.31 (a) Reaction kinetics for Ni/Sn(5 µm)/Ni and Ni/Sn-Ag(7 µm)/Ni diffusion couple made by Ni/Sn electrochemical deposition, (b) SEM micrographs for Ni/Sn/Ni diffusion couple after 28 hrs of annealing at 180°C and (c) SEM micrographs for Ni/Sn-Ag/Ni diffusion couple after 552 hrs of annealing at 150°C [76, 77], SEM micrographs for IMC after isothermally aging of diffusion couple made by Ni electrochemical deposition with Sn balls [75

. , of diffusion couple prepared by electrochemical deposition at (a) 150°C, 2 hrs (b) 150°C, 8 hrs [78], SEM micrographs for Ni/Sn couples showing IMC after annealing

. .. , SEM micrographs for diffusion couple made by NiP sheets with solder balls and reflow for 1 min at 250°C and annealed at 150°C [79], p.30

, Literature review for growth kinetics for Ni, vol.3, p.31

, SEM micrographs for diffusion couple prepared by Ni and Sn plates, showing scalloped and facetted shape Ni 3 Sn 4 IMCs after annealing at 250°C [51, p.32

. , Sn 4 IMC formed in Ni/Sn diffusion couple prepared by Ni sheets and Sn balls, (a) log of Ni 3 Sn 4 thickness vs log of time, (b) initial stages (c) intermediate stages and (d) latter stages [89], Reaction kinetics showing 3 kinetics regime for growth of Ni 3

. , .9 µm after 30 secs, (b) 9.4 µm after 16 min (c) 191 µm after 2 days, TEM micrographs showing the grain structure and size of IMC layer after (d) 10 secs and (e) 60 secs of annealing at 250°C [89], SEM micrograph showing Ni 3 Sn 4 IMC thickness after annealing at 250°C, (a) 1

. , 34 1.40 Comparison of growth kinetics for growth of Ni 3 Sn 4 IMC at 250°C for different diffusion couples prepared with Ni plates and different types of solder alloy, SEM micrographs for diffusion couple prepared by electrochemical deposition annealed at 250°C, (a)

. , 1 (a) Schematic diagram for top and bottom chip (die) before bonding and (b) interconnect after bonding, vol.2

. , Schematic presentation for fabrication of Cu pillars

. , SEM image of Cu pillars after fabrication, vol.40, p.165

. Chapter, LIST OF FIGURES

. .. , Schematic presentation for fabrication of metallic pads, p.40

, SEM image of as deposited metallic pads of 6.5 µm in diameter, p.41

, SEM image for Cu pillar after Cu seed etching, showing Cu and Ti undercut, p.41

. , Schematic drawing showing the difference between (a) isotropic etching and (b) anisotropic etching

. , Difference in the etching rate of Cu by wet etching in two cases: Cu deposited by electrochemical deposition (ECD) and Cu deposited by physical vapour deposition (PVD)

, SEM image of Cu bump after seed etching, red points show the Cu undercut, p.43

. , Optical microscopy image of the field of Cu pillar (a) before etching (b) after seed etching

. , The test vehicle for Cu pillar wafer (a) schematic representation of wafer (b) one field with the description of sub-field and (c) description of distribution of Cu pillar with different diameter

, The test vehicle for metallic pad wafer (a) schematic diagram representation of a single field in wafer with bottom chips, (b) optical image of one field, p.45

, SEM micrographs for Cu pillars 150 µm in diameter fabricated to study the interfacial reactions between Ni and (a) solid Sn-2wt%Ag alloy

.. .. Sn,

. , Schematic representation for electrical measurement (a) Daisy chain and (b) Kelvin chain

. , 16 (a) Electrical test vehicle and a test group (b) schematic representation for conception in the test vehicle, Schematic representation for daisy chain in the electrical test vehicle (b) SEM image for a Daisy chain in top chip: Cu pillar

, Schematic diagram showing the steps of flip chip bonding process (hybridization, p.49

. , 18 (a) Schematic representation of reflow. (b) Schematic representation of a temperature-time reflow profile

. , 50 2.20 SEM image of solder bump of 5µm after reflow

. .. , 53 2.23 Schematic representation for leveling done on FC300, (a) the parallelism before levelling and (b) parallelism after levelling, Schematic representation of alignment and positioning of top and bottom chip

. .. , Schematic diagram of semi open confinement chamber : FC300, vol.54

. .. Different-method-for-underfilling, 55 2.26 SEM images of cross-section prepared (a) with mechanical polishing (b) with ion beam polishing

, Schematic diagram showing difference in orientation of sample surface for ion beam etching for (a) cross-section, (b) contrast to expose grain, p.57

E. .. Principle,

M. and C. , simulation for e-beam penetration in Ni 3 Sn 4 with 20 keV energy, p.59

. Schematic and . .. Ebsd,

. , Principle of X-Ray diffraction (Bragg's law)

. .. Schematic-diagram-for-x-ray-tomography, , vol.61, p.166

. Chapter, LIST OF FIGURES

. , Schematic diagram for performing shear test

. , Ni interface for test vehicle 1 after electroplating process, (a) full pillar (b) enlarged view of the interface between Ni and Sn-Ag alloy, SEM micrographs of the initial state of Sn-Ag alloy

. .. , 68 3.3 SEM micrographs of the initial state of the Sn-Ag alloy/Ni interface for test vehicle 2 after electroplating process, (a) pillar (b) enlarged view of the interface between Ni and Sn-Ag alloy, EDX analysis of test vehicle 1 after depostion

. , 69 3.5 DSC curve during heating (3°C /min) and cooling (3°C/min) for 150 µm diameter pillar (test vehicle 3), SEM micrographs of the initial state of Sn-Ag alloy/Ni interface for test vehicle 3 after electroplating process

. , Binary phase diagram for Sn-Ag [65]

. , Typical DSC curves during heating of 5 µm diameter pillar (test vehicle 1) with a heating rate of 3°C/min

. , µm bumps) (a) after deposition and (b) after reflow at 250°C for 60 secs. The target composition of solder alloy is Sn-2wt%Ag, A typical microstructure of the solder bumps of the test vehicle, vol.1

. .. Secs, 10 (a) General view of a sample after an isothermal holding for 1 minute at 210°C showing the formation of a reaction layer about 1 µm thick all over the solid Sn-Ag/Ni interface. (b) SEM micrographs of the solid Sn-Ag/Ni after 1 minute at 210°C and (c) liquid Sn-Ag/Ni interface after 1 minute at 230°C, EDX analysis of test vehicle 1 (a) after deposition and (b) after reflow at 250°C for 60, vol.73

. , EDX analysis of reaction product formed at the solid Sn-Ag/Ni interface for the samples which were aged at 210°C for 1 hr

. , Binary Ni-Sn phase diagram [66]

. , Average thickness of Ni 3 Sn 4 layer formed at the solid Sn-Ag/Ni interface versus reaction time at 150, 180, 200 and 210°C, initial thickness at time t = 0 : e 0 = 0.12 µm(*)

. , Log-log plot of the variation of ?e with the reaction time at 150, 180, 200 and 210°C. ?e = e-e 0. e and e 0 are the average thickness of Ni 3 Sn 4 layer formed at the solid Sn-Ag/Ni interface at time t = 0 and t respectively

, Thickness (e) of the Ni 3 Sn 4 phase layer for the Sn-2%Ag alloy/Ni diffusion couple and thickness of as a function of the cube root of reaction time, p.80

, Arrhenius plot of Ni 3 Sn 4 later growth in solid Sn-2wt%Ag alloy/Ni system, vol.81, p.167

. Chapter, LIST OF FIGURES

. , Sn chemical potential (b) through the solid Sn/Ni interface when a continuous layer of ?Ni 3 Sn 4 phase is formed at the interface. Schematic presentation of variation of the Gibbs free energy versus Sn concentration in binary Sn-Ni system at T < 230°C, indicating the stable and metastable equilibria between ?-Ni 3 Sn 4 compound and solid Sn or Ni as well as the chemical potentials of Ni and Sn corresponding to these equilibria

. , and with nucleation and growth of new grains at the reactive interfaces (c). (a) The width (d) of Ni 3 Sn 4 grains remains constant during the growth process. (b) The ratio (?) between the thickness (e) of Ni 3 Sn 4 layer and the width (d) remains constant during the growth process ? = e/d = constant), Schematic presentation of Ni 3 Sn 4 grains growth at solid Sn/Ni interface without nucleation of new grains-the length of Ni 3 Sn 4 grains is equal to Ni 3 Sn 4 thickness

, Sn 4 reaction layer formed at solid Sn/Ni interface showing the grains of Ni 3 Sn 4 phase (with 15 µm average length of crosssection) (a) T = 150°C, t = 16 hours-only one range of grains is observed, SEM micrographs of the Ni 3

T. , t = 4 hours-two ranges of grains are observed, p.86

, Representative SEM micrographs of the reaction product formed at the Ni/solid Sn-Ag interface for the samples which were aged at 200°C for 1 day, p.91

, Representative SEM micrographs of the reaction product formed at the Ni/solid Sn-Ag interface for the samples which were aged at 200°C for 4 days, p.91

, Representative SEM micrographs of the reaction product formed at the Ni/solid Sn-Ag interface for the samples which were aged at 200°C for 15 days, p.92

, Representative SEM micrographs of the reaction product formed at the Ni/solid Sn-Ag interface for the samples which were aged at 200°for 35 days, p.92

. , Average thickness of Ni 3 Sn 4 layer formed at the Ni/solid Sn-Ag interface versus reaction time at 200°C

. , Sn 4 reaction layer thickness (e) with the reaction time at 200°C. For t< 4hrs test vehicle 2 is used (Sn=3 µm) while for t> 24 hrs test vehicle 3 is used (Sn=10-24 µm)

. , SEM micrographs of the reactions layer formed at solid Sn/Ni interface at 200°C for 15 days showing the grains of Ni 3 Sn 4 phase (with 15 µm average length of cross-section) and grain of Ni 3 Sn 2

. , General view of a sample after an isothermal holding for 1 minute at 300°C showing the formation of a reaction layer about 1 µm thick all over the Ni/Sn-Ag interface

, SEM micrographs of the reaction product formed at the Ni/liquid Sn-Ag interface for the samples which were aged at 230 to 350°C for 1, 2, 4 and 15 mins 97

. .. Min, 98 3.34 SEM micrographs of the reaction product formed at the Ni/liquid Sn-Ag interface for the samples which were aged at 230 to 350°C for 1, 2, and 4 hrs, EBSD analysis for pillars after annealing at 250°C for 1, vol.98, p.168

. Chapter, LIST OF FIGURES

. , Schematic presentation of variation of the Gibbs free energy formation of (Sn,Ni) liquid phase, (Ni,Sn) solid phase and ?-Ni 3 Sn 4 compound at T > 232°C indicating the stable (-) and metastable (-) equilibria as well as the chemical potentials of Ni and Sn corresponding to these equilibria (e). Variation with the temperature of the concentration of Ni in liquid Sn at the metastable Ni/liquid Sn equilibrium (f) calculated by CALPHAD modelling of the binary Ni-Sn system using data from Gosh

. , Average thickness of Ni 3 Sn 4 layer (e) formed at the Ni/liquid Sn-Ag interface versus reaction time at 230, 250, 300 and 350°C

. , Log-log plot of the variation of ?e with the reaction time at 230, 250, 300 and 350°C. ?e = e-e 0. e and e 0 are the average thickness of Ni 3 Sn 4 layer formed at the Ni/liquid Sn-Ag interface at time t = 0 and t respectively, here e 0 = 0.25 µm

, Arrhenius plot of Ni 3 Sn 4 reaction product growth in Sn-2wt%Ag liquid alloy/solid Ni system logk = f(1/T). k is the growth constant of Ni 3 Sn 4 layer in m.s-n, p.106

. .. , 1 (a) Reflow profile no 1 and (b) schematics for reflow, p.113

. .. , 115 4.5 SEM micrograph for 5 µm diameter Cu/Ni/Sn-Ag pillar reflowed with profile no. 1 in formic acid without seed etching showing different formations. (a) General view and (b) cross-section, SEM image of Cu pillar of 5 µm diameter with seed etching after reflow with profile

]. .. ,

. , 117 4.10 SEM images for Cu pillars reflowed with reflow profile no. 2 in reducing atmosphere without seed etching (a) showing Bump with no solder left, (b) cross-section of bump with no solder left and (c) cross-section of bump with some solder left, SEM image for Cu pillars (without seed etching) reflowed with reflow profile no. 2 in inert atmosphere (a) showing bump and (b) cross-section. .. .. .. 117 4.9 SEM images of the bumps reflowed in inert atmosphere

. , Schematics for bonding at 10 µm pitch, vol.119, p.169

. Chapter, LIST OF FIGURES

. , breaking the assembly) bonding done (a) with liquid flux and (b) with gaseous flux, Pads after bonding and de-bonding

. .. , (a) SEM image for cross-section of Sn interconnect, (b) EDX cartography showing presence of Ni, Au and Sn (c) EDX cartography showing the presence of Ni and (d) EDX cartography showing the presence of Au, Temperature-time profile for assembly of interconnect at 10 µm pitch (a) Process A and (b) Process B, under formic acid, p.123

A. Sn, Cross-section of IMC interconnect form by process B under formic acid (a) SEM image (b) EDX cartography showing the presence of Ni

. , Summary of schematic configuration of different systems after reflow and bonding processes under formic acid atmosphere (with seed etching) and corresponding T(t) profiles, p.125

. , ) during very rapid dissolution of a Au layer in a liquid layer of Sn (thickness l) form initial C = 0 (t = 0) to final concentration C = C f (attained at t = t f ) corresponding to the total dissolution of Au layer. Process limited by the dissolution kinetics

. .. , Calculated ternary phase diagram for Ni-Au-Sn ternary system at 240°C with Thermocalc software (a, b and c) and its schematic presentation (d), p.127

. .. Secs, 24 (a) Micrographs and their EDX cartography for Sn interconnects just after the joining process A and (b) after annealing at 200°C for 30 min (c) 4 hrs and (d), 22 SEM section of test vehicle reflow at 220°C for 60, vol.131

, Isothermal section of the ternary Au-Sn-Ni system at 200°C according

. .. Hrs, 28 (a) SEM micrograph Sn interconnects (process A) after aging at 200°C for 24 hrs and (b) its enlarged SEM micrograph for the interface between Ni and Ni 3 Sn 4 134 4.29 SEM micrograph for Sn interconnect (process A) showing the interface between Ni and Ni 3 Sn 4 after annealing at 200°C for (a) 45, SEM micrographs for annealing of Sn interconnects at 200°C (a) at t=0, (b) t=24 hrs, (c) t=204 hrs and (d) t=1303, vol.134, p.1303

. .. , 135 4.31 SEM micrograph for Sn interconnect (process A) showing the interface between Ni and Ni 3 Sn 4 after annealing for 200hrs at (a) 175°C and (b) 200°C. 136 4.32 SEM micrograph for interconnects showing the interface between Ni and Ni 3 Sn 4 after annealing for 200 hrs at 200°C for (a) Sn interconnect (process A) and (b) IMC interconnects (process B), Graphs between log of thickness of Ni 3 Sn 2 layer vs log of time for annealing of Sn Interconnect (process A), vol.140, p.170

. Chapter, LIST OF FIGURES

. , Schematic diagram for performing shear test

. , 142 4.38 SEM micrographs with EDX cartography for Sn interconnects (a) Cu pillars side and (b) Pads side (c) SEM micrograph of a single interconnect showing the Cu pillar and pad sides

. .. , Schematics of metallic layers present in the interconnect, p.145

, Graph showing resistance for interconnects at 10 µm pitch, p.146

. , pad side) to characterize fabrication process

. .. , Graph showing resistance of just pad and the interconnects, p.148

. , Resistance graphs showing change in resistance for former Sn interconnects and IMC interconnects after annealing at 150, 175 and 200°C. Numbers in the legend represents the sample name

. , 46 (a) Schematic diagram for the test groups across the chip tested for characterization after High Temperature Storage test, (b) variation of the resistance of IMC interconnect with annealing time at T = 175°C at test group I and (c) at test group II. (The blue rectangle indicates the position the examined test group and numbers indicate the sample name), Graph showing decrement in the resistance of just pad after 100 hrs of annealing at 175°C

. , SEM micrographs for IMC interconnects after 200 hrs of annealing at 150°C at the interconnects at the edge of the chip. The blue rectangle indicates the position the examined test group across the chip

. , 150°C (a) at the interconnects at the edge of the chip (b) at the center of the chip. The blue rectangle indicates the position the examined test group across the chip, SEM micrographs for former Sn interconnects after 200 hrs of annealing at

, Resistance curves for Sn Interconnects at different annealing time, p.153

. , SEM micrographs and with contrast for Sn interconnects aged at 1303 hrs at 200°C, showing Cu corrosion

. , A.1 Cu-Cu direct bonding (a) schematics and (b) SEM image after assembly at 10 µm pitch [172]

. , Surface activation bonding (a) schematics and (b) SEM image after assembly at 7.5 µm pitch

A. , Cold insertion mcirotubes (a) schematics and (b) SEM image after assembly at 10 µm pitch

. , Soldering with In bumps (a) schematics and (b) SEM image after assembly at 10 µm pitch

. , Micrograph of Ni/Sn-Ag interface showing a reaction layer for which the average thickness is to be measured, vol.162, p.171

. Chapter, LIST OF FIGURES

C. , Isothermal sections of the ternary Au-Ni-Sn system at (a) 200°C and (b) 300°C from Ref [159] and from Thermocalc software (c) and (d)

, Average thickness (e) of the Ni 3 Sn 4 layer formed at solid Sn-2wt%Ag alloy/Ni interface for different holding temperatures and reaction times, p.78

, Ni 3 Sn 4 layer at solid Sn2wt%Ag alloy/Ni interface and of growth exponent n (see Eq 3.2) at 150 to 210°C. Gibbs free energy formation of Ni 3 Sn 4 phase (?G Ni 3 Sn 4 ) from pure Ni and Sn solids at 150 to 210°C [69, 127, vol.80

. , Ni 3 Sn 4 grains formed at Sn/Ni interface after isothermal holdings at 150°C (5 and 960 mins) and at 200°C (5 and 240 mins)-see Figure 3.23. In all cases only one range of grains is observed (length l = layer thickness = e) except for 240 min at 200°C for which two ranges of grains are observed with average widths and lengths (d 1 , l 1 ) and (d 2 , l 2 ) respectively

, Average thickness of the Ni 3 Sn 4 layer formed at solid Sn-2wt%Ag alloy/Ni interface at 200°C for reaction time between 1 day and 35 days, p.93

, C = C 2 ) and in equilibrium with solid Ni (metastable equilibrium, C = C 1 ) at 250, 300 and 350°C. Values obtained from CALPHAD modelling of the binary Ni-Sn system using data, Molar fraction of Ni in liquid Sn in equilibrium with Ni 3 Sn 4 phase (stable equilibrium

. , Average thickness e of the Ni 3 Sn 4 layer (in µm) formed at liquid Sn-2wt%Ag alloy/solid Ni interface for different holding temperatures and reaction times. *Sn is completely consumed before 240 mins of reaction

. , Calculated values of the kinetic growth constant (k) of Ni 3 Sn 4 layer at liquid Sn-2wt%Ag alloy/solid Ni interface and of growth exponent n (see Eq 3.27) at 230, 250, 300 and 350°C

. Physicochemical-data-for-ni, . Sn, and . Au,

, Thickness of Ni 3 Sn 2 after annealing at 200°C for different time, p.136

, Young's modulus and CTE of materials present in the interconnect, p.138

. , Resistivity of materials present in the interconnect

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