Enhancing Adhesion of Screen‐Printed Silver Nanopaste Films

The interfacial fracture energy of screen‐printed silver nanopaste films is quantitatively measured, and the fundamental adhesion mechanism is investigated. It is found that the interfacial fracture energy at the Ag film/silicon substrate interface is critically affected by the sintering condition. The sintering temperature tunes the interfacial surface morphology of Ag films and the amount of organic residues at the interface. These factors determine the degree of interfacial toughening between the Ag film and the substrate, which directly affects the adhesion properties. The increased surface roughness of the Ag film with sufficient organic residues leads to a larger interfacial toughening at the film/substrate interface, and subsequently to an enhanced interfacial fracture energy of screen‐printed Ag nanopaste films.     

Au–Sapphire (0001) solid–solid interfacial energy

This work presents an experimental methodology for the measurement of interfacial energy (γ_SP) and work of adhesion (W _ad) of a metal–ceramic interface. A thin Au film was dewetted on the basal surface of sapphire substrates to form submicron-sized particles, which were analyzed using the Winterbottom method to determine the equilibrated particle–substrate solid–solid interfacial energy. Electron microscopy showed that a large portion of the particles contained grain boundaries, while all of the single crystalline particles had three distinct morphologies and orientations with the substrate. Two orientation relationships were determined from transmission electron microscopy, for which the interfacial energy in air at 1000 °C was determined: Au (111)–sapphire (0001): γ_SP = 2.15 ± 0.04 J/m², W _ad = 0.49 ± 0.04 J/m²; Au (100)–sapphire (0001): 2.18 ± 0.06 J/m², W _ad = 0.55 ± 0.07 J/m².     

Interface controlled growth of nanostructures in discontinuous Ag and Au thin films fabricated by ion beam sputter deposition for plasmonic applications

The growth of discontinuous thin films of Ag and Au by low energy ion beam sputter deposition is reported. The study focuses on the role of the film?Csubstrate in determining the shape and size of nanostructures achieved in such films. Ag films were deposited using Ar ion energy of 150?eV while the Au films were deposited with Ar ion energies of 250?C450?eV. Three types of interfaces were investigated in this study. The first set of film?Csubstrate interfaces consisted of Ag and Au films grown on borosilicate glass and carbon coated Cu grids used as substrates. The second set of films was metallic bilayers in which one of the metals (Ag or Au) was grown on a continuous film of the other metal (Au or Ag). The third set of interfaces comprised of discontinuous Ag and Au films deposited on different dielectrics such as SiO₂, TiO₂ and ZrO₂. In each case, a rich variety of nanostructures including self organized arrays of nanoparticles, nanoclusters and nanoneedles have been achieved. The role of the film?Csubstrate interface is discussed within the framework of existing theories of thin film nucleation and growth. Interfacial nanostructuring of thin films is demonstrated to be a viable technique to realize a variety of nanostructures. The use of interfacial nanostructuring for plasmonic applications is demonstrated. It is shown that the surface Plasmon resonance of the metal nanostructures can be tuned over a wide range of wavelengths from 400 to 700?nm by controlling the film?Csubstrate interface.     

Modified Ni/Pd/Au-finished DBA substrate for deformation-resistant Ag–Au joint during long-term thermal shock test

An Ag–Au joint developed by Ag paste joining on electroless nickel/electroless palladium/immersion gold (ENEPIG)-plated direct-bonded aluminum (DBA) substrate was employed in SiC (Silicon carbide) power modules. The ENEPIG plating was modified to possess high mechanical strength by thickening the Ni layer to 20 μm. The reliability of SiC/DBA die-attached module by Ag–Au joining was evaluated during a long-term thermal shock test (TST) from ??50 to 250 °C up to 2000 cycles. The shear strength of as-sintered Ag–Au joint was evaluated to be 37.6 MPa, but it showed a significant decrease after 1000 thermal cycles and maintained stably from 1000 cycles to 2000 cycles. Based on the microstructural evolution via EBSD observation, it was confirmed, by modifying ENEPIG, the Ag–Au interfacial deformation derived from Al plastic deformation was successfully suppressed even after 2000 cycles. In this case, the mechanism for shear strength degradation was found to be the interfacial delamination between Ag paste layer and ENEPIG substrate. This can be ascribed to the large thermal stress caused by different coefficients of thermal expansion (CTE) of power module components. This study not only realized the deformation-free structure for Ag–Au joint during long-term thermal cycling but also provided fundamental insights for fracture behaviors of Ag–Au sinter joint.

     

Electronic structure of the buried interface between an organic semiconductor, N,N'-bis(3-methylphenyl)-N,N'-diphenylbenzidine (TPD), and metal surfaces

The electronic structures of buried interfaces between an organic semiconductor, N,N'-bis(3-methylphenyl)-N,N'-diphenylbenzidine (TPD) and metal surfaces of Au, Ag, Al and Ca were examined by the new experimental method that we have developed recently. In this method the energy levels at the organic/metal interface can be examined without changing the film thickness and related physical parameters e.g., the vacuum levels of the sample in contrast to the widely-used thickness-dependent photoemission experiments. The results were discussed in view of large interfacial dipole moment of the TPD and metal (Au and Ag) contacts.     

Thermal fatigue of Ag flake sintering die-attachment for Si/SiC power devices

Emerging SiC power semiconductor devices are expected to work under the high temperature condition of 250–300 °C while the operation of Si devices is limited up to 180 °C. The die-bonding materials for emerging SiC power devices hence need to have sufficient capability in such extreme operating environments. In this study, we investigated the thermomechanical reliability of the die-attach technology using Ag flake paste, which can be processed by low-temperature and low-pressure sintering. The Ag flakes start to sinter immediately after the organic dispersant layer is removed from the flake surface at 160 °C, and die-bonding consequently becomes possible. The tested Si die-attachments joining with the paste maintained high strength (23 MPa) up to 1,000 thermal cycles from ?40 to 180 °C. The stable microstructures without crack and no interfacial debonding assure the reliability of the Ag flake paste die-attach of Si. SiC die-attachments also maintained their high strength (24 MPa) up to 1,000 cycles of ?40 and 250 °C, though a slight degradation appeared after 1,000 cycles. The debondings at the sintered Ag flake paste layer/SiC wafer interface were affected to the joining strength with the Ag flake paste. The obtained results indicate that our Ag flake paste die-attach can be applied to both Si and SiC power devices capable of high temperature operations.     

Quantitative evaluation of the adhesion of metallic coatings using cylindrical substrate

This paper introduces an effective interfacial fracture toughness test based on interface fracture mechanics theory. This testing method uses a circumferentially notched tensile (CNT) specimen, which is ideally suited for determining the interfacial fracture resistance of coatings. Unlike other interfacial fracture tests, this test is simple to prepare, requires minimum test setup and is easy to model. An interfacial pre-crack was generated between a nickel coating and mild steel cylindrical substrate to evaluate adhesion strength. In situ acoustic and SEM analyses were used to determine the crack initiation or the critical load of failure. The critical energy release rate, critical stress intensity factors and phase angle were determined using the J integral which was determined by applying the critical load to the finite element model. A detailed finite element analysis was carried out to study the effect of different interface pre-crack positions and mode mixity on energy release rate for different notch angles and elastic modulus ratios. The cracking resistance of the interface was characterised by the notch angle of CNT specimens. The analysis showed an increase in interfacial fracture toughness as phase angle increases and was significant when the phase angle was large. The combined results of computational and experimental analysis showed that any defect or stress concentration at the interface could significantly weaken the adhesion of coating.     

Improvement of wafer-level Cu-to-Cu bonding quality using wet chemical pretreatment

We have evaluated the effect of wet chemical treatment on the interfacial bonding strength of Cu-to-Cu direct bonding. The oxide on a Cu-deposited wafer can be removed by a solution made of hydrofluoric acid and sulfuric acid (HF/H2SO4) or diluted hydrochloric acid (HCl/H2O), which can also improve the bonding quality of Cu-to-Cu bonds. Two 4-inch Cu-deposited wafers were bonded at 250 degrees C via the thermo-compression method. The interfacial adhesion energy of Cu-to-Cu bonding was quantitatively measured by the four-point bending method. After chemical pretreatment for 30 seconds with HF/H2SO4 and HCl:H2O solutions, the measured interfacial adhesion energies were 4.91 J/m2 and 5.51 J/m2, respectively. Microstructural examination of the Cu bonding interfaces showed that the interfacial bonding quality of Cu-to-Cu bonds improved under proper wet chemical etching conditions. Wafer-level cleaning by wet chemical treatment of the Cu surface was found to be a very effective way to improve the bonding quality of Cu bonds, even at bonding temperatures lower than 300 degrees C.     

Validity requirements of circumferentially notched tensile specimens for the determination of the interfacial fracture toughness of coatings

A simple method was developed for evaluating the interfacial fracture toughness of coatings on substrates using circumferentially notched tensile (CNT) specimens. Mild steel cylindrical substrates of 0°, 15°, 30°, 45° and 60° notch angles with electroplated nickel were tensile tested. A well defined pre-crack was introduced at the interface for the quantitative evaluation of adhesion. In situ acoustic signals and scanning electron microscope were used to analyze the crack initiation and propagation. Finite element analyses were used to evaluate the critical interface energy release rate. The size of the plastic zone was determined for different notch angles to validate application of the linear elastic approach in determining the interfacial fracture toughness. The validity requirements have been proposed for this specimen, considering the yield strength of the coating and substrate, pre-crack position, notch angle and plastic zone size. The obtained interfacial fracture toughness values using CNT specimens was found to be very close to the values obtained by others using standard specimens.     

Analysis of in-plane transonically propagating interface crack with a finite contact zone

The report of Lambros and Rosakis [(1995) J Mech Phys Solids 43(2): 169–188] has focused attention on steady-state transonic interfacial crack growth accounting for the phenomenon of crack face contact in elastic/rigid bimaterial but could not handle issues relating to energy transmission across the interface. The present paper attempts to provide a complete explicit expression of the asymptotic fields induced by transonically propagating interfacial crack in elastic/elastic bimaterial for in-plane case. The energy distribution on the contact area, crack tip and two singular characteristic lines is analysed thoroughly and compared with the dynamic separated J-integrals. The length of the contact zone is also discussed briefly by establishing energy fracture criterion that satisfies contact condition. The two-dimensional in-plane asymptotic deformation field surrounding the contact area of a crack propagating transonically along an elastic/elastic bimaterial interface is observed and discussed thoroughly.     

Finite element analysis of contact induced adhesion failure in multilayer coatings with weak interfaces

Experimental work reveals that the Ag/ZnO interface in the multilayer solar control coatings is weakest and most likely to fail during contact. In this study, a cohesive zone model embedded in a finite element code was used to model delamination in multilayer stack consisting of ZnO/Ag/ZnO on glass during contact. It shows that delamination occurs at the upper ZnO/Ag interface during loading when penetration exceeds a critical value, while, the double pinned buckling delamination failure occurs at the lower Ag/ZnO interface during the unloading cycle. Furthermore, it reveals the model based on mechanism of lateral crack at interface yields reasonably accurate values of interfacial toughness when tensile stress induced delamination occurs during unloading.     

Effect of residual stresses on mechanical properties and interface adhesion strength of SiN thin films

Residual stresses play a significant role in the mechanical reliability of thin films. Thus in this study, the mechanical properties and interface adhesion strengths of SiN thin films containing different residual stresses have been investigated by using nanoindentation and nanoscratch tests. With varied residual stresses from compressive to tensile, the penetration depth of nanoindentation tests shifted to a higher value. The hardness and elastic modulus decreased from 11.0 and 95 GPa, respectively, for the film containing a compressive stress of 235 MPa to 9.6 and 84 GPa for the film with a tensile stress of 86 MPa. With decreasing compressive stress and increasing tensile stress, the interface adhesion energy decreased from 1.8 to 1.5 J/m². Compressive stresses were expected to blunt crack tips and inhibit crack propagation, while tensile stresses enlarged crack opening and facilitated crack propagation, thus changing the mechanical properties of the SiN thin films.     

Interfacial microstructure and defect analysis in Cu(In,Ga)Se([sub]2)-based multilayered film by analytical transmission electron microscopy and focused ion beam

Interfacial microstructures of Cu(In,Ga)Se₂(CIGS)-based multilayered film are closely characterized by TEM (transmission electron microscopy), SEM (scanning electron microscopy) and FIB (focused ion beam). A cross-sectional TEM, energy dispersive X-ray spectroscopy and energy-filtered TEM reveal that a pronounced Cu diffusion occurs across the interface of the CdS/CIGS, which leads to a large amount of Cu rich in the CdS layer and a Cu-deficient sub-surface in the CIGS layer as well as a rough interfacial structure. TEM studies further reveal that the interface microstructures in the multilayered film are dissimilar, both ZnO/CdS and CdS/CIGS interfaces are strongly bonded whereas the CIGS/Mo interface is weakly bonded and interface separation occasionally occurs. Mo back contact layer shows a well adhesion to glass substrate.Detailed observation on defects in the CIGS-based multilayered film is carried out by 3D (3-dimensional) FIB and SEM techniques. Sequential 2D (2-demensional) cross-sectioning shows that dominant growth-defects in the CIGS and top SiO₂ layers are micro-scale crack, appearing as diversified morphologies. The micro-scale crack in the CIGS layer is possibly released by propagating into the adjacent layer while the crack in the SiO₂ layer is relieved usually by forming a small particle behind. It is noted that in the multilayered film the interface frequently acts as crack initiation sites due to distinct thermal expansion coefficients.     

Four-point bend adhesion measurements of copper and permalloy systems

The four-point bend split-beam method is used to quantitatively determine the interfacial fracture resistance and crack velocity as a function of mechanical energy release rate of the weakest interface in a thin film stack. Various interfaces of importance to magnetic storage devices are studied, including copper or nickel-iron (permalloy) on silicon oxynitride with additional adhesion promoters. The dynamics and kinetics of the four-point bend test are fully elucidated. A model for environmentally-controlled crack growth previously applied to bulk ceramics is used here as a model for interfacial crack growth and is found to fit the kinetic data.     

In situ Raman monitoring of competitive adsorption of Ag and Au nanoparticles onto a poly(4-vinyl pyridine) surface

The competitive adsorption of citrate-capped Ag and Au nanoparticles (~25 nm in diameter) onto a poly(4-vinyl pyridine) (P4VP) surface has been investigated by means of Raman scattering spectroscopy. The P4VP film prepared on a glass slide was too thin for its normal Raman spectrum to be observed, but the Raman peaks of P4VP could be detected upon the adsorption of Ag and/or Au nanoparticles onto the film, due to the surface-enhanced Raman scattering (SERS) effect associated with the localized surface plasmon of Ag and/or Au nanoparticles. Neither quartz crystal microbalance nor atomic force microscopy (AFM) nor scanning electron microscopy (SEM) methodologies can distinguish between Ag and Au nanoparticles during their adsorption onto P4VP, but it is possible through Raman scattering spectroscopy because Ag (though not Au) nanoaggregates are SERS active at 514.5 nm excitation, while both Ag and Au nanoaggregates are SERS active at 632.8 nm excitation. Coupled with the AFM data, we were thus able to infer that about 120 Ag nanoparticles per 1 μm(2) were adsorbed, along with 60 Au nanoparticles per 1 μm(2), onto the P4VP film over a period of 1.5 h from a 1 : 1 mixture of Ag and Au sols at 1.6 nM each.     

Investigation of space charge at pentacene/Au interface with UV/ozone treatment by a near-field microwave microprobe

The near-field microwave microprobe (NFMM) and Kelvin-probe measurements were performed to evaluate the conductivity in terms of surface potential of pentacene films on Au electrode. The UV/ozone treated and untreated Au electrodes were prepared to reveal the relationship between the electrical conductivity and interfacial electrostatic charging phenomena. For the pentacene film deposited on the Au electrode with UV/ozone treatment, holes were displaced from Au electrode to pentacene film, resulting the accumulation of apparent positive charges in the interfacial region of pentacene film around Au electrode. The NFMM measurement revealed that the reflection coefficient of microwave, S₁₁ increased with UV/ozone treatment, indicating the resistance decrease of the surface. Accumulation of positive charge in the interfacial region of Au electrode/pentacene film is one of the essential reasons for the increase of the conductivity of pentacene film.     

Influence of NiCr/Au electrodes and multilayer thickness on the electrical properties of PANI/PVS ultrathin film grown by Lbl deposition

In the present work, we concentrate on the study of effects of metallic electrodes, multilayer thickness and temperature in ac and dc electrical conductivity of polyaniline/poly(vinyl sulfonic acid) (PANI/PVS) ultrathin films. The polymer system was obtained from layer-by-layer (Lbl) self-assembly technique on a glass substrate with an electrode array of adhesion layer of NiCr (20 nm) covered with Au (180 nm). We observed a significant and abrupt increase in the value of dc conductivity and a change of ac conductivity behavior of NiCr/Au-PANI/PVS-NiCr/Au structure when the thickness of PANI/PVS system reaches the Au layer. These effects were ascribed to the ideal contact of Au-PANI/PVS and the relative high interfacial contact resistance between PANI/PVS and NiCr, thus reducing the parallel resistance of NiCr/Au-PANI/PVS interfacial layer in an ideal parallel plate capacitor structure. Atomic Force Microscopy images confirm this assumption. Furthermore, the ac conductivity of Au-PANI/PVS-Au structure was typical of solid disordered materials. A model based on carrier hopping in a medium with randomly varying energy barriers was presented for the ac conductivity of the polymer system, which also encompasses the high dielectric constant of PANI/PVS blended films, the neutral contact Au-PANI/PVS, and the electrical resistance of NiCr-PANI/PVS interfacial layer. The model allowed separating the interface and the bulk effects in the electrical response of NiCr/Au-PANI/PVS-NiCr/Au structure and in addition the highest activation energy (35 MeV) correlated with an optimization of hopping distance (30 nm) for carriers jumps in PANI/PVS system.     

Analysis of a compressive shear test for adhesion between elastomeric polymers and rigid substrates

A compressive shear test for investigating adhesion between an elastomeric polymer and a rigid substrate has been studied. The test consists of loading a specimen comprising of a 3-ply laminate: substrate/polymer/ substrate, in compression and shear at a specified angle to the loading direction. Under displacement control and when adhesion is sufficiently low, an interfacial crack nucleates at one interface early during loading and propagates stably up to a critical load at which unstable propagation with an associated load drop ensues. The case of an isothennal hyperelastic material has been analyzed by computing the energy release rate for an interfacial crack as a function of crack length. The analysis shows that for a range of initial crack size interfacial crack propagation is stable until crack length reaches a critical size at which unstable propagation ensues. The energy release rate at this instability is relatively insensitive to angle of loading, strain, and hyperelastic parameters, which allows one to extract an interfacial toughness, ₀, from overall measurement of stress and strain. The analysis has been extended to consider combined hyperelasticity and viscoelasticity by using a cohesive zone model for crack propagation implemented as a cohesive finite element. The energy release rate and cohesive zone analyses give identical results for an hyperelastic material. For a viscoelastic-hyperelastic material, the cohesive zone approach allows the viscous losses in the bulk polymer to be estimated separately from the value of interfacial fracture toughness. Both analyses have been applied to experiments on glass/polyvinyl butyral (Butacite®)/glass laminate specimens. The intrinsic interfacial toughness, consisting of contributions from bond rupture and a near-tip process zone, is found to be rate-dependent and lies in the range 50–200 J m^–2.     

Asymmetric silver to oxide adhesion in multilayers deposited on glass by sputtering

We have developed a wedge-loaded double-cantilever beam adhesion measurement set-up for thin films deposited on glass by sputtering. The test is described in details. Results on the Glass/sublayer/Ag/ZnO multilayer provide evidence that SnO₂ or TiO₂ perform better than ZnO as a sublayer. Then however, rupture within the multilayer shifts to the upper Ag/ZnO interface. The latter is shown to be tougher than the lower ZnO/Ag interface, an asymmetry due to non-equilibrium interfacial structures.     

Evaluation of interfacial fracture toughness of a flip-chip package and a bimaterial system by a combined experimental and numerical method

In this paper, the interfacial fracture toughness of a flip-chip package subjected to a constant concentrated line load and a bimaterial system under thermal loading condition were evaluated using a unique six-axis submicron tester, a thermal vacuum chamber and FEM modeling coupled with a high density laser moiré interferometry. The six-axis submicron tester was used to provide a constant concentrated line load, whereas the moiré interferometry technique was used to monitor the crack length during the test. In addition, a finite element technique was simultaneously used to determine the near crack tip displacement fields of the specimens. The interfacial fracture toughness and phase angle were computed by using these near tip displacement variables through the analytical energy release rate and phase angle expressions derived by authors. The interfacial fracture toughness and the phase angle of the flip-chip package considered at the interface where the passivated silicon chip meets the underfill are 35 J/m² and −65°, respectively, while the interfacial fracture toughness and the phase angle of the tested bimaterial specimen at the interface of the molding compound/silicon with the crack length of 3.3 mm under the temperature rise thermal load from room temperature (20°C) to 138°C are 20.02 J/m² and −54.8°, respectively.