Surface and nanoindentation studies on nanocrystalline titanium diboride thin film deposited by magnetron sputtering

A detailed study on the mechanical, structural and surface characteristics of nanocrystalline TiB₂ films deposited on Si-100 substrates by direct current (DC) magnetron sputtering was carried out. X-ray photoelectron spectroscopy (XPS), atomic force microscope (AFM), nanoindentaion and X-ray diffraction (XRD) studies on these films were performed. Magnetron sputtered titanium diboride coatings had a maximum hardness of 36 GPa and elastic modulus of 360 GPa. From the XRD analyses, the films were found to grow in (00l) direction-oriented perpendicular to the substrate. The AFM analysis of the films showed the variation of grain size between 30 and 50 nm. The high-resolution AFM images revealed arrangements of atoms resembling lattice and the interplanar spacings measured on the image also showed the orientation of grains in the (001) direction. Nanoindentation studies at very shallow depths showed a continuous increase of hardness and modulus with indentation depth up to 40 nm due to tip blunting and presence of oxides on the film surface (confirmed from the XPS study). The elastic recovery was approximately 69% for 100 nm depth whereas it was 52% for 1000 nm depth.     

Quantitative mapping of surface elastic moduli in silica-reinforced rubbers and rubber blends across the length scales by AFM

The surface elastic moduli of silica-reinforced rubbers and rubber blends were investigated by atomic force microscopy (AFM)-based HarmoniX material mapping. Styrene–butadiene rubbers (SBR) and ethylene–propylene–diene rubbers (EPDM) and SBR/EPDM rubber blends with varying concentrations of silica nanoparticles (0, 5, 10, 20, 50 parts per hundred rubber, phr) were prepared to investigate the effect of different composition on the resulting morphology, filler distribution and elastic moduli of a specific rubber or rubber blend sample. For SBR, the elastic modulus values varied from 0.5 MPa for unfilled SBR to 5 MPa for 50 phr reinforced SBR with the increase in the concentration of filler. For EPDM, the corresponding values increased from 1.4 MPa for unfilled EPDM to 4.5 MPa for 50 phr reinforced EPDM. Local stiff and soft domains in silica-reinforced SBR and EPDM rubbers and rubber blends were identified by HarmoniX AFM imaging. While the stiff silica particles show modulus values as high as 2 GPa, the rubber matrix reveals modulus values in the range of ca. 30 MPa for the rubber blends to ca. 300 MPa for the unfilled rubbers. The lower value of elastic modulus of the EPDM phase in the blend, compared to the blank EPDM compound can be attributed to the presence of Sunpar oil in the compound which has a very good affinity with EPDM and decreases the rubber modulus. The elastic moduli maps revealed an increase of the areal fraction of silica particles showing an intrinsic surface modulus value with rising silica content in the compound preparation mixture. HarmoniX AFM measurements revealed the formation of larger silica aggregates in EPDM in contrast to SBR where isolated silica particles were observed. For silica-reinforced rubber blends a phase separation into a soft (ca. 40 MPa) and a significantly harder phase could be observed (ca. 500 MPa–1.5 GPa) indicating the incorporation of silica particles in the SBR phase. Using HarmoniX AFM imaging significantly higher surface elastic moduli were observed compared to those obtained by bulk tensile testing. Possible reasons for the observed differences between bulk modulus values and those measured by AFM are discussed in detail, including the aspect of different averaging procedures like inherent to surface probing by AFM versus bulk tensile testing, different filler distributions in SBR and EPDM and the AFM modulus calibration procedures.     

Effects of rare earth Ce on properties of Sn–9Zn lead-free solder

The influences of different Ce content on the properties of Sn–9Zn lead-free solder were investigated. The results indicate that Ce plays an important role not only in the structure and the solderability, but also in the interfacial structure of Sn–9Zn–xCe/Cu and mechanical property of soldered joint. Sn–9Zn–0.08Ce shows finer and more uniform microstructure than Sn–9Zn, and when the quantity of Ce is 0.5–1 wt%, some dark Sn–Ce compounds appear in the solder. With the addition of 0.08 wt% Ce, the solderability of solder is significantly improved because the surface tension of molten solder is decreased. Adding Ce makes the Cu5Zn8 IMCs formed at the interface of solder/Cu become much thicker than that of Sn–9Zn/Cu because much more content of Zn diffuse to the interface of solder/Cu to react with Cu. Results also indicate that adding 0.08 wt% Ce to the solder enhances mechanical property of soldered joint. When the Ce content is 0.1–0.5 wt%, some hard and brittle Cu–Zn IMCs appear in the bottom of dimples and the pull force of soldered joint decreases.     

A method to quantitatively measure the elastic modulus of materials in nanometer scale using atomic force microscopy

A method is proposed for quantitatively measuring the elastic modulus of materials using atomic force microscopy (AFM) nanoindentation. In this method, the cantilever deformation and the tip-sample interaction during the early loading portion are treated as two springs in series, and based on Sneddon's elastic contact solution, a new cantilever-tip property α is proposed which, together with the cantilever sensitivity A, can be measured from AFM tests on two reference materials with known elastic moduli. The measured α and A values specific to the tip and machine used can then be employed to accurately measure the elastic modulus of a third sample, assuming that the tip does not get significantly plastically deformed during the calibration procedure. AFM nanoindentation tests were performed on polypropylene (PP), fused quartz and acrylic samples to verify the validity of the proposed method. The cantilever-tip property and the cantilever sensitivity measured on PP and fused quartz were 0.514?GPa and 51.99?nm?nA(-1), respectively. Using these measured quantities, the elastic modulus of acrylic was measured to be 3.24?GPa, which agrees well with the value measured using conventional depth-sensing indentation in a commercial nanoindenter.     

Suppressing the growth of interfacial Cu–Sn intermetallic compounds in the Sn–3.0Ag–0.5Cu–0.1Ni/Cu–15Zn solder joint during thermal aging

Evolution of interfacial phase formation in Sn–3.0Ag–0.5Cu/Cu (wt%), Sn–3.0Ag–0.5Cu–0.1Ni/Cu, Sn–3.0Ag–0.5Cu/Cu–15Zn, and Sn–3.0Ag–0.5Cu–0.1Ni/Cu–15Zn solder joints are investigated. Doping Ni in the solder joint can suppress the growth of Cu₃Sn and alter the morphology of the interfacial intermetallic compounds (IMCs), however it shows rapid growth of (Cu,Ni)₆Sn₅ at the Sn–3.0Ag–0.5Cu–0.1Ni/Cu interface. In comparison with the Cu substrates, the Cu–Zn substrates effectively suppress the formation of Cu–Sn IMCs. Among these four solder joints, the Sn–3.0Ag–0.5Cu–0.1Ni/Cu–15Zn solder joint exhibits the thinnest IMC, and only (Cu,Ni)₆(Sn,Zn)₅ formed at the interface after aging. It is revealed that the presence of Ni acts to enhance the effect of Zn on the suppression of Cu–Sn IMCs in the SAC305–0.1Ni/Cu–15Zn solder joint. The limited formation of IMCs is related to the elemental redistribution at the joint interfaces during aging. The Sn–3.0Ag–0.5Cu–0.1Ni/Cu–15Zn joint can act as a stabilized interconnection due to the effective suppression of interfacial reaction.     

Effects of Ag on microstructures,wettabilities of Sn–9Zn–xAg solders as well as mechanical properties of soldered joints

The microstructures, wettabilities and mechanical properties of Sn–9Zn–xAg (x = 0, 0.1, 0.3, 0.5, 1 wt%) lead-free solders were investigated, respectively in this paper. Results show that, when the quantity of Ag added to the solder is 0.3 wt%, the microstructure of the solder becomes finer and more uniform than Sn–9Zn, and when the quantity of Ag is exceeded 0.3 wt% (upto 0.5–1 wt%), the AgZn₃ intermetallic compounds appear in the solder. In particular, adding 0.3 wt% Ag improves the wettability due to the better oxidation resistance of the Sn–9Zn–0.3Ag solder. Results also indicate that adding 0.3 wt% Ag to the solder enhances mechanical property of soldered joint, at which the fracture micrographs show that plenty of small and uniform dimples could be observed on the Sn–9Zn–0.3Ag soldered joints fractures. When the content of Ag is upto 1 wt%, some Cu–Zn and Ag–Zn intermetallic compounds appear on the bottom of dimples, and the mechanical property of the soldered joint decreases.     

Recent advances on Sn–Cu solders with alloying elements: review

Nowadays, a major concern of Sn–Cu based solder alloy today is focused on continuously improving the comprehensive properties of the solder joints formed between the solders and substrates. The key issues and improvements about Sn–Cu–X (X = Ni, rare earths, Zn, Co, Ga, In, Bi, secondary particles etc.) solder are outlined and evaluated in this paper which compared to Sn–Cu solder. It can be summarized that by adding appropriate amounts of certain alloying elements X to Sn–Cu solder, and it is possible to tailor the properties of the solder, such as the melting and solidification behaviors, wettability, microstructure, interfacial reactions and mechanical properties of the solder. The reliability issues related to the implementation of Sn–Cu–X solder in advanced electronics system are also introduced, which indicates that further development on the Sn–Cu–X solders are to be underway.     

Atomic force microscopy investigations on nanoindentation impressions of some metals: effect of piling-up on hardness measurements

In the indentation test, the hardness and the elastic modulus depend strongly on the estimate of the indenter-material contact area at peak load. However, many elastic–plastic behaviours such as elastic recoveries during unloading and piling-up or sinking-in of surface profiles during indentation affect the determination of the hardness and the elastic modulus. So, atomic force microscopy is a method of utmost importance to provide an accurate knowledge of the indentation impression especially when plastic deformations occur, that leads to errors in the determination of the contact area. Atomic force measurements of vanadium, tungsten, molybdenum and tantalum pure metals as well as stainless steels, often used as substrates for thin films depositions, highlight the difficulties to estimate the contact area. The variation of hardness values determined by atomic force microscopy measurements and nanoindentation test is correlated to the formation of folds of 150 and 100 nm high, around the residual impression of vanadium and tungsten indented at 0.1 N, respectively. Some folds which increase with increasing loads are detected on the residual impressions of both 35CD4 and 30NCD16 stainless steels indented under loads of 0.01 N, only. Such structures are related to piling-up of surface profiles that could lead to an underestimate of the contact area in the indentation test. So, the hardness value of tungsten could be closer to 6 than to 7 GPa whereas the effect of piling-up on the estimation of contact area of vanadium could be lower. Almost no deformation is seen on tantalum and molybdenum. So, the hardness values determined by the various methods are consistent. These results show that atomic force microscopy measurements are quite complementary of the nanoindentation test.     

Atomic force microscopy indentation of fluorocarbon thin films fabricated by plasma enhanced chemical deposition at low radio frequency power

Atomic force microscopy (AFM) indentation technique is used for characterization of mechanical properties of fluorocarbon (CF_x) thin films obtained from C₄F₈ gas by plasma enhanced chemical vapour deposition at low r.f. power (5-30 W) and d.c. bias potential (10-80 V). This particular deposition method renders films with good hydrophobic property and high plastic compliance. Commercially available AFM probes with stiff cantilevers (10-20 N/m) and silicon sharpened tips (tip radius < 10 nm) are used for indentations and imaging of the resulted indentation imprints. Force depth curves and imprint characteristics are used for determination of film hardness, elasticity modulus and plasticity index. The measurements show that the decrease of the discharge power results in deposition of films with decreased hardness and stiffness and increased plasticity index. Nanolithography based on AFM indentation is demonstrated on thin films (thickness of 40 nm) with good plastic compliance.     

Impacts of accelerated aging on the mechanical properties of Cu–Nb nanolaminates

Accelerated aging (30 min at 400 °C) has been shown to alter the mechanical properties of Cu–Nb nanolaminate systems. The Cu–Nb nanolaminates produced were 1,000-nm thick with alternating 20 or 100-nm-thick individual layers, which were fabricated by magnetron sputter deposition. Unaged Cu–Nb systems increased in hardness (from 4.3 to 5.5 GPa) with decreasing layer thickness. After aging, the nanolaminates with 20 nm layers softened greatly (5.5 GPa decreased to as little as 1.3 GPa), yet nanolaminates with 100 nm layers hardened slightly (4.3–4.8 GPa). Both nanolaminate structures exhibited significant residual tensile stress, which was further increased by up to 70 % (100 nm layers) and 120 % (20 nm layers) after accelerated aging. X-ray diffraction showed the presence of primary textures and high stress in niobium layers for unaged systems.     

Growth mechanisms of interfacial intermetallic compounds in Sn/Cu–Zn solder joints during aging

The interfacial reactions of Sn/Cu–xZn (x = 15 and 30 at.%) solder joints were investigated. Before aging, [Cu₆(Sn,Zn)₅] and [Cu₆(Sn,Zn)₅/Cu–Zn–Sn] intermetallic compounds (IMCs) formed at the [Sn/Cu–15Zn] and [Sn/Cu–30Zn] interfaces, respectively. After thermal aging at 150 °C for 80 days, [Cu₆(Sn,Zn)₅/Cu₃(Sn,Zn)/Cu(Zn,Sn)/CuZn] and [Cu₆(Sn,Zn)₅/Cu(Zn,Sn)/CuZn] IMCs, respectively, formed at the [Sn/Cu–15Zn] and [Sn/Cu–30Zn] interfaces. Increasing the amount of Zn in the Cu–Zn substrates evidently suppresses the growth of Cu₃Sn and Kirkendall voids at the solder joint interfaces. Transmission electron microscopy images show the different microstructure of CuZn and Cu–Zn–Sn phases in Sn/Cu–Zn joints. These Cu–Zn phases act to inhibit the growth of Cu₆Sn₅ and Cu₃Sn IMCs. As the content of Zn increased in Cu–Zn substrates, both CuZn and Cu(Zn,Sn) grew significantly. In addition, the growth of the Cu₆(Sn,Zn)₅/Cu₃Sn IMCs approached a reaction-controlled process. The formation mechanisms of the CuZn and Cu(Zn,Sn) phases were probed and proposed with regard to the interfacial microstructure, elemental distribution, and the compositional variation at Sn/Cu–xZn interfaces.     

Thermal creep and fracture behaviors of the lead-free Sn–Ag–Cu–Bi solder interconnections under different stress levels

In our previous study, the creep behavior of the lead-free Sn–Ag–Cu–Bi solder joints has been proven to follow the Arrhenius power-law relationship, and the thermal fatigue behavior of the solder joints exhibits the typical creep deformation characteristics with a superposition of the pulsating features. In this study, the thermal creep and fracture behaviors of the lead-free Sn–Ag–Cu–Bi solder interconnections were characterized under different stress levels, with a systematical comparison to that of a traditional Sn60Pb40 near-eutectic solder. The results show that the creep strain rate of both solder connections follows Weertman-Dorn equation, and the calculated creep stress exponent for two solders is reasonably close to other published data. The SEM inspection and analysis of fractographies of creep fractured solder joints manifest that the creep failure of the lead-free Sn–Ag–Cu–Bi solder joint shows obviously intergranular fracture mechanism, while the Sn60Pb40 joint ruptures dominantly by a transgranular sliding mechanism.     

Elastic property of vertically aligned nanowires

An atomic force microscopy (AFM) based technique is demonstrated for measuring the elastic modulus of individual nanowires/nanotubes aligned on a solid substrate without destructing or manipulating the sample. By simultaneously acquiring the topography and lateral force image of the aligned nanowires in the AFM contacting mode, the elastic modulus of the individual nanowires in the image has been derived. The measurement is based on quantifying the lateral force required to induce the maximal deflection of the nanowire where the AFM tip was scanning over the surface in contact mode. For the [0001] ZnO nanowires/nanorods grown on a sapphire surface with an average diameter of 45 nm, the elastic modulus is measured to be 29 +/- 8 GPa.     

Effects of Co additions on electromigration behaviors in Sn–3.0 Ag–0.5 Cu-based solder joint

As the miniaturization trend of electronic packing industry, electromigration (EM) has become a critical issue for fine pitch packaging. The EM effects on microstructure evolution of intermetallic compound layer (IMC) in Sn–3.0 Ag–0.5 Cu + XCo (X = 0, 0.05, 0.2 wt%) solder joint was investigated. Findings of this study indicated that current stressing of Sn–3.0 Ag–0.5 Cu–0.2 Co solder joint with 10⁴ A/cm² at 50 °C for 16 days, no remarkable EM damages exhibited in solder matrix. Whereas, after current stressing at 150 °C for 1 and 3 days, Sn–3.0 Ag–0.5 Cu specimens showed obvious polarity effect between cathode and anode. Different morphology changes were also observed at both sides. After current stressing for 1 day, two IMC layers, Cu₆Sn₅ and Cu₃Sn, with wave type morphology formed at cathode. Sn phases were also observed inside in the IMC layer. However, only Cu₆Sn₅ formed in anode. Three days later, Sn phases were found in anode. Besides, Co additions, aging treatment, Ag₃Sn, and other IMCs improved the resistance of EM by the evidence of retarding polarity effect.     

Influence of sodium chromate and dodecylamine on enhanced dissolution behavior of Cu—Ni alloy induced by AFM tip scratching

The influence of two inhibitors sodium chromate and dodecylamine on enhanced dissolution of Cu–Ni alloy initiated by atomic force microscopy (AFM) tip scratching in 1.5 M NaCl and 0.01 M HCl was investigated. The lateral force traces and force versus distance curves were measured by AFM in distilled water without or with inhibitors to investigate the influence of inhibitors on physical characters of sample surfaces. The results indicated that enhanced dissolution caused by AFM tip scratching was inhibited by adding sodium chromate or dodecylamine into the corrosive solutions, but their inhibition mechanisms are different. The inhibition effect of sodium chromate is due to its oxidation ability to repair the destroyed protection film and the increase of rigidity of metal surface resulted from the formation of oxide film containing Cr elements. On the other hand, the inhibition effect of dodecylamine is due to the organic adsorption film on metal surface to weaken the friction forces between the tip and the sample and to elevate the ionization energy of metal.     

Mechanical properties of conventional and nanostructured plasma sprayed alumina coatings

The hardness and the elastic modulus measured by microindentation of three different types of plasma sprayed alumina coatings have been compared. Usually, such coatings present porosity and heterogeneity which affect the measurement of the mechanical properties. To take such effects into account along with the indentation size effect which is relevant to all hardness studies, the Proportional Specimen Resistance model is applied. The three alumina coatings show closely similar mechanical properties at indentation loads exceeding 1 N, i.e., macrohardness around 5.7 GPa, indentation size effect parameter around 5.5 MPa mm and elastic modulus around 160 GPa. For loads below 1 N, the extrapolated values of the macrohardness of crushed and agglomerated alumina coatings increased to 8.5 GPa, while the indentation size effect parameter has the same value, and the elastic modulus increased to 320 GPa. However, no significant change in the measured values of hardness and the elastic modulus of the nanostructured alumina coating has been observed. This result is attributed to porosity and the bimodal microstructure of the nanostructured coating where a semimolten phase coexists along with the fully molten phases.     

Reliability studies of Sn–9Zn/Cu and Sn–9Zn–0.3Ag/Cu soldered joints with aging treatment

In this study, the interfacial reactions and joint reliabilities of Sn–9Zn/Cu and Sn–9Zn–0.3Ag/Cu were investigated during isothermal aging at 150 °C for aging times of up to 1,000 h. Cu₅Zn₈ IMCs layer is formed at the as-soldered Sn–9Zn/Cu interface. Adding 0.3wt.% Ag results in the adsorption of AgZn₃ on the Cu₅Zn₈ IMCs layer. The as-soldered Sn–9Zn/Cu and Sn–9Zn–0.3Ag/Cu joints have sufficient pull strength. The thickness of the IMCs layer formed at the interface of Sn–9Zn/Cu and Sn–9Zn–0.3Ag/Cu both increase with increasing aging time. Correspondingly, both the pull forces of the Sn–9Zn and Sn–9Zn–0.3Ag soldered joints gradually decrease as the aging time prolonged. However, the thickness of the IMCs layer of Sn–9Zn–0.3Ag/Cu increases much slower than that of Sn–9Zn/Cu and the pull force of Sn–9Zn–0.3Ag soldered joint decreases much slower than that of Sn–9Zn soldered joint. After aging for 1,000 h, some Cu–Sn IMCs form between the Cu₅Zn₈ IMC and the Cu substrate, many voids form at the interface between the Cu₅Zn₈ layer and solder alloy, and some cracks form in the Cu₅Zn₈ IMCs layer of Sn–9Zn/Cu. The pull force Sn–9Zn soldered joint decreases by 53.1% compared to the pull force measured after as-soldered. Fracture of Sn–9Zn/Cu occurred on the IMCs layer on the whole and the fracture micrograph implies a brittle fracture. While the pull force of Sn–9Zn–0.3Ag soldered joint decreases by 51.7% after aging at 150 °C for 1,000 h. The fracture mode of Sn–9Zn–0.3Ag soldered joint is partially brittle at the IMCs layer, and partially ductile at the outer ring of the solder.     

Investigation on properties of Ga to Sn–9Zn lead-free solder

The influences of different Ga content on the properties of Sn–9Zn lead-free solder were investigated. The results indicate that Ga plays an important role not only in the structure and melting behavior, but also in the solderability and mechanical property. Sn–9Zn–0.5Ga shows finer and more uniform microstructure than Sn–9Zn. With the addition of low-melting-point Ga, TL (liquidus temperature) and TS (solidus temperature) of the alloys decreases with increasing of Ga content while △T (liquidus temperature minus solidus temperature) increases. Ga can improve the oxidation resistance and reduce the surface tension of solder, so the solderability of Sn–9Zn–xGa lead-free solder is significantly improved. When the content of Ga is 0.5 wt.%, the pull force of soldered joint is 16.1 N, enhanced by 11% compared to that of Sn–9Zn, and the fracture micrographs show that the joint failed in a ductile manner. The addition of 3 wt.%Ga resulted in a brittle failure. The introduction of 0.5 wt.% Ga into Sn–9Zn alloy improves creep resistance of the solder.     

Creep and fatigue behaviors of the lead-free Sn–Ag–Cu–Bi and Sn60Pb40 solder interconnections at elevated temperatures

Creep and fatigue behaviors of the interconnections soldered by the lead-free Sn–Ag–Cu–Bi solder were investigated at different elevated temperatures (with the homologue temperature in the range of 0.71– 0.82), with a comparison to that of a traditional Sn60Pb40 solder. The results show that the lead-free Sn–Ag–Cu–Bi solder shows a superior anti-creep performance over the Sn60Pb40 solder, in terms of a much lower creep strain rate and a vastly elongated creep fracture lifetime; in the secondary creep regime, the calculated creep-activation energy for two solders is reasonably close to other published data. In addition, it has also been shown that the joints soldered by the lead-free Sn–Ag–Cu–Bi solder exhibits a superb fatigue property.     

Freeze extrusion fabrication of 13–93 bioactive glass scaffolds for bone repair

A solid freeform fabrication technique, freeze extrusion fabrication (FEF), was investigated for the creation of three-dimensional bioactive glass (13–93) scaffolds with pre-designed porosity and pore architecture. An aqueous mixture of bioactive glass particles and polymeric additives with a paste-like consistency was extruded through a narrow nozzle, and deposited layer-by-layer in a cold environment according to a computer-aided design (CAD) file. Following sublimation of the ice in a freeze dryer, the construct was heated according to a controlled schedule to burn out the polymeric additives (below ~500°C), and to densify the glass phase at higher temperature (1 h at 700°C). The sintered scaffolds had a grid-like microstructure of interconnected pores, with a porosity of ~50%, pore width of ~300 μm, and dense glass filaments (struts) with a diameter or width of ~300 μm. The scaffolds showed an elastic response during mechanical testing in compression, with an average compressive strength of 140 MPa and an elastic modulus of 5–6 GPa, comparable to the values for human cortical bone. These bioactive glass scaffolds created by the FEF method could have potential application in the repair of load-bearing bones.