Gold metallizations for eutectic bonding of silicon wafers

Gold eutectic bonding of silicon wafers is a good candidate for wafer level vacuum packaging of vibrating MEMS: in this paper we investigated several e-beam evaporated metallizations stacks including a titanium adhesion layer, an optional diffusion barrier (Ni or Pt) and a gold film for eutectic bonding on Si and SiO₂/Si wafers. Interdiffusion in the multilayers for annealing temperatures (380–430°C) larger than the Au–Si eutectic temperature (363°C) and times corresponding to a bonding process was characterized by RBS, roughness and resistivity measurements. Au/Pt/Ti and Au/Ti/SiO₂ were found to have the best characteristics for bonding. This was confirmed by bonding experiments.

     

Device characteristics for Pt–Ti–O gate Si–MISFETs hydrogen gas sensors

A novel Pt–Ti–O-gate Si–metal–insulator–semiconductor field-effect transistor (MISFET) hydrogen gas sensor has been proposed by Usagawa and Kikuchi (2010) [1]. The sensors consist of unique gate structures composed of Ti and oxygen accumulated regions around Pt grains on top of a novel mixing layer of nanocrystalline TiO_x and superheavily oxygen-doped amorphous Ti formed on SiO₂/Si substrates. The optimum Pt/Ti thickness and annealing conditions for most hydrogen safety monitoring sensor systems are obtained by annealing Pt(15 nm)/Ti(5 nm)-gate Si–MOS structures in air around 400 °C for 2 h. One of the advantages of the Pt–Ti–O-gate Si–MISFETs after 10 min of air-diluted 1000-ppm hydrogen exposure at 115 °C are reproducible and uniform threshold voltage of V_th in addition to large sensing amplitudes at a practically important hydrogen concentration range between 100 ppm and 1%. The analysis of device characteristics of the Pt–Ti–O-gate Si–MISFETs hydrogen sensors concludes that the oxidation process of the Ti layer is consistently explained by an oxidation model that the oxygen invasion into Ti layer comes from open air through Pt grain boundaries and at the same time Ti will evacuate into the Pt surface through Pt grain boundaries. During the course of this process, the invading oxygen will be balanced with the evacuating Ti so that the Ti layer keeps nearly the same thickness with the as grown states. Ti and oxygen will remains around Pt grains named Ti and oxygen merged corridors.     

Au–Sn flip-chip solder bump for microelectronic and optoelectronic applications

As an alternative to the time-consuming solder pre-forms and pastes currently used, a co-electroplating method of eutectic Au–Sn alloy was used in this study. Using a co-electroplating process, it was possible to plate the Au–Sn solder directly onto a wafer at or near the eutectic composition from a single solution. Two distinct phases, Au₅Sn (ζ-phase) and AuSn (δ-phase), were deposited at a composition of 30 at.%Sn. The Au–Sn flip-chip joints were formed at 300 and 400°C without using any flux. In the case where the samples were reflowed at 300°C, only an (Au,Ni)₃Sn₂ IMC layer formed at the interface between the Au–Sn solder and Ni UBM. On the other hand, two IMC layers, (Au,Ni)₃Sn₂ and (Au,Ni)₃Sn, were found at the interfaces of the samples reflowed at 400°C. As the reflow time increased, the thickness of the (Au,Ni)₃Sn₂ and (Au,Ni)₃Sn IMC layers formed at the interface increased and the eutectic lamellae in the bulk solder coarsened.     

Electrical and morphological characterization of platinum thin-films with various adhesion layers for high temperature applications

In this paper we report on the morphological and electrical properties of platinum (Pt) thin-films with Titanium (Ti) and, alternatively, Titanium dioxide (TiO₂) as adhesion layers for high temperature applications. All films were sputter deposited on silicon substrates and afterwards annealed in air up to 800 °C. The results show that Ti diffuses into Pt grain boundaries forming oxide precipitates (TiO_x) in the Pt grain boundaries. The resistivity of Pt/Ti thin-films increased continuously with annealing temperature up to 500 °C and decreases again continuously above 500 °C. In contrast, TiO₂ demonstrates a dense stable oxide layer after annealing. Pt/TiO₂ thin-films show a continuous decrease in the sheet resistance with increasing the annealing temperature. Accordingly, TiO₂ thin-film is the preferable adhesive layer for Pt over Ti thin-films for high temperature applications.

     

Micromachined ultrasonic transducers based on lead zirconate titanate (PZT) films

The design, fabrication and measuring of piezoelectric micromachined ultrasonic transducers (pMUTs), including the deposition and patterning of PZT films, was investigated. The (100) preferential orientation of PZT film have been deposited on Pt/Ti/SiO₂/Si (100) substrates by modified sol–gel method. PZT film and Pt/Ti electrode were patterned by novel lift-off using ZnO as a sacrificial layer avoiding shortcomings of dry and wet etching methods. pMUT elements have been fabricated by an improved silicon micromachining process and their properties were also characterized. As measured results, the pMUT tends to operate in a standard plate-mode. The receive sensitivity and transmit sensitivity of pMUT element whose active area only has 0.25 mm² are ?218 dB (ref. 1 V/μPa) and 139 dB (ref. 1 μPa/V), respectively.     

Manufacture of microfluidic glass chips by deep plasma etching, femtosecond laser ablation, and anodic bonding

Two dry subtractive techniques for the fabrication of microchannels in borosilicate glass were investigated, plasma etching and laser ablation. Inductively coupled plasma reactive ion etching was carried out in a fluorine plasma (C₄F₈/O₂) using an electroplated Ni mask. Depth up to 100 μm with a profile angle of 83°–88° and a smooth bottom of the etched structure (Ra below 3 nm) were achieved at an etch rate of 0.9 μm/min. An ultrashort pulse Ti:sapphire laser operating at the wavelength of 800 nm and 5 kHz repetition rate was used for micromachining. Channels of 100 μm width and 140 μm height with a profile angle of 80–85° were obtained in 3 min using an average power of 160 mW and a pulse duration of 120 fs. A novel process for glass–glass anodic bonding using a conductive interlayer of Si/Al/Si has been developed to seal microfluidic components with good optical transparency using a relatively low temperature (350°C).     

High temperature stability of electrically conductive Pt–Rh/ZrO2 and Pt–Rh/HfO2 nanocomposite thin film electrodes

Nanocomposite films made up of either Pt–Rh/ZrO₂ or Pt–Rh/HfO₂ materials were co-deposited using multiple e-beam evaporation sources onto langasite (La₃Ga₅SiO₁₄) substrates, both as blanket films and as patterned interdigital transducer electrodes for surface acoustic wave sensor devices. The films and devices were tested after different thermal treatments in a tube furnace up to 1,200 °C. X-ray diffraction and electron microscopy results indicate that Pt–Rh/HfO₂ films are stabilized by the formation of monoclinic HfO₂ precipitates after high temperature exposure, which act as pinning sites to retard grain growth and prevent agglomeration of the conductive cubic Pt–Rh phase. The Pt–Rh/ZrO₂ films were found to be slightly less stable, and contain both tetragonal and monoclinic ZrO₂ precipitates that also helps prevent Pt–Rh agglomeration. Film conductivities were measured versus temperature for Pt–Rh/HfO₂ films on a variety of substrates, and it was concluded that La and/or Ga diffusion from the langasite substrate into the nanocomposite films is detrimental to film stability. An Al₂O₃ diffusion barrier grown on langasite using atomic layer deposition was found to be more effective than a SiAlON barrier layer in minimizing interdiffusion between the nanocomposite film and the langasite crystal at temperatures above 1,000 °C.     

Low temperature Si/Si wafer direct bonding using a plasma activated method

Manufacturing and integration of micro-electro-mechanical systems (MEMS) devices and integrated circuits (ICs) by wafer bonding often generate problems caused by thermal properties of materials. This paper presents a low temperature wafer direct bonding process assisted by O₂ plasma. Silicon wafers were treated with wet chemical cleaning and subsequently activated by O₂ plasma in the etch element of a sputtering system. Then, two wafers were brought into contact in the bonder followed by annealing in N₂ atmosphere for several hours. An infrared imaging system was used to detect bonding defects and a razor blade test was carried out to determine surface energy. The bonding yield reaches 90%–95% and the achieved surface energy is 1.76 J/m² when the bonded wafers are annealed at 350 °C in N₂ atmosphere for 2 h. Void formation was systematically observed and elimination methods were proposed. The size and density of voids greatly depend on the annealing temperature. Short O₂ plasma treatment for 60 s can alleviate void formation and enhance surface energy. A pulling test reveals that the bonding strength is more than 11.0 MPa. This low temperature wafer direct bonding process provides an efficient and reliable method for 3D integration, system on chip, and MEMS packaging.     

Effect of interfacial SiO2 thickness for low temperature O2 plasma activated wafer bonding

It was experimentally demonstrated that bonding strength strongly depends on the total SiO₂ thickness near the bonding interface for a given O₂ plasma surface activation. Systematic experiments of Si/SiO₂ and SiO₂/SiO₂ wafer bonding are performed for analyzing the evolution of the bonding surface energy with the interfacial oxide thickness. Optimum plasma exposure time increases with the interfacial SiO₂ thickness to achieve the maximum bonding strength in SiO₂/SiO₂ or SiO₂/Si. An optimal process option for plasma activated SiO₂/SiO₂ wafer bonding is proposed.     

Fabrication, packaging, and characterization of p-SOI Wheatstone bridges for harsh environments

Strain gauges in p-type silicon-on-insulator (SOI) were investigated for data logging during deep drilling. Different metallization systems (Ti/Pt/Au, Ti/Pd/Au, and Ti/TiN/Au) were tested for high temperatures by measuring the specific resistance over time. Pressure-assisted Pick-and-Place silver sintering was applied to attach the fabricated p-SOI Wheatstone bridges on substrate carriers. The influence of the joining technique on the offset voltage was investigated as well as the temperature behavior during temperature cycling (50?cycles from 30°C up to 250°C). Furthermore, the temperature dependence of noise was analyzed.     

Calculation of phase diagrams for the metastable Al-Fe phases forming in direct-chill (DC)-cast aluminum alloy ingots

In direct-chill (DC)-cast 1xxx-and 5xxx-series Al sheet-ingots, the presence of mainly Fe and some Si, and cooling rates increasing from ≤1 °C/s in the ingot center to ~20 °C/s near the surface cause the formation of metastable intermetallic Al₆Fe and Al_mFe compounds in addition to the stable Al₃Fe, and hence the fir-tree defect. Since the Al-Fe and Al-Fe-Si phase diagrams are not useful in predicting the metastable phase formation, a binary phase diagram study was conducted to calculate the Al-Al₆Fe and Al-Al_mFe metastable phase equilibria using a thermodynamic software and an Al-alloy database. The Al-Al₃Fe phase diagram was calculated using the existing Gibbs energy data which gives the eutectic point at 1.85wt% Fe and the eutectic temperature as 654 °C. The missing Gibbs energy data for the metastable phases were estimated using substitutional and graphical methods and the phase diagrams were calculated. In the Al-Al₆Fe phase diagram, the eutectic temperature is depressed from 654 °C (equilibrium) to 648 °C and the eutectic point is shifted from 1.85wt% Fe to 3.4wt% Fe. In the Al-Al_mFe phase diagram, the eutectic temperature is 643 °C and the eutectic point is at 4.6wt% Fe. The verification of the calculated eutectic temperatures was carried out by DSC measurements which were conducted on samples removed from Al-Fe alloy rods directionally grown in a Bridgman-type solidification furnace. A good agreement is observed between the calculated and measured values.     

CALPHAD: Phase diagram of the system KFK2MoO4SiO2

The phase diagrams of the binary systems KFK₂MoO₄, KFSiO₂, and K₂MoO₄SiO₂, as well as that of the ternary system KFK₂MoO₄SiO₂ in the range up to 50 mole % SiO₂, were measured using the thermal analysis method. The thermodynamically consistent phase diagrams were calculated using the coupled analysis of the thermodynamic and phase diagram data.In the system KFK₂MoO₄ the intermediate compound K₃FMoO₄, melting congruently at 751 °C, is formed. This compound divides this system into two simple eutectic ones. The coordinates of the individual eutectic points are: E₁: 30.5 mole % K₂MoO₄, 720.4 °C, and E₂: 58.8 mole % K₂MoO₄, 744.9 °C. In the binary system KFSiO₂ the liquidus curve of KF shows an inflex point, characteristic for reciprocal systems with chemical reaction taking place between components. Similar course of the liquidus curve of K₂MoO₄ was found in the binary system K₂MoO₄SiO₂, indicating the presence of the chemical reaction between components as well. The strong positive deviation from ideal behavior of the ternary system KFK₂MoO₄SiO₂ was ascribed to the possible formation of heteropolyanions [SiMo₁₂O₄₀]⁴⁻ in the melt.In the investigated concentration range of the ternary system no eutectic point has been found. It lies most probably beyond the investigated part of the system. The standard deviation of approximation of the calculated ternary phase diagram is ± 5.9 °C, which is approximately on the same level of magnitude as the estimated experimental error of ± 4 °C.     

Piezoelectric thin films formed by MOD on cantilever beams for micro sensors and actuators

Novel piezoelectric cantilever beams for micro sensors and actuators based on PZT thin films have been batch fabricated by surface micromachining. Lead zirconate titanate (PZT) thin film is formed by metalorganic deposition (MOD) on Pt/Ti/SiO₂/Si (1 0 0) substrates and Pt/Ti/LTO/Si₃N₄ cantilever beams and then annealed at 700 °C in air. The PZT thin film is 0.5 m thick and has dielectric permittivity of 1698, remanent polarization of 13.66 C/cm², and coercive field of 44.5 kV/cm. The influence of deposition temperatures on PZT thin film stress has been investigated. When continuously controlling the deposition temperatures, the stress of the thin film is reduced from 0.313 × 10⁸ to 0.269 × 10⁸ N/m, that is 16.4% decrease. With the total 120 designed devices on 4-inch wafers, the number of functional devices is increased from 82 to 97, that is 12.47%.Tianhong Cui joined the faculty of Institute for Micromanufacturing at Louisisana Tech University in 1999. He received his B.S. from Nanjing University of Aeronautics & Astronautics in 1991, and his Ph.D. from Chinese Academy of Sciences in 1995. He has conducted research and development work for the realization of microsensors and microactuators since 1992. Prior to joining the IfM in 1999, he was at the National Laboratory of Metrology in Japan as a Research Fellow under STA fellowship, and previous to that, served as a Postdoctoral Research Associate at the University of Minnesota. His current research interests include MEMS, polymer micro/nanoelectronics, and nanotechnology.     

Experimental determination of phase equilibria in the Y–Co–Ti system through diffusion couples and equilibrium alloys

Two isothermal sections of the Y–Co–Ti system at 600 °C and 800 °C were constructed for the first time using the diffusion couple technique and the equilibrium alloy method in combination with scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), electron probe microanalysis (EPMA), and X-ray diffraction (XRD). The stable ternary intermetallic compound YCo_12-xTi_x was detected and was confirmed to have a ThMn₁₂-type structure. The composition range in this ternary compound was measured to be 8.3–18.2 at.% at 600 °C and 8.9–19.1 at.% at 800 °C, resulting in the stable formation of YCo_12-xTi_x with x = 1.1–2.4 at 600 °C and x = 1.2–2.5 at 800 °C. The experimental results measured by EDS and EPMA demonstrate that the maximum solubilities of Ti in YCo₂, YCo₃, Y₂Co₇ and Y₂Co₁₇ compounds at 600 °C are 3.3, 5.6, 5.7 and 6.6 at.%, respectively, while the maximum solubilities of Y in Co₃Ti, Co₂Ti(h), Co₂Ti(c) and CoTi compounds are 2.7, 2.1, 2.6, 3.8 and 1.1 at.%. Meanwhile, the maximum solubilities of Ti in YCo₃, Y₂Co₇, YCo₅ and Y₂Co₁₇ compounds at 800 °C were determined to be 5.4, 3.2, 2.5 and 5.4 at.%, respectively, while the maximum solubilities of Y in Co₂Ti(c), Co₂Ti(h) and Co₃Ti compounds were measured to be 2.5, 2.1 and 3.8 at.%. The phase equilibria of the Y–Co–Ti system obtained in this work would provide the experimental information for phase stability of YCo_12-xTi_x compound and then explore the design of Y–Co–Ti based magnetic alloys with good magnetic properties.     

Phase equilibria of the Cu–Zr–Si system at 750 and 900 °C

Phase equilibria in the ternary Cu–Zr–Si system at 750 and 900 °C have been experimentally investigated via electron probe micro-analyzer (EPMA) and X-ray diffraction (XRD) analysis on the equilibrated alloys. The results show the presence of eight three-phase regions at 750 °C and seven three-phase regions at 900 °C. Four ternary phase: τ₁ (Zr₃Cu₄Si₆, tI26-Zr₃Cu₄Si₆), τ₄ (Zr₃Cu₄Si₄, oI22-Gd₃Cu₄Ge₄), τ₅ (ZrCuSi, oP12-Co₂Si), and τ₆ (Zr₃Cu₄Si₂, 2hP9-Fe₂P) were confirmed to exist in the Cu–Zr–Si ternary system at 750 and 900 °C. At 900 °C, the dark gray phase, the chemical composition of which is close to η-Cu₃Si, is confirmed to be the liquid phase. Moreover, the solubilities of Cu in ZrSi₂, SiZr and Zr₃Si₂ are considerably small. The solubility of Zr in η-Cu₃Si is determined to be negligible. The newly determined phase equilibria of the Cu–Zr–Si system in this work can provide important experimental data for the thermodynamic assessment of the Cu–Zr–Si system and to develop the Cu–Zr–Si alloys and related transition metal silicides.     

Wafer-level bonding and direct electrical interconnection of stacked 3D MEMS by a hybrid low temperature process

The presented fabrication technology enables the direct integration of electrical interconnects during low temperature wafer bonding of stacked 3D MEMS and wafer-level packaging. The low temperature fabrication process is based on hydrophilic direct bonding of plasma activated Si/SiO₂ surfaces and the simultaneous interconnection of two metallization layers by eutectic bonding of ultra-thin AuSn connects. This hybrid wafer-level bonding and interconnection technology allows for the integration of metal interconnects and multiple materials in stacked MEMS devices. The process flow is successfully validated by fabricating test structures made out of a two wafer stack and featuring multiple ohmic electrical interconnects.     

Solder bonding with a buffer layer for MOEMS packaging using induction heating

In this paper, the selective induction heating technology is applied to glass–glass and glass–silicon solder bonding for MOEMS (optical MEMS) packaging. The Ni bumping with a buffer layer is successful to release the thermal stress for avoiding delamination. The Au wetting layer must be thick enough to prevent from being solved entirely into Sn, and it will improve bonding strength. The bonding specimens are soaked into 25°C water and placed into 85°C/85% RH oven, respectively. No moisture penetrates into the cavity after 1 day in both test conditions. In the test condition of 125°C leakage-test liquid (Galden HS260), no bubble is observed. The lowest bonding strength is 3 MPa.

     

Thermodynamic reassessments of the Ti–Si–C/Ti–Si–N systems and thermodynamic calculations of CVD TiSiCN hard-coating based on the Ti–Si–C–N quaternary system

The Ti–Si–C and Ti–Si–N systems were thermodynamically reassessed by using the CALculation of PHAse Diagram (CALPHAD) approach. A more suitable Gibbs energies expression of Ti₃SiC₂ was obtained to fit better with heat capacity data in the Ti–Si–C system. The thermodynamic parameters of the Ti–Si–N system were adjusted based on the revised Ti–Si system. A self-consistent thermodynamic database of the quaternary Ti–Si–C–N system was established. The calculated thermodynamic data and phase diagrams agree well with the experimental data. The CVD (Chemical Vapor Deposition) process for TiSiCN coatings was simulated using the newly evaluated thermodynamic parameters of the Ti–Si–C–N system. A good agreement between the predicted coating composition and the experimental ones was achieved, verifying the reliability of the thermodynamic database obtained in the present work.     

Low temperature carbon nanotube and hexagonal diamond deposition with photo-enhanced chemical vapor deposition

Deposition of carbon nanotube and hexagonal diamond thin films at low substrate temperature with photo-enhanced chemical vapor deposition is described here. Extensive experimentation is conducted to optimize the catalyst layer utilized for deposition by varying Al/Ni/Al metal layer thicknesses on SiO₂ coated Si substrates. The coated substrates are annealed to transform the thin metal layers into nanoparticles. Suitable catalyst layer thicknesses obtained are 3/2/3, 5/1/5 and 5/3/5 nm for Al/Ni/Al sandwich metal layers. Suitable annealing conditions are in the range of 350–450 °C for substrate temperature and from 0.22 to 10 Torr for chamber pressure in ammonia ambient for 25 min. Carbon tetrachloride (CCl₄) is used as a carbon precursor in this work. Argon to CCl₄ flow ratio is varied in 1.5–19 range, chamber pressure is varied in 3–10 Torr range, and the substrate temperature is varied in 350–450 °C range. Carbon nanotubes (CNT) growth is observed at lower chamber pressure, lower partial pressure of CCl₄, lower substrate temperature and for thin Ni catalyst layer. The optimal CNT deposition condition observed is 5 Torr total chamber pressure, 9:1 partial pressure ratio of Ar to CCl₄, 400 °C substrate temperature and 5/1/5 nm thick Al/Ni/Al catalyst layers. The hexagonal diamond deposition is observed at a higher chamber pressure, higher partial pressure of CCl₄, higher substrate temperature and for a thicker Ni catalyst layer. The optimal condition for hexagonal diamond deposition observed is 10 Torr total chamber pressure, 7:3 partial pressure ratio of Ar to CCl₄, 450 °C substrate temperature and 5/3/5 nm thick Al/Ni/Al catalyst sandwich layers.