Investigation of Cu‑Cu bonding for 2.5D and 3D system integration using self‑assembled monolayer as oxidation inhibitor

Das Cu-Cu-Bonden ist eine vielversprechende lötfreie Fine-Pitch-Verbindungstechnologie für die 2,5D- und 3D-Systemintegration. Diese Bondtechnologie wurde in den letzten Jahren intensiv untersucht und wird derzeit für miniaturisierte mikroelektronische Produkte eingesetzt. Allerdings, stellt das Cu‑Cu-Bonden zum einen sehr hohe Anforderungen an die Oberflächenplanarität und -reinheit, und zum anderen sollten die Bondpartner frei von Oxiden sein. Oxidiertes Cu erfordert erhöhte Bondparameter, um die Oxidschicht zu durchbrechen und zuverlässige Cu-Cu-Verbindungen zu erzielen. Diese Bondbedingungen sind für viele sensible Bauelemente nicht geeignet. Aus diesem Grund sollten alternative Technologien mit einer einfachen Technik zum Schutz von Cu vor Oxidation gefunden werden. In dieser Arbeit werden selbstorganisierte Monolagen (SAMs) für den Cu-Oxidationsschutz und die Verbesserung der Cu-Cu-Thermokompression- (TC) und Ultraschall- (US) Flip-Chip-Bondtechnologien untersucht. Die Experimente werden an Si-Chips mit galvanisch aufgebrachten Cu-Microbumps und Cu-Schichten durchgeführt. Die Arbeit beinhaltet die umfassende Charakterisierung der SAM für den Cu-Schutz, die Bewertung der technologischen Parameter für das TC- und US-Flip-Chip-Bonden sowie die Charakterisierung der Cu-Cu-Bondqualität (Scherfestigkeitstests, Bruchflächen- und Mikrostrukturanalysen). Eine Lagerung bei tiefen Temperaturen (bei ‑18 °C und ‑40 °C) bestätigte die langanhaltende Schutzwirkung der kurzkettigen SAMs für das galvanisch abgeschiedene Cu ohne chemisch-mechanische Politur. Der Einfluss der Tieftemperaturlagerung an Luft und der thermischen SAM-Desorption in einer Inertgasatmosphäre auf die TC-Verbindungsqualität wird im Detail analysiert. Die Idee, mit Hilfe der US-Leistung SAM mechanisch zu entfernen und gleichzeitig das US-Flip-Chip-Bonden zu starten, wurde in der Literatur bisher nicht systematisch untersucht. Die Methode ermöglicht kurze Bondzeiten, niedrige Bondtemperaturen und das Bonden an Umgebungsluft. Sowohl beim TC- als auch beim US-Flip-Chip-Bonden zeigt es sich, dass die Scherfestigkeit bei den Proben mit SAM-Passivierung um ca. 30 % höher ist als bei unbeschichteten Proben. Das Vorhandensein von Si- und Ti-Bruchflächen nach den Scherfestigkeitstests ist für die Proben mit der SAM-Passivierung typisch, was auf eine höhere Festigkeit solcher Verbindungen im Vergleich zu ungeschützten Proben schließen lässt. Die Transmissionselektronenmikroskopie (TEM) zeigt keine SAM-Spuren im zentralen Bereich der Cu-Cu-Grenzfläche nach dem US-Flip-Chip-Bonden. Die Ergebnisse dieser Arbeit zeigen die Verbesserung der Bondqualität durch den Einsatz von SAM zum Schutz des Cu vor Oxidation im Vergleich zum üblicherweise angewandten Cu-Vorätzen. Das gefundene technologische Prozessfenster für das US-Flip-Chip-Bonden an Luft bietet eine hohe Bondqualität bei 90 °C und 150 °C, bei 180 MPa, bei einer Bonddauer von 1 s an. Die in dieser Arbeit gewonnenen Erkenntnisse sind ein wichtiger Beitrag zum Verständnis des SAM-Einflusses auf Chips mit galvanischen Cu-Microbumps, bzw. Cu-Schichten, und zur weiteren Anwendung der Cu-Cu-Fine-Pitch-Bondtechnologie in der Mikroelektronik.Cu-Cu bonding is one of the most promising fine-pitch interconnect technologies with solder elimination for 2.5D and 3D system integration. This bonding technology has been intensively investigated in the last years and is currently in application for miniaturized microelectronics products. However, Cu-Cu bonding has very high demands on the sur-face planarity and purity, and the bonding partners should be oxide-free. Oxidized Cu requires elevated bonding parameters in order to break through the oxide layer and achieve reliable Cu-Cu interconnects. Those bonding conditions are undesirable for many devices (e.g. due to the temperature/pressure sensitivity). Therefore, alternative technologies with a simple technique for Cu protection from oxidation are required. Self-assembled monolayers (SAMs) are proposed for the Cu protection and the improvement of the Cu-Cu thermocompression (TC) and ultrasonic (US) flip-chip bonding technologies in this thesis. The experiments were carried out on Si dies with electroplated Cu microbumps and Cu layers. The thesis comprises the comprehensive characterization of the SAM for Cu protection, evaluation of technological parameters for TC and US flip-chip bonding as well as characterization of the Cu-Cu bonding quality (shear strength tests, fracture surface and microstructure analyses). The storage at low temperatures (at ‑18 °C and ‑40 °C) confirmed the prolonged protective effect of the short-chain SAMs for the electroplated Cu without chemical-mechanical polishing. The influence of the low-temperature storage in air and the thermal SAM desorption in an inert gas atmosphere on the TC bonding quality was analyzed in detail. The approach of using US power to mechanically remove SAM and simultaneously start the US flip-chip bonding has not been systematically investigated before. The method provides the benefit of short bonding time, low bonding temperature and bonding in ambient air. Both the TC and US flip-chip bonding results featured the shear strength that is approximately 30 % higher for the samples with SAM passivation in comparison to the uncoated samples. The presence of Si and Ti fracture surfaces after the shear strength tests is typical for the samples with the SAM passivation, which suggests a higher strength of such interconnects in comparison to the uncoated samples. The transmission electron microscopy (TEM) indicated no SAM traces at the central region of the Cu-Cu bonding interface after the US flip-chip bonding. The results of this thesis show the improvement of the bonding quality caused by the application of SAM for Cu protection from oxidation in comparison to the commonly applied Cu pre-treatments. The found technological process window for the US flip-chip bonding in air offers high bonding quality at 90 °C and 150 °C, at 180 MPa, for the bonding duration of 1 s. The knowledge gained in this thesis is an important contribution to the understanding of the SAM performance on chips with electroplated Cu microbumps/layers and further application of the Cu-Cu fine-pitch bonding technology for microelectronic devices

Novel fine pitch interconnection methods using metallised polymer spheres

There is an ongoing demand for electronics devices with more functionality while reducing size and cost, for example smart phones and tablet personal computers. This requirement has led to significantly higher integrated circuit input/output densities and therefore the need for off-chip interconnection pitch reduction. Flip-chip processes utilising anisotropic conductive adhesives anisotropic conductive films (ACAs/ACFs) have been successfully applied in liquid crystal display (LCD) interconnection for more than two decades. However the conflict between the need for a high particle density, to ensure sufficient the conductivity, without increasing the probability of short circuits has remained an issue since the initial utilization of ACAs/ACFs for interconnection. But this issue has become even more severe with the challenge of ultra-fine pitch interconnection. This thesis advances a potential solution to this challenge where the conductive particles typically used in ACAs are selectively deposited onto the connections ensuring conductivity without bridging. The research presented in this thesis work has been undertaken to advance the fundamental understanding of the mechanical characteristics of micro-sized metal coated polymer particles (MCPs) and their application in fine or ultra-fine pitch interconnections. This included use of a new technique based on an in-situ nanomechanical system within SEM which was utilised to study MCP fracture and failure when undergoing deformation. Different loading conditions were applied to both uncoated polymer particles and MCPs, and the in-situ system enables their observation throughout compression. The results showed that both the polymer particles and MCP display viscoelastic characteristics with clear strain-rate hardening behaviour, and that the rate of compression therefore influences the initiation of cracks and their propagation direction. Selective particle deposition using electrophoretic deposition (EPD) and magnetic deposition (MD) of Ni/Au-MCPs have been evaluated and a fine or ultra-fine pitch deposition has been demonstrated, followed by a subsequent assembly process. The MCPs were successfully positively charged using metal cations and this charging mechanism was analysed. A new theory has been proposed to explain the assembly mechanism of EPD of Ni/Au coated particles using this metal cation based charging method. The magnetic deposition experiments showed that sufficient magnetostatic interaction force between the magnetized particles and pads enables a highly selective dense deposition of particles. Successful bonding to form conductive interconnections with pre-deposited particles have been demonstrated using a thermocompression flip-chip bonder, which illustrates the applicable capability of EPD of MCPs for fine or ultra-fine pitch interconnection

Mid-IR type-II InAs/GaSb nanoscale superlattice sensors

The detection of mid-wavelength infrared radiation (MWIR) is very important for many military, industrial and biomedical applications. Present-day commercially available uncooled IR sensors operating in MWIR region (2-5μm) use microbolometric detectors which are inherently slow. Available photon detectors (mercury cadmium telluride (MCT), bulk InSb and quantum well infrared detectors (QWIPs))overcome this limitation. However, there are some fundamental issues decreasing their performance and ability for high temperature operation, including fast Auger recombination rates and high thermal generation rate. These detectors operate at low temperatures (77K-200K) in order to obtain high signal to noise ratio. The requirement of cooling limits the lifetime, increases the weight and the total cost, as well as the power budget, of the whole infrared system. In recent years, InAs/GaSb superlattice based detectors have appeared as an interesting alternative to the present-day IR detector systems. These heterostructures have a type-II band alignment such that the conduction band of InAs layer is lower than the valence band of GaSb layer. The effective bandgap of these structures can be adjusted from 0.4 eV to values below 0.1 eV by varying the thickness of constituent layers leading to an enormous range of detector cutoff wavelengths (3-30μm). The InAs/GaSb SLs have a higher degree of uniformity than the MCT alloys, making them attractive for large area focal plane arrays. They provide a smaller leakage current due to larger effective electron mass, which suppresses tunneling. This material system is also characterized by high operating temperatures and long Auger recombination rates. This suggests the potential for using the SLs technology for realizing high operating temperature devices. This work is focused on the development of mid-IR InAs/GaSb SLs sensors with high-operating temperature. Contributions of this thesis include 1) development of growth and processing procedure for the n-on-p and p-on-n design of SL detectors leading to improved detector performance, 2) careful evaluation of characteristics of SL detectors, 3) methods of reduction of surface component of dark current passivation techniques)

Microscale Infrared Technologies for Spectral Filtering and Wireless Neural Dust

Pivotal technologies, such as optical computing, autonomous vehicles, and biomedical implantables, motivate microscale infrared (IR) components. Hyperspectral imagers (HSI), for example, require compact and narrowband filters to obtain high-spatial and -spectral resolution images. HSIs acquire continuous spectra at each pixel, enabling non-destructive analyses by resolving IR scattering/absorption signatures. Toward this end, dielectric subwavelength gratings (SWG) are intriguing filter candidates since they are low-loss, have no moving parts, and exhibit narrow spectral features. Wireless neural implantables are another apropos microscale IR technology. Wireless IR data and power transfer disposes of infection-prone percutaneous wires by leveraging the IR transparency window in biological tissue. This dissertation contains two related topics. The first details SWG IR filters, and the second studies progress toward wireless neural motes. This work extends the capabilities of SWG IR filters. Following a theoretical overview, mid-wave infrared (MWIR, 3-7 um) transmittance filters are experimentally demonstrated using the zero-contrast grating scheme. Via a facile silicon fabrication process, we realize narrowband polarization-dependent and polarization-independent MWIR transmittance filters with some of the highest Q observed in MWIR SWGs. An empirical study confirms the relationship between filter performance and grating size, an important trade-off for HSIs. We then demonstrate GaAs SWG filters for monolithic integration with active optoelectronic devices. The GaAs SWGs perform comparably to their silicon counterparts. To enable narrowband filtering at normal incidence, we investigate symmetry-breaking in geometrically asymmetric gratings. The presented SWG geometries access quasi-bound states in the continuum (BIC). Studies in Fano resonance and diffraction efficiency symmetry provide physical insight. Asymmetric 1D and 2D SWGs furnish polarization-dependent and -independent filtering, respectively. We experimentally demonstrate normal incidence long-wave IR (LWIR, 7-12 um) transmittance filtering in asymmetric SWGs and confirm symmetry-breaking implications. A reduced-symmetry hexagonal pattern presents an early design for truly polarization-independent quasi-BIC coupling in SWGs. Advancements in implantable neural devices promise great leaps in brain mapping and therapeutic intervention. To meet this challenge, we investigated a wireless neural mote system using near-infrared (NIR, 800 nm – 3 um) photovoltaics and LEDs to wirelessly harvest power and transmit data. The neural recorders consist of three subsystems: an epitaxial GaAs-based optoelectronic chip, a Si CMOS IC, and a carbon fiber probe. Though this work encompasses the efforts of many, this dissertation outlines contributions in a few critical areas. To overcome low-flux LED emission, we devise an optical setup with ≈0.1% photon detection efficiency. Monte Carlo techniques model NIR scattering in biological tissue. Another steep challenge is the heterogeneous integration of the three material systems in a compact (200x170x150 um^3) package. To relay data and power between the GaAs and CMOS chips, through-wafer vias are critical. Using a novel selective copper plating technique, we demonstrate through-wafer GaAs vias with <2 Ohm series resistance. Additionally, conductive blind vias are presented for carbon fiber probe insertion. A self-aligned parylene etch mask permits sub-kOhm connection to a buried metal contact while maintaining GOhm substrate isolation. Both via structures meet the requirements of being low-resistance, insulated from the substrate, and amendable to thinned wafer processing. Finally, we demonstrate extensive processing on thinned chips and advances toward full heterogeneous integration via flip-chip alignment and solder bump bonding.PHDElectrical and Computer EngineeringUniversity of Michigan, Horace H. Rackham School of Graduate Studieshttp://deepblue.lib.umich.edu/bitstream/2027.42/169986/1/barrowm_1.pd

NANO-PARTICLE REINFORCED SOLDERS FOR MICROELECTRONIC INTERCONNECT APPLICATIONS

Ph.DDOCTOR OF PHILOSOPH

Tunable Functionality of Pure Nano Cu- and Cu-based Oxide Flexible Conductive Thin Film with Superior Surface Modification

Flexible and soft conductive thin film using pure Cu and Cu-based oxide nanostructures equally benefit from the versatility of their assembling individual materials and robustness of device design components. Their small-scale soft conductive thin film made of curved elastomeric bilayers driven by the responsive forces acting by the embedded printed liquid of pure Cu and/or Cu-based oxide nanostructures channels carrying alternating currents of those compact integrated circuits. As such, the localised oxide growth of those complex multiphase thin film architectures is the empirical knowledge that guides to further understanding of many interrelated factors of their intrinsic multiscale physical-electro-chemical interactions characteristics. Although not much literatures have been reported on the soft, flexible pure Cu and Cu-based oxide nanostructured thin films, still, the compelling unusual shapes/forms/construct of such nanostructures in the preparation of those superior functionalities thin film using various curvilinear shapes would seem to establish a predominant foundation in technologically important MEMS/NEMS devices. Herein, this article attempts to summarise the recent advances, challenges, and prospects of employing pure Cu and Cu-based oxide nanostructures in both fundamental and applied tunable functionality of varying dimensionality. Also, special emphasis on the emerging related critical issues and outlook of technical challenges that pave to research improvement opportunities are included

NOVEL SURFACE CHEMISTRY OF SINGLE MOLECULES AND SELF-ASSEMBLEDSTRUCTURES BY SCANNING TUNNELING MICROSCOPY

This thesis demonstrates the richness of Scanning Tunneling Microscopy (STM) as amethod to understand surface chemistry and physics and to explore the new frontiers in singlemoleculesurface reactions and molecular self-assembly. Organosulfur molecules on the Au(111)surface were studied to address unresolved and controversial issues about self-assembledmonolayers of alkanethiol molecules on gold surfaces. The key new finding is that the thermalsurface chemistry of alkanethiol molecules occurs in a dynamic chemical environment thatinvolves reactive gold adatoms to which the alkanethiol molecules chemically bond. Theproblem of alkanethiol self-assembly is thus transformed from the realm of adsorption on asurface toward organometallic surface chemistry, which is anticipated to have broad implicationsfor the field. Molecules containing a disulfide (S-S) bond were also found to be a spectacularmodel system for exploring electron-induced surface chemistry. In particular, the atomicallylocalizedinjection of electrons from the metal tip of the tunneling microscope is capable ofproducing highly delocalized chemical reactions by means of surface current of hot-electrons.Chemical reactions can therefore be a unique approach to the measurement of the local transportof hot-electrons on metal surfaces. Finally the concepts of self-assembly and electron-inducedchemistry are combined through an observation of an unusual process that flips the chirality ofmolecules self-assembled on the surface by a radical-like chain reaction. This experimentdemonstrates how self-assembly enables a new reaction coordinate by optimizing the stericfactor of the chemical reaction

Atomic-Scale Insights into Light Emitting Diode

In solid-state lightning, GaN-based vertical LED technology has attracted tremendous attention because its luminous efficacy has surpassed the traditional lightning technologies, even the 2014 Nobel Prize in Physics was awarded for the invention of efficient blue LEDs, which enabled eco-friendly and energy-saving white lighting sources. Despite today’s GaN-based blue VLEDs can produce IQE of 90% and EQE of 70-80%, still there exist a major challenge of efficiency droop. Nonetheless, state-of-the-art material characterization and failure analysis tools are inevitable to address that issue. In this context, although LEDs have been characterized by different microscopy techniques, they are still limited to either its semiconductor or active layer, which mainly contributes towards the IQE. This is also one of the reason that today’s LEDs IQE exceeded above 80% but EQE of 70-80% remains. Therefore, to scrutinize the efficiency droop issue, this work focused on developing a novel strategy to investigate key layers of the LED structure, which play the critical role in enhancing the EQE = IQE x LEE factors. Based on that strategy, wafer bonding, reflection, GaN-Ag interface, MQWs and top-textured layers have been systematically investigated under the powerful advanced microscopy techniques of SEM-based TKD/EDX/EBSD, AC-STEM, AFM, Raman spectroscopy, XRD, and PL. Further, based on these correlative microscopy results, optimization suggestions are given for performance enhancement in the LEDs. The objective of this doctoral research is to perform atomic-scale characterization on the VLED layers/interfaces to scrutinize their surface topography, grain morphology, chemical composition, interfacial diffusion, atomic structure and carrier localization mechanism in quest of efficiency droop and reliability issues. The outcome of this research advances in understanding LED device physics, which will facilitate standardization in its design for better smart optoelectronics products

Fundamentals and Recent Advances in Epitaxial Graphene on SiC

This book is a compilation of recent studies by recognized experts in the field of epitaxial graphene working towards a deep comprehension of growth mechanisms, property engineering, and device processing. The results of investigations published within this book develop cumulative knowledge on matters related to device-quality epaxial graphene on SiC, bringing this material closer to realistic applications