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

A review of advances in pixel detectors for experiments with high rate and radiation

The Large Hadron Collider (LHC) experiments ATLAS and CMS have established hybrid pixel detectors as the instrument of choice for particle tracking and vertexing in high rate and radiation environments, as they operate close to the LHC interaction points. With the High Luminosity-LHC upgrade now in sight, for which the tracking detectors will be completely replaced, new generations of pixel detectors are being devised. They have to address enormous challenges in terms of data throughput and radiation levels, ionizing and non-ionizing, that harm the sensing and readout parts of pixel detectors alike. Advances in microelectronics and microprocessing technologies now enable large scale detector designs with unprecedented performance in measurement precision (space and time), radiation hard sensors and readout chips, hybridization techniques, lightweight supports, and fully monolithic approaches to meet these challenges. This paper reviews the world-wide effort on these developments.Comment: 84 pages with 46 figures. Review article.For submission to Rep. Prog. Phy

Heterogeneous Integration on Silicon-Interconnect Fabric using fine-pitch interconnects (≤10 �m)

Today, the ever-growing data-bandwidth demand is pushing the boundaries of the traditional printed circuit board (PCB) based integration schemes. Moreover, with the apparent saturation of semiconductor scaling, commonly called Moore's law, system scaling warrants a paradigm shift in packaging technologies, assembly techniques, and integration methodologies. In this work, a superior alternative to PCBs called the Silicon-Interconnect Fabric (Si-IF) is investigated. The Si-IF is a silicon-based, package-less, fine-pitch, highly scalable, heterogeneous integration platform for wafer-scale systems. In this technology, unpackaged dielets are assembled on the Si-IF at small inter-dielet spacings (≤100 �m) using fine-pitch (≤10 �m) die-to-substrate interconnects. A novel assembly process using a solder-less direct metal-metal (gold-gold and copper-copper) thermal compression bonding was developed. Using this process, sub-10 �m pitch interconnects with a low specific contact resistance of ≤0.7 Ω-�m2 were successfully demonstrated. Because of the tightly packed Si-IF assembly, the communication links between the neighboring dies are short (≤500 �m) with low loss (≤2 dB), comparable to on-chip connections. Consequently, simple buffers can transfer data between dies using a Simple Universal Parallel intERface for chips (SuperCHIPS) at low latency (<30 ps), low energy per bit (≤0.03 pJ/b), and high data-rates (up to 10 Gbps/link), corresponding to an aggregate bandwidth up to 8 Tbps/mm. The benefits of the SuperCHIPS protocol were experimentally demonstrated to provide 5-90X higher data-bandwidth, 8-30X lower latency, and 5-40X lower energy per bit compared to existing integration schemes. This dissertation addresses the assembly technology and communication protocols of the Si-IF technology

MEMS suljenta kuparin lämpöpuristusliitännällä

Copper thermocompression is a promising wafer-level packaging technique, as it allows the bonding of electric contacts simultaneously to hermetic encapsulation. In thermocompression bonding the bond is formed by diffusion of atoms from one bond interface to another. The diffusion is inhibited by barrier forming surface oxide, high surface roughness and low temperature. Aim of this study was to establish a wafer-level packaging process for MEMS (Mi-croElectroMechanical System) mirror and MEMS gyroscope. The cap wafer of the MEMS mirror has an antireflective coating that limits the thermal budget of the bonding process to 250°C. This temperature is below the eutectic temperature of most common eutectic bonding materials, such as Au-Sn (278°C), Au-Ge (361°C) and Au-Si (370°C). Thus a thermocompression bonding method needed to be developed. Copper was used as a bonding material due to its low cost, high self-diffusivity and resistance to oxidation in ambient air. The bond structures were fabricated using three different methods and the bonding was further enhanced by annealing. The bonded structures were characterized with scanning acoustic microscopy, scanning electron microscope and the bond strength was determined by shear testing. Exposing the bond structures to etchant during Cu seed layer removal was found to drastically increase the surface roughness of bond structures. This increase proved detrimental to bond strength and dicing yield and thus covering the bond surface during wet etching is recommended. The native oxidation on copper surfaces was completely removed with combination of ex situ acetic acid wet etch and in situ forming gas anneal. Successful thermocompression bonding process using sputtered copper films was established at a low temperature of 200°C, well below the thermal limitation set by the antireflective coating. The established wafer bonding process had high yield of 97% after dicing. The bond strength was evaluated by maximum shear strength and recorded at 75 MPa, which is well above the MIL-STD-883E standard (METHOD 2019.5) rejection limit of 6.08 MPa.Kuparin lämpöpuristusliitäntä on lupaava kiekkotason pakkausmenetelmä, sillä se mahdollistaa sekä sähköisten liitäntöjen, että hermeettisen suljennan toteuttamisen samanaikaisesti. Lämpöpuristusliitännässä sidos muodostuu atomien diffuusiosta liitospinnalta toiselle. Diffuusiota rajoittavat estokerroksen muodostava pinta oksidi, korkea pinnan karheus ja matala lämpötila. Diplomityön tavoitteena oli luoda kiekkotason pakkausmenetelmä mikroelektromekaaniselle (MEMS, MicroElectroMechanical System) peilille ja MEMS gyroskoopille. Peilin lasisen kansikiekon pinnalla oleva antiheijastava kalvo rajoitti liitännässä käytettävän lämpötilan korkeintaan 250°C:een, mikä on alempi lämpötila kuin useimpien kiekkoliitännässä käytettyjen materiaaliparien eutektinen piste. Esimerkkinä mainittakoon mm. Au-Sn (278°C), Au-Ge (361°C) ja Au-Si (370°C). Kuparin alhainen hinta, korkea ominaisdiffuusio ja hidas hapettuminen ilmakehässä puoltavat sen valintaa liitäntämateriaaliksi. Liitäntärakenteet valmistettiin kolmella menetelmällä ja liitännän vahvuutta parannettiin lämpökäsittelyllä. Liitetyt rakenteet karakterisoitiin pyyhkäisy elektronimikroskoopin, akustisen mikroskoopin ja liitoslujuus-mittauksen avulla. Liitospintojen altistamisen hapolle havaittiin lisäävän pinnankarkeutta ja olevan siten haitallista liitokselle ja laskevan saantoa. Liitospintojen suojaaminen siemenkerroksen syövytyksen aikana on suotavaa. Pintaoksidi pystytään poistamaan täysin suorittamalla oksidin märkäetsaus jääetikalla sekä lämpökäsittely N2/H2 atmosfäärissä. Sputteroidut kuparikalvot pystyttiin liittämään onnistuneesti yhteen 200°C lämpötilassa, mikä on alle anti-heijastavan pinnan asettaman lämpötilarajan. Tällä liitäntä menetelmällä saavutettiin kiekkoliitoksella yhteen liitettyjen sirujen sahauksessa korkea 97% saanto. Liitoslujuus määritettiin maksimi-leikkausvoiman avulla ja sen suuruudeksi mitattiin 75 MPa. Lujuus oli yli kymmenkertainen MIL-STD-883E standardin (METHOD 2019.5) asettamaan hylkäysrajaan 6.08 MPa nähden

Progress in corrosion science at atomic and nanometric scales

International audienceContemporary aspects of corrosion science are reviewed to show how insightful a surface science approach is to understand the mechanisms of corrosion initiation at the atomic and nanometric scales. The review covers experimental approaches using advanced surface analytical techniques applied to single-crystal surfaces of metal and alloys exposed to corrosive aqueous environments in well-controlled conditions and analysed in situ under electrochemical control and/or ex situ by scanning tunnelling microscopy/spectroscopy, atomic force microscopy and x-ray diffraction. Complementary theoretical approaches based on atomistic modeling are also covered. The discussed aspects include the metal-water interfacial structure and the surface reconstruction induced by hydroxide adsorption and formation of 2D (hyd)oxide precursors, the structure alterations accompanying anodic dissolution processes of metals without or with 2D protective layers and selective dissolution (i.e. dealloying) of alloys, the atomic structure, orientation and surface hydroxylation of ultrathin passive films, the role of step edges at the exposed surface of oxide grains on the dissolution of passive films and the effect of grain boundaries in polycrystalline passive films acting as preferential sites of passivity breakdown, the differences in local electronic properties measured at passive films grain boundaries, and the structure of adlayers of organic inhibitor molecules

High performance 3-folded symmetric decoupled MEMS gyroscopes

This thesis reports, for the first time, on a novel design and architecture for realizing inertial grade gyroscope based on Micro-Electro-Mechanical Systems (MEMS) technology. The proposed device is suitable for high-precision Inertial Navigation Systems (INS). The new design has been investigated analytically and numerically by means of Finite Element Modeling (FEM) of the shapes, resonance frequencies and decoupling of the natural drive and sense modes of the various implementations. Also, famous phenomena known as spring softening and spring hardening are studied. Their effect on the gyroscope operation is modeled numerically in Matlab/Simulink platform. This latter model is used to predict the drive/sense mode matching capability of the proposed designs. Based on the comparison with the best recently reported performance towards inertial grade operation, it is expected that the novel architecture further lowers the dominant Brownian (thermo-mechanical) noise level by more than an order of magnitude (down to 0.08º/hr). Moreover, the gyroscope\u27s figure of merit, such as output sensitivity (150 mV/º/s), is expected to be improved by more than two orders of magnitude. This necessarily results in a signal to noise ratio (SNR) which is up to three orders of magnitude higher (up to 1,900mV/ º/hr). Furthermore, the novel concept introduced in this work for building MEMS gyroscopes allows reducing the sense parasitic capacitance by up to an order of magnitude. This in turn reduces the drive mode coupling or quadrature errors in the sensor\u27s output signal. The new approach employs Silicon-on-Insulator (SOI) substrates that allows the realization of large mass (\u3e1.6mg), large sense capacitance (\u3e2.2pF), high quality factors (\u3e21,000), large drive amplitude (~2-4 µm) and low resonance frequency (~3-4 KHz) as well as the consequently suppressed noise floor and reduced support losses for high-performance vacuum operation. Several challenges were encountered during fabrication that required developing high aspect ratio (up to 1:20) etching process for deep trenches (up to 500 µm). Frequency Response measurement platform was built for devices characterization. The measurements were performed at atmospheric pressures causing huge drop of the devices performance. Therefore, various MEMS gyroscope packaging technologies are studied. Wafer Level Packaging (WLP) is selected to encapsulate the fabricated devices under vacuum by utilizing wafer bonding. Through Silicon Via (TSV) technology was developed (as connections) to transfer the electrical signals (of the fabricated devices) outside the cap wafers

Towards A Graphene Chip System For Blood Clotting Disease Diagnostics

Point of care diagnostics (POCD) allows the rapid, accurate measurement of analytes near to a patient. This enables faster clinical decision making and can lead to earlier diagnosis and better patient monitoring and treatment. However, despite many prospective POCD devices being developed for a wide range of diseases this promised technology is yet to be translated to a clinical setting due to the lack of a cost-effective biosensing platform.This thesis focuses on the development of a highly sensitive, low cost and scalable biosensor platform that combines graphene with semiconductor fabrication tech-niques to create graphene field-effect transistors biosensor. The key challenges of designing and fabricating a graphene-based biosensor are addressed. This work fo-cuses on a specific platform for blood clotting disease diagnostics, but the platform has the capability of being applied to any disease with a detectable biomarker.Multiple sensor designs were tested during this work that maximised sensor ef-ficiency and costs for different applications. The multiplex design enabled different graphene channels on the same chip to be functionalised with unique chemistry. The Inverted MOSFET design was created, which allows for back gated measurements to be performed whilst keeping the graphene channel open for functionalisation. The Shared Source and Matrix design maximises the total number of sensing channels per chip, resulting in the most cost-effective fabrication approach for a graphene-based sensor (decreasing cost per channel from £9.72 to £4.11).The challenge of integrating graphene into a semiconductor fabrication process is also addressed through the development of a novel vacuum transfer method-ology that allows photoresist free transfer. The two main fabrication processes; graphene supplied on the wafer “Pre-Transfer” and graphene transferred after met-allisation “Post-Transfer” were compared in terms of graphene channel resistance and graphene end quality (defect density and photoresist). The Post-Transfer pro-cess higher quality (less damage, residue and doping, confirmed by Raman spec-troscopy).Following sensor fabrication, the next stages of creating a sensor platform involve the passivation and packaging of the sensor chip. Different approaches using dielec-tric deposition approaches are compared for passivation. Molecular Vapour Deposi-tion (MVD) deposited Al2O3 was shown to produce graphene channels with lower damage than unprocessed graphene, and also improves graphene doping bringing the Dirac point of the graphene close to 0 V. The packaging integration of microfluidics is investigated comparing traditional soft lithography approaches and the new 3D printed microfluidic approach. Specific microfluidic packaging for blood separation towards a blood sampling point of care sensor is examined to identify the laminar approach for lower blood cell count, as a method of pre-processing the blood sample before sensing.To test the sensitivity of the Post-Transfer MVD passivated graphene sensor de-veloped in this work, real-time IV measurements were performed to identify throm-bin protein binding in real-time on the graphene surface. The sensor was function-alised using a thrombin specific aptamer solution and real-time IV measurements were performed on the functionalised graphene sensor with a range of biologically relevant protein concentrations. The resulting sensitivity of the graphene sensor was in the 1-100 pg/ml concentration range, producing a resistance change of 0.2% per pg/ml. Specificity was confirmed using a non-thrombin specific aptamer as the neg-ative control. These results indicate that the graphene sensor platform developed in this thesis has the potential as a highly sensitive POCD. The processes developed here can be used to develop graphene sensors for multiple biomarkers in the future

Electrochemical processes and systems: application for tutors

The features of redox reactions and the principles of their balancing according to the medium composition are considered. The basic representations about electrochemical processes and systems are outlined. The reactions and principles of chemical sources of electric energy and electrolysis systems functioning are analyzed. A general idea is given about the chemical properties of metals, corrosion resistance in environments of various aggressiveness, and the protection principles are given. Multivariate tasks and exercises for students, and PhD student’s classroom and independent work are offered. For teachers, PhD students and students of universities of specialties "Chemical technologies and engineering", "Biotechnologies and bioengineering", "Oil and gas engineering and technologies".Розглянуто особливості окисно-відновних реакцій і принципи їх балансування залежно від складу середовища. Викладено фундаментальні уявлення про електрохімічні процеси і системи. Проаналізовано перебіг реакцій і принципи функціонування хімічних джерел електричної енергії та систем електролізу. Узагальнено уявлення щодо хімічних властивостей металів, корозійної стійкості у середовищах різної агресивності та наведено принципи організації захисту від руйнування. Запропоновано багатоваріантні завдання та вправи для аудиторної та самостійної роботи студентів і аспірантів. Розраховано на викладачів, аспірантів і студентів вищих навчальних закладів спеціальностей "Хімічні технології та інженерія”, "Біотехнології та біоінженерія", "Нафтогазова інженерія та технології"