TOWARDS INTEGRATION OF GRAPHENE IN ADVANCED CMOS INTERCONNECT TECHNOLOGY

The integration of graphene into existing state-of-the-art semiconductor manufacturing is a topic of worldwide interest. With its unprecedented electrical, thermal and mechanical properties, graphene is ideally suited for back-end of line (BEOL) technology to boost the performance of on-chip copper (Cu) interconnects. However, the lack of BEOL compatible methods has stymied the true evaluation of Cu/graphene hybrid (Cu-G) technology. The objectives of this thesis proposal are to demonstrate BEOL-compatible graphene growth techniques, and explore various avenues for practical integration of graphene in order to achieve better electrical, thermal and reliability metrics than traditional interconnect technology

Scaling and process effect on electromigration reliability for Cu/low k interconnects

textThe microelectronics industry has been managing the RC delay problem arising from aggressive line scaling, by replacing aluminum (Al) by copper (Cu) and oxide dielectric by low-k dielectric. Electromigration (EM) turned out to be a serious reliability problem for Cu interconnects due to the implementation of mechanically weaker low-k dielectrics. In addition, line width and via size scaling resulted in the need of a novel diffusion barrier, which should be uniform and thin. The objective of this dissertation is to investigate the impacts of Ta barrier process, such as barrier-first and pre-clean first, and scaling of barrier and line/via on EM reliability of Cu/low-k interconnects. For this purpose, EM statistical test structures, having different number of line segments, line width, and via width, were designed. The EM test structures were fabricated by a dualdamascene process with two metal layers (M1/Via/M2), which were then packaged for EM tests. The package-level EM tests were performed in a specially designed vacuum chamber with pure nitrogen environment. The novel barrier deposition process, called barrier-first, showed a higher (jL)[subscript c] product and prolonged EM lifetime, compared with the conventional Ta barrier deposition process, known as pre-clean first. This can be attributed to the improved uniformity and thickness of the Ta layer on the via and trench, as confirmed by TEM. As for the barrier thickness effect, the (jL)c product decreased with decreasing thickness, due to reduced Cu confinement. A direct correlation between via size and EM reliability was found; namely, EM lifetime and statistics degraded with via size. This can be attributed to the fact that critical void length to cause open circuit is about the size of via width. To investigate further line scaling effect on EM reliability, SiON (siliconoxynitride) trenchfilling process was introduced to fabricate 60-nm lines, corresponding to 45-nm technology, using a conventional, wider line lithograph technology. The EM lifetime of 60-nm fine lines with SiON filling was longer than that of a standard damascene structure, which can be attributed to a distinct via/metal-1 configuration in reducing process-induced defects at the via/metal-1 interface.Materials Science and Engineerin

Porous Low-Dielectric-Constant Material for Semiconductor Microelectronics

To provide high speed, low dynamic power dissipation, and low cross-talk noise for microelectronic circuits, low-dielectric-constant (low-k) materials are required as the inter- and intra-level dielectric (ILD) insulator of the back-end-of-line interconnects. Porous low-k materials have low-polarizability chemical compositions and the introducing porosity in the film. Integration of porous low-k materials into microelectronic circuits, however, poses a number of challenges because the composition and porosity affected the resistance to damage during integration processing and reduced the mechanical strength, thereby degrading the properties and reliability. These issues arising from porous low-k materials are the subject of the present chapter

차세대 반도체 배선을 위한 코발트 합금 자가형성 확산방지막 재료 설계 및 전기적 신뢰성에 대한 연구

학위논문(박사) -- 서울대학교대학원 : 공과대학 재료공학부, 2022.2. 주영창.Recently, the resistance-capacitance (RC) delay of the Cu interconnects in metal 1 (M1) level has been increased rapidly due to the reduction of the interconnect linewidth along with the transistor scaling down, and the interconnect reliability becomes a severe issue again. In order to overcome interconnect performance problems and move forward to the next-generation interconnects system, study on low resistivity (ρo) and low electron mean free path (λ) metals was conducted. Generally, metals such as Cobalt (Co), Ruthenium (Ru), and Molybdenum (Mo) are mentioned as candidates for next-generation interconnect materials, and since they have a low ρo × λ value, it is expected that the influence of interface scatterings and surface scattering can be minimized. However, harsh operating environments such as high electric fields, critical Joule heating, and reduction of the pitch size are severely deteriorating the performance of electronic devices as well as device reliability. For example, since time dependent dielectric breakdown (TDDB) problems for next-generation interconnect system have been reported recently, it is necessary to study alternative barrier materials and processes to improve the interconnect reliability. Specifically, extrinsic dielectric breakdown due to penetration of Co metal ions in high electric fields has been reported as a reliability problem to be solved in Co interconnect systems. Therefore, there is a need for new material system design and research on a robust diffusion barrier that prevents metal ions from penetrating into the dielectric, thereby improving the reliability of Co interconnects. Moreover, in order to lower the resistance of the interconnect, it is necessary to develop an ultra-thin barrier. This is because even a barrier with good reliability characteristics will degrade chip performance if it takes up a lot of volume in the interconnect. The recommended thickness for a single diffusion barrier layer is currently reported to be less than 2.5 nm. As a result, it is essential to develop materials that comprehensively consider performance and reliability. In this study, we designed a Co alloy self-forming barrier (SFB) material that can make sure of low resistance and high reliability for Co interconnects, which is attracting attention as a next-generation interconnect system. The self-forming barrier methodology induces diffusion of an alloy dopant at the interface between the metal and the dielectric during the annealing process. And the diffused dopant reacts with the dielectric to form an ultra-thin diffusion barrier. Through this methodology, it is possible to improve reliability by preventing the movement of metal ions. First of all, material design rules were established to screen the appropriate alloy dopants and all CMOS-compatible metals were investigated. Dopant resistivity, intermetallic compound formation, solubility in Co, activity coefficient in Co, and oxidation tendency is considered as the criteria for the dopant to escape from the Co matrix and react at the Co/SiO2 interface. In addition, thermodynamic calculations were performed to predict which phases would be formed after the annealing process. Based on thermodynamic calculations, 5 dopant metals were selected, prioritized for self-forming behavior. And the self-forming material was finally selected through thin film and device analysis. We confirmed that Cr, Zn, and Mn out-diffused to the surface of the thin film structure using X-ray photoelectron spectroscopy (XPS) depth profile and investigated the chemical state of out-diffused dopants through the analysis of a binding energy. Cr shows the most ideal self-forming behavior with the SiO2 dielectric and reacted with oxygen to form a Cr2O3 barrier. In metal-insulator-semiconductor (MIS) structure, out-diffused Cr reacts with SiO2 at the interface and forms a self-formed single layer. It was confirmed that the thickness of the diffusion barrier layer is about 1.2 nm, which is an ultra-thin layer capable of minimizing the total effective resistance. Through voltage-ramping dielectric breakdown (VRDB) tests, Co-Cr alloy showed highest breakdown voltage (VBD) up to 200 % than pure Co. The effect of Cr doping concentration and heat treatment condition applicable to the interconnect process was confirmed. When Cr was doped less than 1 at%, the robust electrical reliability was exhibited. Also, it was found that a Cr2O3 interfacial layer was formed when annealing process was performed at 250 °C or higher for 30 minutes or longer. In other words, Co-Cr alloy is well suited for the interconnect process because current interconnect process temperature is below 400 °C. And when the film thickness was lowered from 150 nm to 20 nm, excellent VBD values were confirmed even at high Cr doping concentration (~7.5 at%). It seems that the amount of Cr present at the Co/SiO2 interface plays a very important role in improving the Cr oxide SFB quality. Physical modeling is necessary to understand the amount of Cr at the interface according to the interconnect volumes and the reliability of the Cr oxide self-forming barrier. TDDB lifetime test also performed and Co-Cr alloy interconnect shows a highly reliable diffusion barrier property of self-formed interfacial layer. The DFT analysis also confirmed that Cr2O3 is a very promising barrier material because it showed a higher energy barrier value than the TiN diffusion barrier currently being studied. A Co-based self-forming barrier was designed through thermodynamic calculations that take performance and reliability into account in interconnect material system. A Co interconnect system with an ultra-thin Cr2O3 diffusion barrier with excellent reliability is proposed. Through this design, it is expected that high-performance interconnects based on robust reliability in the advanced interconnect can be implemented in the near future.최근 반도체 소자 스케일링에 따른 배선 선폭 감소로 M0, M1영역에서의 metal 비저항이 급격히 증가하여 배선에서의 RC delay가 다시 한번 크게 문제가 되고 있다. 이를 해결하기 위해서 차세대 배선 시스템에서는 낮은 비저항과 electron mean free path (EMFP)을 가지는 물질 연구가 진행되었다. 대표적으로 Co, Ru, Mo와 같은 금속들이 차세대 배선 재료 후보로 언급되고 있으며 낮은 ρ0 × λ 값을 갖기 때문에 interface (surface) scattering과 grain boundary scattering 영향을 최소화할 수 있을 것으로 보고 있다. 하지만 가혹한 electrical field와 높은 Joule heating이 발생하는 동작 환경으로 인해 performance뿐만 아니라 소자 신뢰성이 더 열악한 상황에 놓여있다. 예를 들어 차세대 금속에 대한 time dependent dielectric breakdown (TDDB) 신뢰성 문제가 보고되고 있기 때문에 이를 보안할 확산방지막 물질 및 공정연구가 필요하다. 특히 높은 전기장에서 Co ion이 유전체로 침투하여 extrinsic dielectric breakdown 신뢰성 문제가 최근 보고되고 있다. 따라서 금속 이온이 유전체 내부로 침투하는 것을 방지하여, Co 배선의 신뢰성을 향상시킬 수 견고한 확산방지막 개발 및 새로운 배선 시스템 설계가 필요한 시점이다. 또한, 배선 저항을 낮추기 위해서는 매우 얇은 확산방지막 개발이 필요하다. 신뢰성이 좋은 확산방지막이라도 배선에서 많은 영역을 차지할 경우 전체 성능이 저하되기 때문이다. Cu 확산방지막으로 사용되고 있는 TaN 층은 2.5 nm 보다 얇을 경우 신뢰성이 급격히 나빠지므로 2.5 nm보다 얇은 두께의 견고한 확산방지막 개발이 필요하다. 본 연구는 차세대 반도체 배선 물질로 주목받고 있는 Co 금속에 대하여 저저항·고신뢰성을 확보할 수 있는 Co alloy 자가형성 확산방지막 (Co alloy self-forming barrier, SFB) 소재 디자인하였다. 자가형성 확산방지막 방법론은 열처리 과정에서 금속과 유전체 계면에서 도펀트가 확산하게 된다. 그리고 확산되니 도펀트는 얇은 확산방지막을 형성하는 방법론이다. 이 방법론을 통해 금속 이온의 이동을 방지하여 Co 배선 신뢰성을 향상시킬 수 있을 것으로 예상하였다. 우선, Co 합금상에서 적절한 도펀트를 찾기 위해서 CMOS 공정에 적용 가능한 금속들을 선별하였다. 도펀트 저항, 금속간 화합물 형성 여부, Co내 고용도, Co alloy에서의 활성계수, 산화도, Co/SiO2 계면에서의 안정상을 열역학적 계산을 통해서 물질 선정 기준으로 세웠다. 열역학적 계산을 기반으로 9개의 도펀트 금속이 선택되었으며, Co 합금 자가형성 확산방지막 기준에 따라서 우선 순위를 지정하였다. 그리고 최종적으로 박막과 소자 신뢰성 평가를 통해서 가장 적합한 자가형성 확산방지막 물질을 선정하였다. X-ray photoelectron spectroscopy (XPS) 분석을 이용하여 Cr, Zn, Mn이 박막 구조의 표면으로 외부 확산 여부를 확인하고 결합 에너지 분석을 통해 외부로 확산된 도펀트의 화학적 상태를 조사하였다. 분석 결과 Cr, Zn, Mn이 유전체 계면으로 확산되어 산소와 반응하여oxide/silicate 확산 방지막 (e.g. Cr2O3, Zn2SiO4, MnSiO3)을 형성한 것을 확인하였다. 그 중 Cr은 SiO2 유전체와 함께 가장 이상적인 자기 형성 거동을 나타내며 산소와 반응하여 Cr2O3 층을 형성하는 것을 확인하였다. MIS (Metal-Insulator-Semiconductor) 구조에서도 외부로 확산된 Cr은 계면에서 SiO2와 반응하여 Cr2O3 자가형성 확산방지막이 형성되었다. 확산방지층의 두께는 약 1.2nm로 전체 유효저항을 최소화할 수 있는 충분히 얇은 두께를 확보하였다. VRDB (Voltage-Ramping Dielectric Breakdown) 테스트를 통해 Co-Cr 합금은 순수 Co보다 최대 200% 높은 항복 전압 (breakdown voltage)을 보였다. 반도체 배선 공정에 적용할 수 있는 Cr 도핑 농도와 열처리 조건의 영향을 확인하였다. Cr이 1at% 미만으로 도핑되었을 때 우수한 전기적 신뢰성을 나타내었다. 또한, 250℃ 이상에서 30분 이상 열처리를 하였을 때 Cr2O3 계면층이 형성됨을 알 수 있었다. 즉, 현재 배선 공정 온도가 400°C 미만이기 때문에 Co-Cr 합금이 배선 공정에 적용 가능함을 확인하였다. TDDB 수명 테스트도 수행되었으며 Co-Cr 합금 배선은 자체 형성된 계면층의 매우 안정적인 확산 장벽 특성을 보여주었다. DFT 분석은 Cr2O3자가형성 확산방지막이 현재 연구되고 있는 TiN 확산 장벽보다 더 높은 에너지 장벽 값을 보여주기 때문에 매우 유망한 확산방지막임을 보여주었다. 본 연구는 반도채 배선 물질 시스템에서 성능과 신뢰성을 고려한 열역학적 계산을 통해 Co 기반 자가형성 확산방지막을 설계하였다. 실험 결과 신뢰성이 우수하고 아주 얇은 Cr2O3 확산방지막이 있는 Co-Cr 합금이 제안하였다. 물질 설계와 전기적 신뢰성 검증을 Co/Cr2O3/SiO2 물질 시스템을 제안하였고 앞으로의 다가올 차세대 배선에서 구현될 수 있을 것으로 기대된다.Abstract i Table of Contents v List of Tables ix List of Figures xii Chapter 1. Introduction 1 1.1. Scaling down of VLSI systems 1 1.2. Driving force of interconnect system evolution 7 1.3. Driving force of beyond Cu interconnects 11 1.4. Objective of the thesis 18 1.5. Organization of the thesis 21 Chapter 2. Theoretical Background 22 2.1. Evolution of interconnect systems 22 2.1.1. Cu/barrier/low-k interconnect system 22 2.1.2. Process developments for interconnect reliability 27 2.1.3. 3rd generation of interconnect system 31 2.2 Thermodynamic tools for Co self-forming barrier 42 2.2.1 Binary phase diagram 42 2.2.2 Ellingham diagram 42 2.2.3 Activity coefficient 43 2.3. Reliability of Interconnects 45 2.3.1. Current conduction mechanisms in dielectrics 45 2.3.2. Reliability test vehicles 50 2.3.3. Dielectric breakdown assessment 52 2.3.4. Dielectric breakdown mechanisms 55 2.3.5. Reliability test: VRDB and TDDB 56 2.3.6. Lifetime models 57 Chapter 3. Experimental Procedures 60 3.1. Thin film deposition 60 3.1.1. Substrate preparation 60 3.1.2. Oxidation 61 3.1.3. Co alloy deposition using DC magnetron sputtering 61 3.1.4. Annealing process 65 3.2. Thin film characterization 67 3.2.1. Sheet resistance 67 3.2.2. X-ray photoelectron spectroscopy (XPS) 68 3.3. Metal-Insulator-Semiconductor (MIS) device fabrication 70 3.3.1. Patterning using lift-off process 70 3.3.2. TDDB packaging 72 3.4. Reliability analysis 74 3.4.1. Electrical reliability analysis 74 3.4.2. Transmission electron microscopy (TEM) analysis 75 3.5. Computation 76 3.5.1 FactsageTM calculation 76 3.5.2. Density Functional Theory (DFT) calculation 77 Chapter 4. Co Alloy Design for Advanced Interconnects 78 4.1. Material design of Co alloy self-forming barrier 78 4.1.1. Rule of thumb of Co-X alloy 78 4.1.2. Co alloy phase 80 4.1.3. Out-diffusion stage 81 4.1.4. Reaction step with SiO2 dielectric 89 4.1.5. Comparison criteria 94 4.2. Comparison of Co alloy candidates 97 4.2.1. Thin film resistivity evaluation 97 4.2.2. Self-forming behavior using XPS depth profile analysis 102 4.2.3. MIS device reliability test 110 4.3 Summary 115 Chapter 5. Co-Cr Alloy Interconnect with Robust Self-Forming Barrier 117 5.1. Compatibility of Co-Cr alloy SFB process 117 5.1.1. Effect of Cr doping concentration 117 5.1.2. Annealing process condition optimization 119 5.2. Reliability of Co-Cr interconnects 122 5.2.1. VRDB quality test with Co-Cr alloys 122 5.2.2. Lifetime evaluation using TDDB method 141 5.2.3. Barrier mechanism using DFT 142 5.3. Summary 145 Chapter 6. Conclusion 148 6.1. Summary of results 148 6.2. Research perspectives 150 References 151 Abstract (In Korean) 166 Curriculum Vitae 169박

A survey of carbon nanotube interconnects for energy efficient integrated circuits

This article is a review of the state-of-art carbon nanotube interconnects for Silicon application with respect to the recent literature. Amongst all the research on carbon nanotube interconnects, those discussed here cover 1) challenges with current copper interconnects, 2) process & growth of carbon nanotube interconnects compatible with back-end-of-line integration, and 3) modeling and simulation for circuit-level benchmarking and performance prediction. The focus is on the evolution of carbon nanotube interconnects from the process, theoretical modeling, and experimental characterization to on-chip interconnect applications. We provide an overview of the current advancements on carbon nanotube interconnects and also regarding the prospects for designing energy efficient integrated circuits. Each selected category is presented in an accessible manner aiming to serve as a survey and informative cornerstone on carbon nanotube interconnects relevant to students and scientists belonging to a range of fields from physics, processing to circuit design

Coatings for ALD Reactors to Prevent Metal Contamination on Semiconductor Products

Atomic layer deposition (ALD) is a promising processing method for the next generation semiconductor devices. Major advantages of ALD include conformality, uniformity over large areas, precise thickness control, repeatability and high quality of films produced. ALD thin film deposition is done inside an ALD reactor. Typical construction materials of ALD reactors include metal alloys such as stainless steel, aluminum and titanium. These materials contain multiple metallic elements that can be detrimental to the performance, reliability and yield of semiconductor devices. In order to process semiconductor devices with ALD, metal impurity levels originating from the ALD reactor must be controlled. Allowed levels of metal impurities in semiconductor processing are stringent and showing a tightening trend. This has led into the development of new methods for contamination control together with the adoption of more sensitive and robust detection methods for metallic impurities, such as inductively coupled plasma mass spectrometry (ICP-MS). This master thesis focuses on the metallic impurities originating from an ALD reactor and their prevention with ALD coatings. Three typical construction materials, aluminum, titanium and stainless steel were examined. The studied coatings were ALD deposited aluminum oxide (Al2O3), hafnium oxide (HfO2) and their nanolaminate (Al2O3/HfO2). The ability of the coatings to prevent metal impurity transfer from the metals to silicon substrates through the gas phase was studied by exposing the coated metals to two ALD precursors, trimethyl aluminum (TMA) and tris(dimethylamino) cyclopentadienyl hafnium (CpHf(NMe2)3). Metal impurity concentrations on silicon were measured with ICP-MS. Since academic literature concerning control of metal contamination from ALD reactors does not directly exist, the literature part of this thesis was based on relevant related topics. The selected topics included the development of semiconductor industry, role of ALD in this development and new ALD materials and chemistries required. Additionally, protective ALD films and the effects of metal impurities in semiconductor products were reviewed. The overall conclusion of this study was that the ALD coatings provide a worthy solution for metal contamination control. Some differences between the passivation efficiencies of different metal – coating systems were found

Advances in electronic packaging technologies by ultra-small microvias, super-fine interconnections and low loss polymer dielectrics

The fundamental motivation for this dissertation is to address the widening interconnect gap between integrated circuit (IC) demands and package substrates specifically for high frequency digital-RF systems applications. Moore's law for CMOS ICs predicts that transistor density on ICs will double approximately every 18 months. The current state-of-the-art in IC package substrates is at 20µm lines/spaces and 50-60µm microvia diameter using epoxy dielectrics with loss tangent above 0.01. The research targets are to overcome the barriers of current technologies and demonstrate a set of advanced materials and process technologies capable of 5-10µm lines and spaces, and 10-30µm diameter microvias in a multilayer 3-D wiring substrate using 10-25µm thin film dielectrics with loss tangent in the <0.005. The research elements are organized as follows with a clear focus on understanding and characterization of fundamental materials structure-processing-property relationships and interfaces to achieve the next generation targets. (a) Low CTE Core Substrate, (b) Low Loss Dielectrics with 25µm and smaller microvias, (c) Sub-10µm Width Cu Conductors, and (d) Integration of the various dielectric and conductor processes.Ph.D.Committee Chair: Tummala, Rao; Committee Member: Iyer, Mahadevan; Committee Member: Saxena, Ashok; Committee Member: Swaminathan, Madhavan; Committee Member: Wong, Chingpin

Copper to copper bonding by nano interfaces for fine pitch interconnections and thermal applications

Ever growing demands for portability and functionality have always governed the electronic technology innovations. IC downscaling with Moore s law at IC level and system miniaturization with System-On-Package (SOP) paradigm at system level, have resulted and will continue to result in ultraminiaturized systems with unprecedented functionality at reduced cost. However, system miniaturization poses several electrical and thermal challenges that demand innovative solutions including advanced materials, bonding and assembly techniques. Heterogeneous material and device integration for thermal structures and IC assembly are limited by the bonding technology and the electrical and thermal impedance of the bonding interfaces. Solder - based bonding technology that is prevalent today is a major limitation to future systems. The trend towards miniaturized systems is expected to drive downscaling of IC I/O pad pitches from 40µm to 1- 5µm in future. Solder technology imposes several pitch, processability and cost restrictions at such fine pitches. Furthermore, according to International Technology Roadmap for Semiconductors (ITRS-2006), the supply current in high performance microprocessors is expected to increase to 220 A by 2012. At such supply current, the current density will exceed the maximum allowable current density of solders. The intrinsic delay and electromigration in solders are other daunting issues that become critical at nanometer sized technology nodes. In addition, formation of intermetallics is also a bottleneck that poses significant mechanical issues. Similarly, thermal power dissipation is growing to unprecedented high with a projected power of 198 W by 2008 (ITRS 2006). Present thermal interfaces are not adequate for such high heat dissipation. Recently, copper based thin film bonding has become a promising approach to address the abovementioned challenges. However, copper-copper direct bonding without using solders has not been studied thoroughly. Typically, bonding is carried out at 400oC for 30 min followed by annealing for 30 min. High thermal budget in such process makes it less attractive for integrated systems because of the associated process incompatibilities. Hence, there is a need to develop a novel low temperature copper to copper bonding process. In the present study, nanomaterials - based copper-to-copper bonding is explored and developed as an alternative to solder-based bonding. To demonstrate fine pitch bonding, the patterning of these nanoparticles is crucial. Therefore, two novel self-patterning techniques based on: 1.) Selective wetting and 2.) Selective nanoparticle deposition, are developed to address this challenge. Nanoparticle active layer facilitates diffusion and, thus, a reliable bond can be achieved using less thermal budget. Quantitative characterization of the bonding revealed good metallurgical bonding with very high bond strength. This has been confirmed by several morphological and structural characterizations. A 30-micron pitch IC assembly test vehicle is used to demonstrate fine pitch patternability and bonding. In conclusion, novel nanoparticle synthesis and patterning techniques were developed and demonstrated for low-impedance and low-cost electrical and thermal interfaces.M.S.Committee Chair: Rao R. Tummala; Committee Member: C. P. Wong; Committee Member: P. M. Ra