Broadband dielectric spectroscopic detection of volatile organic compounds with ZnO nanorod gas sensors.

Metal-oxide (MO) semiconductor gas sensors based on chemical resistivity necessarily involve making electrical contacts to the sensing materials. These contacts are imperfect and introduce errors into the measurements. In this paper, we demonstrate the feasibility of using contactless broadband dielectric spectroscopy (BDS)-based metrology in gas monitoring that avoids distortions in the reported resistivity values due to probe use, and parasitic errors (i.e. tool-measurand interactions). Specifically, we show how radio frequency propagation characteristics can be applied to study discrete processes on MO sensing material, such as zinc oxide (i.e. ZnO) surfaces, when exposed to a redox-active gas. Specifically, we have used BDS to investigate the initial oxidization of ZnO gas sensing material in air at temperatures below 200 °C, and to show that the technique affords new mechanistic insights that are inaccessible with the traditional resistance-based measurements.

Broadband Dielectric Spectroscopy as a Potential Label-Free Method to Rapidly Verify Ultraviolet-C Radiation Disinfection.

Microwave (MW) sensing offers noninvasive, real-time detection of the electromagnetic properties of biological materials via the highly concentrated electromagnetic fields, for which advantages include wide bandwidth, small size, and cost-effective fabrication. In this paper, we present the application of MW broadband dielectric spectroscopy (BDS) coupled to a fabricated biological thin film for evaluating ultraviolet-C (UV-C) exposure effects. The BDS thin film technique could be deployed as a biological indicator for assessing whole-room UV-C surface disinfection. The disinfection process is monitored by BDS as changes in the electrical properties of surface-confined biological thin films photodegraded with UV-C radiation. Fetal bovine serum (FBS, a surrogate for protein) and bacteriophage lambda double-stranded deoxyribonucleic acid (dsDNA) were continuously monitored with BDS during UV-C radiation exposure. The electrical resistance of FBS films yielded promising yet imprecise readings, whereas the resistance of dsDNA films discernibly decreased with UV-C exposure. The observations are consistent with the expected photo-oxidation and photodecomposition of protein and DNA. While further research is needed to characterize these measurements, this study presents the first application of BDS to evaluate the electrical properties of solid-state biological thin films. This technique shows promise toward the development of a test method and a standard biological test to determine the efficacy of UV-C disinfection. Such a test with biological indicators could easily be applied to hospital rooms between patient occupancy for a multipoint evaluation to determine if a room meets a disinfection threshold set for new patients.

Models for an Ultraviolet-C Research and Development Consortium.

The development of an international, precompetitive, collaborative, ultraviolet (UV) research consortium is discussed as an opportunity to lay the groundwork for a new UV commercial industry and the supply chain to support this industry. History has demonstrated that consortia can offer promising approaches to solve many common, current industry challenges, such as the paucity of data regarding the doses of ultraviolet-C (UV-C, 200 nm to 280 nm) radiation necessary to achieve the desired reductions in healthcare pathogens and the ability of mobile disinfection devices to deliver adequate doses to the different types of surfaces in a whole-room environment. Standard methods for testing are only in the initial stages of development, making it difficult to choose a specific UV-C device for a healthcare application. Currently, the public interest in UV-C disinfection applications is elevated due to the spread of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2), the virus that causes the respiratory coronavirus disease 19 (COVID-19). By channeling the expertise of different UV industry stakeholder sectors into a unified international consortium, innovation in UV measurements and data could be developed to support test methods and standards development for UV healthcare equipment. As discussed in this paper, several successful examples of consortia are applicable to the UV industry to help solve these types of common problems. It is anticipated that a consortium for the industry could lead to UV applications for disinfection becoming globally prolific and commonplace in residential, work, business, and school settings as well as in transportation (bus, rail, air, ship) environments. Aggressive elimination of infectious agents by UV-C technologies would also help to reduce the evolution of antibiotic-resistant bacteria.

Ultraviolet Radiation Technologies and Healthcare-Associated Infections: Standards and Metrology Needs.

The National Institute of Standards and Technology (NIST) hosted an international workshop on ultraviolet-C (UV-C) disinfection technologies on January 14-15, 2020, in Gaithersburg, Maryland, in collaboration with the International Ultraviolet Association (IUVA). This successful public event, as evidenced by the participation of more than 150 attendees, with 65% from the ultraviolet technology industry, was part of an ongoing collaborative effort between NIST and the IUVA and its affiliates to examine the measurement and standards needs for pathogen abatement with UV-C in the healthcare whole-room environment. Prior to and since this event, stakeholders from industry, academia, government, and public health services have been collaboratively engaged with NIST to accelerate the development and use of accurate measurements and models for UV-C disinfection technologies and facilitate technology transfer. The workshop served as an open forum to continue this discussion with a technical focus centered on the effective design, use, and implementation of UV-C technologies for the prevention and treatment of healthcare-associated infections (HAIs) in complex hospital settings. These settings include patient rooms, operating rooms, common staging areas, ventilation systems, personal protective equipment, and tools for the reprocessing and disinfecting of instruments or devices used in medical procedures, such as catheters and ventilators. The critical need for UV-C technologies for disinfection has been amplified by the outbreak of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2), the virus that causes coronavirus disease 2019 (COVID-19), stimulating an even greater emphasis on identifying testing and performance metrology needs. This paper discusses these topics based on the international workshop and community activities since the workshop, including a public World-Wide-Web-based seminar with more than 500 registered attendees on September 30, 2020; an international conference on UV-C technologies for air and surface disinfection, December 8-9, 2020; and a webinar on returning to normalcy with the use of UV-C technologies, April 27 and 29, 2021. This article also serves as an introduction to a special section of the Journal of Research of the National Institute of Standards and Technology, where full papers address recent technical, noncommercial, UV-C technology and pathogen-abatement investigations. The set of papers provides keen insights from the vantage points of medicine and industry. Recent technical developments, successes, and needs in optics and photonics, radiation physics, biological efficacy, and the needs of future markets in UV-C technologies are described to provide a concise compilation of the community's efforts and the state of the field. Standards needs are identified and discussed throughout this special section. This article provides a summary of the essential role of standards for innovation and implementation of UV-C technology for improved patient care and public health.

The Impact of Organic Additives on Copper Trench Microstructure.

Organic additives are typically used in the pulse electrodeposition of copper (Cu) to prevent void formation during the filling of high aspect ratio features. In this work, the role of bath chemistry as modified by organic additives was investigated for its effects on Cu trench microstructure. Polyethylene glycol (PEG), bis(3-sulfopropyl) disulfide (SPS), and Janus green b (JGB) concentrations were varied in the Cu electrodeposition bath. Results indicated a correlation between the JGB/SPS ratio and the surface roughness and residual stresses in the Cu. Electron backscattering diffraction (EBSD) and transmission Kikuchi diffraction (TKD) were used to study the cross-sectional microstructure in the trenches. Finer grain morphologies appeared in trenches filled with organic additives as compared to additive-free structures. Cu trench (111) texture also decreased with increasing organic additive concentrations due to more pronounced influence of sidewall seed layers on trench features. Twin density in the microstructure closely tracked calculated stresses in the Cu trenches. A comprehensive microstructural analysis was conducted in this study, on an area of focus that has garnered little attention from the literature, yet can have a major impact on microelectronic reliability.

The Influence of Pulsed Electroplating Frequency and Duty Cycle on Copper Film Microstructure and Stress State.

In this work we studied the impact of pulse electroplating parameters on the cross-sectional and surface microstructures of blanket copper films using electron backscattering diffraction and x-ray diffraction. The films evaluated were highly (111) textured in the direction perpendicular to the film surface. The degree of preferential orientation was found to decrease with longer pulse on-times, due to strain energy driven growth of other grain orientations. Residual biaxial stresses were also measured in the films and higher pulse frequencies during deposition led to smaller biaxial stresses in the films. Film stress was also found to correlate with the amount of twinning in the copper film cross-sections. This has been attributed to the twins' thermal stability and mechanical properties.

Metrology for 2D materials: a perspective review from the international roadmap for devices and systems.

The International Roadmap for Devices and Systems (IRDS) predicts the integration of 2D materials into high-volume manufacturing as channel materials within the next decade, primarily in ultra-scaled and low-power devices. While their widespread adoption in advanced chip manufacturing is evolving, the need for diverse characterization methods is clear. This is necessary to assess structural, electrical, compositional, and mechanical properties to control and optimize 2D materials in mass-produced devices. Although the lab-to-fab transition remains nascent and a universal metrology solution is yet to emerge, rapid community progress underscores the potential for significant advancements. This paper reviews current measurement capabilities, identifies gaps in essential metrology for CMOS-compatible 2D materials, and explores fundamental measurement science limitations when applying these techniques in high-volume semiconductor manufacturing.

Broadband Microwave Signal Dissipation in Nanostructured Copper Oxide at Air-Film Interface.

Contactless broadband microwave spectroscopy (a.k.a., broadband dielectric spectroscopy (BDS)) enables the accurate operando analysis of the electrical and magnetic properties without compromising the kinetic conditions of the experiment. The BDS method is sensitive to the actual electronic structure of species, and it is most relevant to redox reactions involving charge-transfer. In this paper, using BDS, we have studied and characterized the oxidation of a copper layer in a purposely built prototypical 3-D integrated circuit (3D-IC) during cycled high-temperature storage. We show that the microwave signal loss in these devices is attributable to the energy dissipation through the signal's interactions with the copper oxidation product. The results demonstrate that contactless BDS could be leveraged into an excellent metrology for applications that use metal oxide as sensing elements.

Generating Multiscale Gold Nanostructures on Glass without Sidewall Deposits Using Minimal Dry Etching Steps.

The advent of recent technologies in the nanoscience arena requires new and improved methods for the fabrication of multiscale features ( e.g., from micro- to nanometer scales). Specifically, biological applications generally demand the use of transparent substrates to allow for the optical monitoring of processes of interest in cells and other biological materials. Whereas wet etching methods commonly fail to produce essential nanometer scale features, plasma-based dry etching can produce features down to tens of nanometers. However, dry etching methods routinely require extreme conditions and extra steps to obtain features without residual materials such as sidewall deposits (veils). This work presents the development of a gold etching process with gases that are commonly used to etch glass. Our method can etch gold films using reactive ion etching (RIE) at room temperature and mild pressure in a trifluoromethane (CHF3)/oxygen (O2) environment, producing features down to 50 nm. Aspect ratios of 2 are obtainable in one single step and without sidewall veils by controlling the oxygen present during the RIE process. This method generates surfaces completely flat and ready for the deposition of other materials. The gold features that were produced by this method exhibited high conductivity when carbon nanotubes were deposited on top of patterned features (gold nanoelectrodes), hence demonstrating an electrically functional gold after the dry etching process. The production of gold nanofeatures on glass substrates would serve as biocompatible, highly conductive, and chemically stable materials in biological/biomedical applications.

Contactless Resonant Cavity Dielectric Spectroscopic Studies of Cellulosic Paper Aging.

The current analytical techniques for characterizing printing and graphic arts substrates, particularly those used to date and authenticate provenance, are destructive. This limits the amount of data that can be captured from an individual sample. For samples being evaluated in forensic and archeological investigations, any loss or degradation of the materials is undesirable. Furthermore, it is difficult to produce statistically relevant data for such analytes. We have shown elsewhere that a contactless microwave resonant cavity dielectric spectroscopy technique can discriminate between paper samples made from different plant fiber species based on their lignin content. In this publication, we demonstrate the utility of the contactless resonant cavity dielectric spectroscopy (RCDS) technique in the characterization of naturally and artificially aged paper samples. Based on our experimental results, we suggest that the technique could be used in forensic and archeological investigations of unique paper products.

Method Development for Contactless Resonant Cavity Dielectric Spectroscopic Studies of Cellulosic Paper.

The current analytical techniques for characterizing printing and graphic arts substrates are largely ex situ and destructive. This limits the amount of data that can be obtained from an individual sample and renders it difficult to produce statistically relevant data for unique and rare materials. Resonant cavity dielectric spectroscopy is a non-destructive, contactless technique which can simultaneously interrogate both sides of a sheeted material and provide measurements which are suitable for statistical interpretations. This offers analysts the ability to quickly discriminate between sheeted materials based on composition and storage history. In this methodology article, we demonstrate how contactless resonant cavity dielectric spectroscopy may be used to differentiate between paper analytes of varying fiber species compositions, to determine the relative age of the paper, and to detect and quantify the amount of post-consumer waste (PCW) recycled fiber content in manufactured office paper.

Microwave Monitoring of Atmospheric Corrosion of Interconnects.

Traditional metrology has been unable to adequately address the reliability needs of emerging integrated circuits at the nano scale; thus, new metrology and techniques are needed. In this paper, we use microwave propagation characteristics (insertion loss and dispersion) to study the atmospheric interconnect corrosion under accelerated stress conditions. The results presented in this work indicate that the corrosion resilience of the test device is limited by the thermal aging of the passivation layer.

Dielectric spectroscopic studies of biological material evolution and application to paper.

Current product composition and quality test methods for the paper and pulp industry are mainly based on manual ex-situ wet-bench chemistry techniques. For example, the standard method for determining the furnish of paper, TAPPI T 401 "Fiber analysis of paper and paperboard," relies on the experience and visual acuity of a specially trained analyst to determine the individual plant species present and to quantify the amount of each constituent fiber type in a sheet of paper. Thus, there is a need for a fast, nondestructive analytical technique that leverages intrinsic attributes of the analytes. In this paper, we demonstrate an application of dielectric spectroscopy (DS) as a potential metrology to differentiate between nonwood pulp and wood pulp fibers. This in-situ, noncontact and nondestructive assessment method has inherent forensic capabilities and is also amiable to quality assurance techniques such as gauge capability studies and real-time statistical process control (SPC). APPLICATION: The dielectric spectroscopy results presented in this paper can nondestructively determine the amount of lignin in paper products and are in principle comparable to the performance specifications of the TAPPI Standard Test Method T 401 and should enable the sources of printing substrates to be both authenticated and validated in real time in a paper testing laboratory environment.

Innovative Approaches to Combat Healthcare-Associated Infections Using Efficacy Standards Developed Through Industry and Federal Collaboration.

Nation-wide, healthcare-associated infections (HAIs) infect one in every 25 hospital patients, account for more than 100,000 deaths and increase medical costs by around $96-147B, each year. Ultraviolet-C (UV-C) antimicrobial devices are shown to reduce the incidence of many of these HAIs by 35% or more, through the deactivation of the pathogen's DNA chain following irradiation with a wavelength of ~254 nm. This irradiation does not kill the cells, per se but effectively prevents the cells from multiplying. Clinical case reductions of 30-70% in Clostridium difficile (C. diff.) have been reported with similar results for methicillin-resistant Staphylococcus aureus (MRSA), and others. The methodology works, but, the adoption of UV-C technology by the healthcare industry has been sporadic. This is largely due to the lack of definitive knowledge and uniform performance standards or measures for efficacy to help healthcare managers make informed, credible investment decisions. The leveling of the playing field with scientifically certifiable data of the efficacy of antimicrobial devices will enhance acceptance by the healthcare industry and public, at large, as well as facilitate science-based decision making. The National Institute of Standards and Technology (NIST) has engaged with the International Ultra Violet Association (IUVA) and its member companies and affiliates to explore ways to develop needed standards, determine appropriate testing protocols, and transfer the technology to help to reduce these inharmonious market conditions. Collaborative efforts are underway to develop science-based answers to the healthcare industry's questions surrounding standards and measures of device disinfection efficacy, as well as reliability, operations and durability. These issues were recently discussed at the IUVA 2018 America's Conference in Redondo Beach, CA in several panel sessions. A major output of the sessions was the formation of a formal IUVA Working Group for the development of antimicrobial standards and initiatives for the healthcare industry. The goal of this working group is to provide global guidance, with specific programs and deliverables, on the use of UV technologies and standards to combat HAIs and to further the stated aims of the IUVA on its outreach to the healthcare industry. This paper reviews the strong collaboration between NIST and its industry partners pursuing the development of standards, guidelines and guidance documents related to healthcare applications that include standard methods for validating performance of UV devices and test guidelines for efficacy measurements. In addition, an overview of the issues, problems, and a summary of the needs confronting future growth and success of the UV industry in the Nation's healthcare application space is provided.

Microwave evaluation of electromigration susceptibility in advanced interconnects.

Traditional metrology has been unable to adequately address the needs of the emerging integrated circuits (ICs) at the nano scale; thus, new metrology and techniques are needed. For example, the reliability challenges in fabrication need to be well understood and controlled to facilitate mass production of through-substrate-via (TSV) enabled three-dimensional integrated circuits (3D-ICs). This requires new approaches to the metrology. In this paper, we use the microwave propagation characteristics to study the reliability issues that precede the physical damage caused by electromigration in the Cu-filled TSVs. The pre-failure microwave insertion losses and group delay are dependent on both the device temperature and the amount of current forced through the devices-under-test. The microwave insertion losses increase with the increase in the test temperature, while the group delay increases with the increase in the forced direct current magnitude. The microwave insertion losses are attributed to the defect mobility at the Cu-TiN interface, and the group delay changes are due to resistive heating in the interconnects, which perturbs the dielectric properties of the cladding dielectrics of the copper fill in the TSVs. https://doi.org/10.1063/1.4992135.

Broadband Dielectric Spectroscopic Characterization of Thermal Stability of Low-k Dielectric Thin Films for Micro- and Nanoelectronic Applications.

In this paper, we discuss the use of broadband microwaves (MW) to characterize the thermal stability of organic and hybrid silicon-organic thin films meant for insulation applications in micro- and nanoelectronic devices. We take advantage of MW propagation characteristics to extract and examine the relationships between electrical properties and the chemistry of prototypical low-k materials. The impact of thermal anneal at modest temperatures is examined to shed light on the thermal-induced performance and reliability changes within the dielectric films. These changes are then correlated with the chemical changes in the films, and could provide basis for rational selection of organic dielectrics for integrated devices.

Towards Understanding Early Failures Behavior during Device Burn-In: Broadband RF Monitoring of Atomistic Changes in Materials.

In this paper, we attempt to understand the physico-chemical changes that occur in devices during device "burn-in". We discuss the use of low frequency dielectric spectroscopy to detect, characterize and monitor changes in electrical defects present in the dielectrics of through silicon vias (TSV) for three dimensional (3D) interconnected integrated circuit devices, as the devices are subjected to fluctuating thermal loads. The observed changes in the electrical characteristics of the interconnects were traceable to changes in the chemistry of the isolation dielectric used in the TSV construction. The observed changes provide phenomenological insights into the practice of burn-in. The data also suggest that these "chemical defects" inherent in the 'as-manufactured' products may be responsible for some of the unexplained early reliability failures observed in TSV enabled 3D devices.

Dielectric Spectroscopic Detection of Early Failures in 3-D Integrated Circuits.

The commercial introduction of three dimensional integrated circuits (3D-ICs) has been hindered by reliability challenges, such as stress related failures, resistivity changes, and unexplained early failures. In this paper, we discuss a new RF-based metrology, based on dielectric spectroscopy, for detecting and characterizing electrically active defects in fully integrated 3D devices. These defects are traceable to the chemistry of the insolation dielectrics used in the through silicon via (TSV) construction. We show that these defects may be responsible for some of the unexplained early reliability failures observed in TSV enabled 3D devices.

Influence of metal-MoS2 interface on MoS2 transistor performance: comparison of Ag and Ti contacts.

In this work, we compare the electrical characteristics of MoS2 field-effect transistors (FETs) with Ag source/drain contacts with those with Ti and demonstrate that the metal-MoS2 interface is crucial to the device performance. MoS2 FETs with Ag contacts show more than 60 times higher ON-state current than those with Ti contacts. In order to better understand the mechanism of the better performance with Ag contacts, 5 nm Au/5 nm Ag (contact layer) or 5 nm Au/5 nm Ti film was deposited onto MoS2 monolayers and few layers, and the topography of metal films was characterized using scanning electron microscopy and atomic force microscopy. The surface morphology shows that, while there exist pinholes in Au/Ti film on MoS2, Au/Ag forms a smoother and denser film. Raman spectroscopy was carried out to investigate the metal-MoS2 interface. The Raman spectra from MoS2 covered with Au/Ag or Au/Ti film reveal that Ag or Ti is in direct contact with MoS2. Our findings show that the smoother and denser Au/Ag contacts lead to higher carrier transport efficiency.

Toward clean and crackless transfer of graphene.

We present the results of a thorough study of wet chemical methods for transferring chemical vapor deposition grown graphene from the metal growth substrate to a device-compatible substrate. On the basis of these results, we have developed a "modified RCA clean" transfer method that has much better control of both contamination and crack formation and does not degrade the quality of the transferred graphene. Using this transfer method, high device yields, up to 97%, with a narrow device performance metrics distribution were achieved. This demonstration addresses an important step toward large-scale graphene-based electronic device applications.