List of MOS sensors with the sensitivity for the different morphologies of ZnO nanostructures.
\\n\\n
More than half of the publishers listed alongside IntechOpen (18 out of 30) are Social Science and Humanities publishers. IntechOpen is an exception to this as a leader in not only Open Access content but Open Access content across all scientific disciplines, including Physical Sciences, Engineering and Technology, Health Sciences, Life Science, and Social Sciences and Humanities.
\\n\\nOur breakdown of titles published demonstrates this with 47% PET, 31% HS, 18% LS, and 4% SSH books published.
\\n\\n“Even though ItechOpen has shown the potential of sci-tech books using an OA approach,” other publishers “have shown little interest in OA books.”
\\n\\nAdditionally, each book published by IntechOpen contains original content and research findings.
\\n\\nWe are honored to be among such prestigious publishers and we hope to continue to spearhead that growth in our quest to promote Open Access as a true pioneer in OA book publishing.
\\n\\n\\n\\n
\\n"}]',published:!0,mainMedia:null},components:[{type:"htmlEditorComponent",content:'
Simba Information has released its Open Access Book Publishing 2020 - 2024 report and has again identified IntechOpen as the world’s largest Open Access book publisher by title count.
\n\nSimba Information is a leading provider for market intelligence and forecasts in the media and publishing industry. The report, published every year, provides an overview and financial outlook for the global professional e-book publishing market.
\n\nIntechOpen, De Gruyter, and Frontiers are the largest OA book publishers by title count, with IntechOpen coming in at first place with 5,101 OA books published, a good 1,782 titles ahead of the nearest competitor.
\n\nSince the first Open Access Book Publishing report published in 2016, IntechOpen has held the top stop each year.
\n\n\n\nMore than half of the publishers listed alongside IntechOpen (18 out of 30) are Social Science and Humanities publishers. IntechOpen is an exception to this as a leader in not only Open Access content but Open Access content across all scientific disciplines, including Physical Sciences, Engineering and Technology, Health Sciences, Life Science, and Social Sciences and Humanities.
\n\nOur breakdown of titles published demonstrates this with 47% PET, 31% HS, 18% LS, and 4% SSH books published.
\n\n“Even though ItechOpen has shown the potential of sci-tech books using an OA approach,” other publishers “have shown little interest in OA books.”
\n\nAdditionally, each book published by IntechOpen contains original content and research findings.
\n\nWe are honored to be among such prestigious publishers and we hope to continue to spearhead that growth in our quest to promote Open Access as a true pioneer in OA book publishing.
\n\n\n\n
\n'}],latestNews:[{slug:"stanford-university-identifies-top-2-scientists-over-1-000-are-intechopen-authors-and-editors-20210122",title:"Stanford University Identifies Top 2% Scientists, Over 1,000 are IntechOpen Authors and Editors"},{slug:"intechopen-authors-included-in-the-highly-cited-researchers-list-for-2020-20210121",title:"IntechOpen Authors Included in the Highly Cited Researchers List for 2020"},{slug:"intechopen-maintains-position-as-the-world-s-largest-oa-book-publisher-20201218",title:"IntechOpen Maintains Position as the World’s Largest OA Book Publisher"},{slug:"all-intechopen-books-available-on-perlego-20201215",title:"All IntechOpen Books Available on Perlego"},{slug:"oiv-awards-recognizes-intechopen-s-editors-20201127",title:"OIV Awards Recognizes IntechOpen's Editors"},{slug:"intechopen-joins-crossref-s-initiative-for-open-abstracts-i4oa-to-boost-the-discovery-of-research-20201005",title:"IntechOpen joins Crossref's Initiative for Open Abstracts (I4OA) to Boost the Discovery of Research"},{slug:"intechopen-hits-milestone-5-000-open-access-books-published-20200908",title:"IntechOpen hits milestone: 5,000 Open Access books published!"},{slug:"intechopen-books-hosted-on-the-mathworks-book-program-20200819",title:"IntechOpen Books Hosted on the MathWorks Book Program"}]},book:{item:{type:"book",id:"5265",leadTitle:null,fullTitle:"Metallic Glasses - Formation and Properties",title:"Metallic Glasses",subtitle:"Formation and Properties",reviewType:"peer-reviewed",abstract:"Metallic glasses and amorphous materials have attracted much more attention in the last two decades. 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\r\n\tTo understand the brain means to be able to reliably manipulate it and predict its response. Neuroscientists have long used electrophysiological techniques to stimulate particular brain areas or even single neurons. Electrical stimuli activate neural circuitry, often without being able to stop the neuronal activity. Neuropharmacological tools are based on drugs that are slow in their effects or not specific enough to stimulate individual cells. In 2005, a set of new techniques started to emerge that combined optical stimuli with genetic tools in order to control events in individual cells. The field of optogenetics has since revolutionized experimental approaches to study cell signaling, metabolism, brain circuits, and organismal behavior. Genetic tools allow the insertion of genes into cells that afterward respond to specific wavelengths of light. Subsequently, light can turn on or off specific signal cascades in cells and even trigger or inhibit the behavior of organisms.
\r\n\r\n\tThis book will illustrate optogenetics in all its dimensions, from historical perspectives to technological advances, as well as the use of optogenetic tools in health and disease, in various animal models and organisms. Targeted at students and researchers in biological, engineering, medical, and related disciplines, this book will provide an overview of the current work that is being done in this exciting, new field and will highlight any gaps and areas of optogenetics that would benefit from further exploration.
",isbn:"978-1-83969-377-9",printIsbn:"978-1-83969-376-2",pdfIsbn:"978-1-83969-378-6",doi:null,price:0,priceEur:0,priceUsd:0,slug:null,numberOfPages:0,isOpenForSubmission:!1,hash:"3ae7e24d8f03ff3932bceee4b8d3e727",bookSignature:"Dr. Thomas Heinbockel",publishedDate:null,coverURL:"https://cdn.intechopen.com/books/images_new/7921.jpg",keywords:"Monitoring Intracellular Chloride, Optogenetics in Insects, Genetically Encoded Calcium Indicators, Optogenetic Reporters, Channelrhodopsin, Optogenetics in Biomedical Engineering, Optogenetics in Visual Impairments, Light-Induced Neuron and Glia Cell Function, Neuronal Circuit Activation With Optogenetics, Silencing of Cellular Activity, Optical Control of Cell-Cell Interactions, Light Control Proteins",numberOfDownloads:null,numberOfWosCitations:0,numberOfCrossrefCitations:0,numberOfDimensionsCitations:0,numberOfTotalCitations:0,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"November 20th 2020",dateEndSecondStepPublish:"December 18th 2020",dateEndThirdStepPublish:"February 16th 2021",dateEndFourthStepPublish:"May 7th 2021",dateEndFifthStepPublish:"July 6th 2021",remainingDaysToSecondStep:"2 months",secondStepPassed:!0,currentStepOfPublishingProcess:4,editedByType:null,kuFlag:!1,biosketch:"Internationally trained and experienced researcher of novel areas in neuroscience, affiliated with Howard University College of Medicine, seasoned educator of health sciences students, with a strong background as a journal reviewer and book editor.",coeditorOneBiosketch:null,coeditorTwoBiosketch:null,coeditorThreeBiosketch:null,coeditorFourBiosketch:null,coeditorFiveBiosketch:null,editors:[{id:"70569",title:"Dr.",name:"Thomas",middleName:null,surname:"Heinbockel",slug:"thomas-heinbockel",fullName:"Thomas Heinbockel",profilePictureURL:"https://mts.intechopen.com/storage/users/70569/images/system/70569.jfif",biography:"Thomas Heinbockel, Ph.D., is a Professor and Interim Chair in the Department of Anatomy, Howard University College of Medicine, Washington, DC. Dr. Heinbockel’s laboratory engages in multidisciplinary research to elucidate organizational principles of neural systems in the brain, specifically the limbic and olfactory system. His research has been directed at understanding brain mechanisms of information processing and their relation to neurological and neuropsychiatric disorders. His laboratory also works on translational projects, specifically, the development of novel anti-epileptic drugs and pharmacotherapeutic treatment options for drug addiction. His laboratory analyzes drug actions at the epi- and genetic level using next-generation sequencing technology. The goal of his studies is to conduct innovative basic and applied research on fundamental biological mechanisms involved in disease conditions (Covid-19, HIV). Dr. Heinbockel studied biology at the Philipps-University, Marburg, Germany. His studies of the brain started during his M.S. thesis work at the Max-Planck-Institute for Behavioral Physiology, Starnberg/Seewiesen, Germany. Subsequently, he completed a Ph.D. in Neuroscience at the University of Arizona, Tucson, Arizona, USA. After graduating, he worked as a Research Associate at the Institute of Physiology, Otto-von-Guericke-University School of Medicine, Magdeburg, Germany. Prior to his arrival at Howard University, Dr. Heinbockel held joint research faculty appointments in the Department of Anatomy & Neurobiology and the Department of Physiology at the University of Maryland School of Medicine, Baltimore, Maryland, USA. He still maintains an adjunct appointment in these departments.",institutionString:"Howard University",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"10",totalChapterViews:"0",totalEditedBooks:"7",institution:{name:"Howard University",institutionURL:null,country:{name:"United States of America"}}}],coeditorOne:null,coeditorTwo:null,coeditorThree:null,coeditorFour:null,coeditorFive:null,topics:[{id:"6",title:"Biochemistry, Genetics and Molecular Biology",slug:"biochemistry-genetics-and-molecular-biology"}],chapters:null,productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"},personalPublishingAssistant:{id:"252211",firstName:"Sara",lastName:"Debeuc",middleName:null,title:"Ms.",imageUrl:"https://mts.intechopen.com/storage/users/252211/images/7239_n.png",email:"sara.d@intechopen.com",biography:"As an Author Service Manager my responsibilities include monitoring and facilitating all publishing activities for authors and editors. From chapter submission and review, to approval and revision, copyediting and design, until final publication, I work closely with authors and editors to ensure a simple and easy publishing process. I maintain constant and effective communication with authors, editors and reviewers, which allows for a level of personal support that enables contributors to fully commit and concentrate on the chapters they are writing, editing, or reviewing. I assist authors in the preparation of their full chapter submissions and track important deadlines and ensure they are met. I help to coordinate internal processes such as linguistic review, and monitor the technical aspects of the process. As an ASM I am also involved in the acquisition of editors. 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Csoka",coverURL:"https://cdn.intechopen.com/books/images_new/7480.jpg",editedByType:"Edited by",editors:[{id:"70569",title:"Dr.",name:"Thomas",surname:"Heinbockel",slug:"thomas-heinbockel",fullName:"Thomas Heinbockel"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"6694",title:"New Trends in Ion Exchange Studies",subtitle:null,isOpenForSubmission:!1,hash:"3de8c8b090fd8faa7c11ec5b387c486a",slug:"new-trends-in-ion-exchange-studies",bookSignature:"Selcan Karakuş",coverURL:"https://cdn.intechopen.com/books/images_new/6694.jpg",editedByType:"Edited by",editors:[{id:"206110",title:"Dr.",name:"Selcan",surname:"Karakuş",slug:"selcan-karakus",fullName:"Selcan Karakuş"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"1591",title:"Infrared Spectroscopy",subtitle:"Materials Science, Engineering and Technology",isOpenForSubmission:!1,hash:"99b4b7b71a8caeb693ed762b40b017f4",slug:"infrared-spectroscopy-materials-science-engineering-and-technology",bookSignature:"Theophile Theophanides",coverURL:"https://cdn.intechopen.com/books/images_new/1591.jpg",editedByType:"Edited by",editors:[{id:"37194",title:"Dr.",name:"Theophanides",surname:"Theophile",slug:"theophanides-theophile",fullName:"Theophanides Theophile"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"3092",title:"Anopheles mosquitoes",subtitle:"New insights into malaria vectors",isOpenForSubmission:!1,hash:"c9e622485316d5e296288bf24d2b0d64",slug:"anopheles-mosquitoes-new-insights-into-malaria-vectors",bookSignature:"Sylvie Manguin",coverURL:"https://cdn.intechopen.com/books/images_new/3092.jpg",editedByType:"Edited by",editors:[{id:"50017",title:"Prof.",name:"Sylvie",surname:"Manguin",slug:"sylvie-manguin",fullName:"Sylvie Manguin"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}}]},chapter:{item:{type:"chapter",id:"41489",title:"Metal-Oxide Nanowires for Gas Sensors",doi:"10.5772/54385",slug:"metal-oxide-nanowires-for-gas-sensors",body:'In past decades, gas sensors based on the metal oxide semiconductors (MOSs) have been studied in diverse field for wide applications. A gas sensor is a device that can be used to detect various gas such as ethanol, LPG, CO2 and CO gases etc. The gas sensors based on MOSs such as SnO2, TiO2, WO3, ZnO, Fe2O3, and In2O3 have an important role in environmental monitoring, chemical process controlling, personal safety (Q. Wan et al., 2004), industrial process controls, for the detection of toxic environmental pollutants in human health, and for the prevention of hazardous gas leaks, which comes from the manufacturing processes (K. Arshak&I. Gaidan, 2005), wine quality monitoring, and traffic safety (X.F. Song et al., 2009).
The first generation of MOS gas sensors were based on thick films of SnO2 since 1960s which was firstly reported by Taguchi (E. Comini et al., 2009). The MOS gas sensors have some advantages such as small size, low-power-consumption (E. Comoni et al., 2009), simple construction, good sensing properties (K. Arshak&I. Gaidan, 2005), and high compatibility with microelectronic processing (E. Comini et al., 2002). So, they have rapidly gained attention over the years.
Recently, various morphologies of MOS nanostrcutures such as wire-like, belt-like, rod-like, and tetrapods have been widely investigated for gas sensor applications. It is well-known that the sensitivity characteristics of these sensors strongly depend on the morphology of MOS. Especially, one-dimensional nanostructures such as nanowires, nanobelts, nanoneedles have gained a lot of interest for nanodevice design and fabrication (Wang et al., 2008). The sensors based on MOS nanowires are promising due to feasibility for ultrahigh sensitive sensors or ppb-level sensors. These nanowires can be prepared by various techniques such as pulse laser deposition (PLD), chemical vapor deposition (CVD), thermal evaporation, metal-catalyzed molecular beam epitaxy (CBE) and thermal oxidation technique. Moreover, there are many reports on gas sensor based on the nanowires.
The fundamental mechanism of gas sensing based on MOS depend on the reaction between the surface complexes such as O-, O2-, H+, and OH- reactive chemical species and the gas molecules (reducing/oxidizing gas) to be detected (E. Comini et al., 2009). Thus, it is important to understand the surface reactions between semiconductor surface and target gas for improving the sensing characteristics. Typically, the important parameters in sensor development are sensitivity, selectivity, and stability that called “3S” (E. Comini et al., 2009). However, in this chapter we will mostly discuss on only the sensitivity parameter.
The sensitivity of sensors based on bulk and thin film MOS is typically low. Thus, sensitivity improvement has been extensively studied by using several techniques. The two techniques that commonly used for sensitivity improvement are in the following:
Using nanostructures
The MOS sensors based on various nanostructures such as nanowires, nanobelts, nanoparticles, nanrods, and nanotubes etc. have been demonstrated to be excellent candidates for ultrahigh sensitivity due to their high surface-to-volume ratio. A large surface-to-volume ratio means that a significant fraction of atoms (or molecules) are much quantity on the surface. So, the reaction between target gas and reactive chemical species (O-, O2-, H+, and OH-) on the surface can extremely occur. A list of MOS sensors with the sensitivity for the different morphologies of ZnO nanostructures is summarized in Table 1. It can be seen that the sensor sensitivity strongly depends on size and morphology of ZnO nanostructures.
Adding noble metal\n\t\t\t\t\t
The noble metals such as Au, Pt, Pd, and Ag on the surface of MOSs can act as a catalyst to modify surface reactions of MOSs toward sensing gas and result in high sensitivity. The ZnO sensors with noble metal additive are also listed in Table 1.
Usually, the gas sensors based on MOS nanostructures exhibit high sensitivity and sometimes up to a few hundred folds over a conventional MOS sensor at a moderate concentration. On the other hand, the sensors based on a larger size of MOS such as in the form of thin film or micro-tetrapod shows lower sensitivity. Several models have been proposed to explain sensitivity characteristics of MOS sensors and still be a subject of discussion.
There are many reports about gas sensor model that are used to explain sensor response characteristics. Wang and co-workers have proposed a surface-depletion model and a contact-controlled model that are used to describe the sensing mechanism of resistance-type metal-oxide semiconductor sensors (Feng et al., 2005). The surface-depletion controlled model is used to explain the sensing mechanism of semiconducting oxide sensors based on nanocrystal/nanowire/nanobelt structures, while the contact-controlled model is proposed to explain the contact between the outer ends of the rods. This leads to the formation of many junctions in the sensors that significantly modify the potential barrier of contact between rods. These barriers can control the transport of electrons between the rods resulting in the change of the sensor resistance. Chen and co-workers (Chen et al., 2006) have used space-charge model to explain the sensitivity improvement when the grain size is close to or smaller than the Debye length (2Ld).
In this chapter, we investigate the sensing characteristics of the MOS nanowire sensors and present the sensitivity formulas that are developed in order to explain all circumstances of gas sensors based on MOS nanowires. The size and morphology dependences on the sensitivity are explained in terms of the two important parameters including surface-to-volume ratio and depletion layer width. The developed formulas will be discussed and related to the experimental sensing characteristics of ZnO sensors.
\n\t\t\t\tMaterials\n\t\t\t | \n\t\t\t\n\t\t\t\tMorphology\n\t\t\t | \n\t\t\t\n\t\t\t\tDiameter (nm)\n\t\t\t | \n\t\t\t\n\t\t\t\tTarget gas\n\t\t\t | \n\t\t\t\n\t\t\t\tSensitivity (ppm)\n\t\t\t | \n\t\t||||||||||
\n\t\t\t\t1\n\t\t\t | \n\t\t\t\n\t\t\t\t10\n\t\t\t | \n\t\t\t\n\t\t\t\t25\n\t\t\t | \n\t\t\t\n\t\t\t\t50\n\t\t\t | \n\t\t\t\n\t\t\t\t100\n\t\t\t | \n\t\t\t\n\t\t\t\t150\n\t\t\t | \n\t\t\t\n\t\t\t\t200\n\t\t\t | \n\t\t\t\n\t\t\t\t300\n\t\t\t | \n\t\t\t\n\t\t\t\t500\n\t\t\t | \n\t\t\t\n\t\t\t\t1000\n\t\t\t | \n\t\t\t\n\t\t\t\t2000\n\t\t\t | \n\t\t||||
ZnO (Son et al., 2008) | \n\t\t\tnanowire | \n\t\t\t20 | \n\t\t\tEthanol | \n\t\t\t~16 | \n\t\t\t\n\t\t\t | ~40 | \n\t\t\t~54 | \n\t\t\t~62 | \n\t\t\t~70 | \n\t\t\t~70 | \n\t\t\t\n\t\t\t | - | \n\t\t\t- | \n\t\t\t\n\t\t |
ZnO (Xu et al., 2008) | \n\t\t\tnanorod | \n\t\t\t40-80 | \n\t\t\tEthanol | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | 7.3 | \n\t\t\t- | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | - | \n\t\t\t- | \n\t\t\t\n\t\t |
ZnO (Chen et al., 2006) | \n\t\t\tnanorod | \n\t\t\t<15 | \n\t\t\tEthanol | \n\t\t\t\n\t\t\t | 20.5 | \n\t\t\t\n\t\t\t | 104.9 | \n\t\t\t176.8 | \n\t\t\t\n\t\t\t | 224.2 | \n\t\t\t\n\t\t\t | 267.7 | \n\t\t\t- | \n\t\t\t\n\t\t |
ZnO (Bie et al., 2007) | \n\t\t\tnanorod | \n\t\t\t10-30 | \n\t\t\tEthanol | \n\t\t\t\n\t\t\t | ~5 | \n\t\t\t\n\t\t\t | ~10 | \n\t\t\t18.29 | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | ~32 | \n\t\t\t~42 | \n\t\t\t\n\t\t |
ZnO (Li et al., 2009) | \n\t\t\tnanoneedle | \n\t\t\t5-10 | \n\t\t\tEthanol | \n\t\t\t11 | \n\t\t\t56 | \n\t\t\t\n\t\t\t | 116 | \n\t\t\t176 | \n\t\t\t\n\t\t\t | ~300 | \n\t\t\t\n\t\t\t | ~650 | \n\t\t\t- | \n\t\t\t\n\t\t |
ZnO (Wan et al., 2004) | \n\t\t\tnanowire | \n\t\t\t25 | \n\t\t\tEthanol | \n\t\t\t~2.5 | \n\t\t\t\n\t\t\t | ~8 | \n\t\t\t~16 | \n\t\t\t~33 | \n\t\t\t\n\t\t\t | ~47 | \n\t\t\t\n\t\t\t | - | \n\t\t\t- | \n\t\t\t\n\t\t |
ZnO (Feng et al., 2005) | \n\t\t\tflowerlike | \n\t\t\t150 | \n\t\t\tEthanol | \n\t\t\t2.2 | \n\t\t\t5.8 | \n\t\t\t\n\t\t\t | 11.4 | \n\t\t\t14.6 | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | 25.2 | \n\t\t\t30.1 | \n\t\t\t\n\t\t |
ZnO (Li et al., 2007) | \n\t\t\tnanorod | \n\t\t\t15 | \n\t\t\tEthanol | \n\t\t\t4.1 | \n\t\t\t10.7 | \n\t\t\t\n\t\t\t | 18.1 | \n\t\t\t29.7 | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | ~72 | \n\t\t\t100 | \n\t\t\t\n\t\t |
ZnO (Yang et al., 2008) | \n\t\t\tnanorod | \n\t\t\t50 | \n\t\t\tEthanol | \n\t\t\t10 | \n\t\t\t18 | \n\t\t\t\n\t\t\t | 60 | \n\t\t\t100 | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | - | \n\t\t\t- | \n\t\t\t\n\t\t |
ZnO (Chen et al., 2008) | \n\t\t\tnanotube | \n\t\t\t250 | \n\t\t\tEthanol | \n\t\t\t2.6 | \n\t\t\t\n\t\t\t | \n\t\t\t | - | \n\t\t\t24.1 | \n\t\t\t\n\t\t\t | 34.8 | \n\t\t\t\n\t\t\t | 59.3 | \n\t\t\t- | \n\t\t\t\n\t\t |
ZnO (Choopun et al., 2007) | \n\t\t\tnanobelt | \n\t\t\t50-150 | \n\t\t\tEthanol | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | 7.3 | \n\t\t\t\n\t\t\t | 12 | \n\t\t\t\n\t\t\t | \n\t\t\t | 21.1 | \n\t\t\t23.2 | \n\t\t\t\n\t\t |
ZnO (Hongsith et al., 2008) | \n\t\t\tnanowire | \n\t\t\t60-180 | \n\t\t\tEthanol | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | - | \n\t\t\t5.07 | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | 9.79 | \n\t\t\t14 | \n\t\t\t14 | \n\t\t
ZnO (Wongrat et al., 2009) | \n\t\t\tnanowire | \n\t\t\t100-500 | \n\t\t\tEthanol | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | 2 | \n\t\t\t3 | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | 5 | \n\t\t\t8 | \n\t\t\t\n\t\t |
SnO2 (Neri et al., 2006) | \n\t\t\tnanopowder | \n\t\t\t6-100 | \n\t\t\tEthanol | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | ~7 | \n\t\t\t~8.6 | \n\t\t\t~10 | \n\t\t\t\n\t\t\t | \n\t\t\t | - | \n\t\t\t- | \n\t\t\t\n\t\t |
SnO2 (Lee et al., 2008) | \n\t\t\tnanorod | \n\t\t\t<100 | \n\t\t\tEthanol | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | - | \n\t\t\t- | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | - | \n\t\t\t~40 | \n\t\t\t\n\t\t |
ZnO (Liu et al., 2010) | \n\t\t\tnanotube | \n\t\t\t200 | \n\t\t\tH2\n\t\t\t | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | - | \n\t\t\t2.3 | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | - | \n\t\t\t- | \n\t\t\t\n\t\t |
ZnO (Bie et al., 2007) | \n\t\t\tnanorod | \n\t\t\t10-30 | \n\t\t\tH2\n\t\t\t | \n\t\t\t\n\t\t\t | ~5 | \n\t\t\t\n\t\t\t | ~7 | \n\t\t\t10.41 | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | ~22 | \n\t\t\t~24 | \n\t\t\t\n\t\t |
SnO2 (Zhang et al., 2010) | \n\t\t\tnanofiber | \n\t\t\t80-120 | \n\t\t\tH2\n\t\t\t | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | ~2 | \n\t\t\t~5 | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | ~8 | \n\t\t\t~10 | \n\t\t\t\n\t\t |
SnO2 (Lee et al., 2008) | \n\t\t\tnanorod | \n\t\t\t<100 | \n\t\t\tH2\n\t\t\t | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | - | \n\t\t\t- | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | - | \n\t\t\t~10 | \n\t\t\t\n\t\t |
SnO2-Pd (Zhang et al., 2010) | \n\t\t\tnanofiber | \n\t\t\t80-120 | \n\t\t\tH2\n\t\t\t | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | ~5 | \n\t\t\t~8 | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | ~15 | \n\t\t\t~26 | \n\t\t\t\n\t\t |
SnO2-Pd (Lee et al., 2008) | \n\t\t\tnanorod | \n\t\t\t<100 | \n\t\t\tH2\n\t\t\t | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | ~33 | \n\t\t\t- | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | - | \n\t\t\t~700 | \n\t\t\t\n\t\t |
ZnO-Au (Hongsith et al., 2008) | \n\t\t\tnanowire | \n\t\t\t60-180 | \n\t\t\tEthanol | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | - | \n\t\t\t6 | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | 12 | \n\t\t\t24 | \n\t\t\t37 | \n\t\t
SnO2-Pt (Neri et al., 2006) | \n\t\t\tnanopowder | \n\t\t\t6-100 | \n\t\t\tEthanol | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | ~18 | \n\t\t\t26.5 | \n\t\t\t~31 | \n\t\t\t\n\t\t\t | \n\t\t\t | - | \n\t\t\t- | \n\t\t\t\n\t\t |
SnO2-Pd (Lee et al., 2008) | \n\t\t\tnanorod | \n\t\t\t<100 | \n\t\t\tEthanol | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | ~15 | \n\t\t\t- | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | - | \n\t\t\t~125 | \n\t\t\t\n\t\t |
ZnO-Au (Li et al., 2007) | \n\t\t\tnanorod | \n\t\t\t15 | \n\t\t\tEthanol | \n\t\t\t\n\t\t\t | 20.1 | \n\t\t\t\n\t\t\t | 41.8 | \n\t\t\t89.5 | \n\t\t\t\n\t\t\t | \n\t\t\t | 193.6 | \n\t\t\t- | \n\t\t\t- | \n\t\t\t\n\t\t |
ZnO-Au (Wongrat et al., 2009) | \n\t\t\tnanowire | \n\t\t\t100-500 | \n\t\t\tEthanol | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | 7 | \n\t\t\t10 | \n\t\t\t\n\t\t\t | \n\t\t\t | \n\t\t\t | 20 | \n\t\t\t32 | \n\t\t\t\n\t\t |
List of MOS sensors with the sensitivity for the different morphologies of ZnO nanostructures.
Normally, the gas sensor based on MOS has an optimum operating temperature at high temperature about 250-350°C. When the MOS is heated at lower temperature about 100-200°C, oxygen molecules in the atmosphere are adsorbed on its surface and form oxygen ion molecules by attracting an electron from the conduction band of MOS as shown in the Eq. (1).
At higher temperature, the oxygen ion molecules are dissociated into oxygen ion atoms with singly or doubly negative electric charges by attracting an electron again from the conduction band as shown in Eq. (2) and (3)
where kOxy is the reaction rate constant. The oxygen ions on the surface of MOS are extremely active with the target gas molecule and give up the electrons from the surface back to the conduction band of MOS. The generally chemical reaction between gas molecule and oxygen ions is shown in Eq. (4)\n\t\t\t
where
The chemical reaction causes change of the carrier concentration in the conductivity and thus, change of sensor resistance. The change of sensor resistance depends on a type of MOSs. A schematic diagram for change of the sensor resistance upon exposure to the target gas (reducing gas) in the cases of n-type and p-type MOS sensors is illustrated in Fig 1 and will be discussed in the following.
Since majority carriers in n-type MOSs are electron, the resistance of n-type MOS sensor decreases when the temperature increases due to their semiconducting properties. However under oxygen ambient, from Eq. (1)-(3), the electrons in the conduction band of n-type MOS are removed by the adsorbed oxygen ions. This causes a decrease of the carrier concentration and thus, an increase of resistance of n-type MOS sensor at operating temperature. When the n-type MOS sensor is under the target gas ambient (reducing gas), the electrons obtained from the chemical reaction as in Eq. (5) are given back to the conduction band leading to a decrease of the sensor resistance.
In another hand, the majority carriers in p-type MOSs are holes. Similar to n-type MOSs, the sensor resistance of p-type MOS decreases when the temperature increases. However, under oxygen ambient, p-type MOS generates holes when the oxygen ions are adsorbed on the surface via the excited electrons from valence band. This process results in raising the number of charge carriers, which leads to a decrease of the sensor resistance (opposite to n-type). When the p-type MOS sensor is under the target gas ambient (reducing gas), the electrons inject into the valence band and recombine with the holes and this method resulting in reducing the number of holes, which leads to an increase of the sensor resistance (opposite to n-type).
Schematic diagram for change of the sensor resistance upon exposure to the target gas (reducing gas) in the cases of n-type and p-type MOS sensors.
It should be noted that in the case of an oxidizing gas the change of resistance will be just opposite to the above discussions.
In addition, from Eq. (4), a rate equation of an electron density can be written as
where n is the electron density or the electron concentration under the gas atmosphere, and kgas is the reaction rate constant or reaction rate coefficient described as
where Ea is the activation energy of a reaction, kB is the Boltzmann constant and T is absolute temperature. By integrating Eq. (5) at an equilibrium state under gas ambient and air ambient and using the carrier concentration defined as n=α/R (where R is a resistance and α is a proportional constant), a sensitivity relation can be obtained as (Hongsith et. al, 2010)
Sometimes, a compact form of the sensitivity relation on gas concentration,
where a is a controllable parameter.
The sensitivity formula in Eq. (8) can be applied to explain very well in the case of thin film and bulk. In the case of nanostructure, however, two important parameters including surface-to-volume ratio and depletion layer width need to consider in order to explain the sensing characteristics.
Generally, this surface-to-volume ratio can be related to the density of the adsorbed oxygen ions. Thus, we have proposed that the density of adsorbed oxygen ions can be written in term of surface-to-volume ratio as
where σ0 is a number of oxygen ions per unit area, Φ is a ratio of surface area per volume of material Vm, and Vs is a system volume. By substituting Eq. (10) onto Eq. (8) gives
The Eq. (11) can be applied to explain very well in the case of sensors based on MOS nanowires. At the begining, it is quite amazed that sensors based on MOS nanowires exhibited the sensitivity higher than that of thin film or bulk even though the nanowires were not aligned along the conductive direction. For example, sensors based on thin films with perpendicular spike nanowires as shown in Fig.2 exhibit the sensitivity of higher than sensor based on thin film structure. The explanation of sensitivity enhancement is clear with using the Eq. (11) which is due to an increase of surface-to-volume ratio.
a) sensors based on thin film structrue and (b) based on thin films with perpendicular spike nanowires. The sensitivity enhancement of nanowire sensors can be explained by Eq. (11) which is due to an increase of surface-to-volume ratio.
The sensitivity ratio as a function of diameter where L = 10 μm of a gas sensor based on vertical alignment ZnO nanorods with diamerter D and length L and a gas sensor based on ZnO thin films with an area of 1 cm2.
From Eq. (11), the sensitivity strongly depends on the surface-to-volume ratio (Φ) as discussed earlier. For example, let consider a thin film with an area of 1 cm2 as shown in Fig. 2 (a). Then, given cylindrical nanostructures of 10 μm in length with various diameters are grown on this area, as shown in Fig. 2 (b). The surface-to-volume ratio can be calculated and put in Eq. (11) for the sensitivity ratio as
The sensitivity ratio as a function of diameter is plotted as shown in Fig. 3. It can be seen that the sensor sensitivity enhances as decreasing the diameter due to an increase of surface-to-volume ratio and rapidly enhances at small diameter.
Typically, the sensor resistance is contributed from two parts including the resistance along a cylindrical nanowire, and the resistance between nanowires. The resistance along the nanowire is due to surface depletion layer and conductive channel. The resistance between nanowires is due to band bending (potential barrier between wires) which depend on a size of nanostructure.
First, let consider for only the resistance along the nanowire by neglecting the resistance between nanowires. According to the depletion layer or the space charge model, Ld (Debye length), can be expressed by
where ε is a static dielectric constant, q is an electrical charge of a carrier, and n is a carrier concentration. It can be seen that at steady operating temperature, the Debye length depends only on the carrier concentration. Let consider in Eq. (13), at the optimum operating temperature based on pure or undoped MOS nanowire sensor, the Ld can be regarded as a constant value and equals to a value of the depletion layer width.
In this model, a cylinder, which is one of the most basic geometric shapes in one-dimension, is considered and a conductive channel is assumed to be along the axis of the cylinder. At an operating temperature, the oxygen ions are adsorbed by attaching an electron on the surface of the cylinder. Therefore, the depletion layer is formed on the surface of cylinder with a thickness of Ld, and then a size of conductive channel is reduced along the radial direction as shown in Fig. 4.
When exposed to the reducing gas atmosphere, gas reacts with oxygen ions on the surface and gives back electrons to MOS sensors resulting in increasing conductive channel (decreasing depletion layer width). The conductive channel can be related to the carrier concentration, and can be written in term of the depletion layer width (Ld) as
where n0 is a carrier concentration of a intrinsic material, n\' represents a carrier concentrationof the Debye length, and D is a diameter of the cylinder. Thus, the effect of the depletion layer on sensitivity based on cylindrical MOS nanowire are given by inserting Eq. (14) in Eq. (11) and obtained
Let compare a diameter of cylinder D to the Debye length (Ld). Since the Debye length is in the order of nanometer, it can be divided into three conditions.
Under condition D >> 2Ld, Eq. (15) turns in to Eq. (11)\n\t\t\t\t\t\t
In this condition, a diameter of cylinder is much larger than micrometer which is the case of microstructure or bulk materials. The depletion layer width is very small compared with the cylindrical diameter (D >> 2Ld) and Eq. (15) can be approximated to Eq. (11) which is an equation that has no depletion layer effect.
D> 2Ld, Eq. (15) can be approximated to Eq. (11)
When a diameter of cylinder is in the order of nanometer but still larger than Debye length (D > Ld), Eq. (15) again can be approximated to Eq. (11) with no depletion layer effect. However, the sensor sensitivity strongly depends on the oxygen ion density due to the surface-to-volume ratio, Φ, parameter.
D~2Ld, sensor sensitivity strongly depends on D
When a cylindrical diameter decreases down to the order of nanometer and is comparable to the Debye length (D ~ 2Ld), the depletion layer has strong effect and the sensor sensitivity is strongly dependent on a cylindrical diameter. Thus, Eq. (15) can be used to explain sensitivity of all structural size ranging from nanometer to bulk and can be regarded as a general form of sensitivity formula in order to explain the sensing characteristics.
Schematic diagram of the depletion layer on the surface of cylinder with a thickness (or width) of Ld, under condition of D>>2Ld, D>>2Ld, and D~2Ld (not in scale).
Second, let consider for a case that sensor resistance is contributed from both along nanowire and between nanowires. So, the sensor resistance is due to both effects of surface deletion layer and band bending (potential barrier). It should be noted that band bending has also effect on the surface depletion layer. Since the sensor resistance strongly depend on a size of nanowire, let compare a diameter of a cylindrical nanowire D with a depletion layer width (w). It can be divided into three cases.
Under\n\t\t\t\t\t\tD>>2w (large size)
In this case, the depletion layer width is much narrow compared to a diameter of the cylinder so the depletion layer has small effect on the electron density in the wires. However, it does greatly affect the potential barrier of the contacts between the wires. Thus, the sensor resistance is dominantly controlled by the potential barrier in this case.
From the oxygen adsorption reaction as given in Eq. (1)-(3) which oxygen ion specie is O2-, at equilibrium condition it can be deduced by using the mass action law that
where kOxy is an equilibrium constant of oxygen adsorption reaction which is defined as kOxy = ka/kd, whereka and kdis a reaction constant for oxygen adsorption and desorption
reactions, respectively.
where n0 is a density of donor electron, which is assumed to be constant throughout MOS and the relation between VB and w is shown as (Yamazoe & Shimanoe, 2008):
Here Ld is the Debye length defined by LD = (εkT/q2Nd)1/2, and β = q/kT, where k and T are Boltzmann constant and temperature, respectively. In addition, n0 is the density of conduction electrons and apparently is equal to the density of donors, nd. By using Eq. (18), we can rewrite it as (Yamazoe & Shimanoe, 2008):
Since the sensor resistance is dominantly controlled by the potential barrier in this case, the sensor resistance R, which is inversely proportional to the electron density is given as (Yamazoe & Shimanoe, 2008)
where R0 is a resistance under the flat band condition, m is the reduced depletion depth which is defined by m=w/Ld. Moreover, if there are no electron-trapping sites other than the adsorbed oxygen ion O2- on the surface, the depletion layer width (w) can be related to density of O2- per unit area
From Eq. (22), the larger depletion layer width results in higher density of O2- per unit area
nd is density of donor electron, which is assumed to be constant, w is the depletion layer width. From Eq. (23) (under D>>2w), it can be seen that the gas sensing mechanism is controlled by the potential barrier of the contact between wires. Furthermore, the potential barriers are independent of the cylinder size and therefore, the sensitivity is independent of the diameter of nanowire, D.
Under D>2w
In this case, the depletion layer has effect on both electron density in the wires and the potential barrier of the contacts between the wires. Thus, the sensor resistance is controlled by surface depletion layer and the potential barrier in this case.The conductance related to the nanowire after oxygen adsorption is given as:
where μ0 is the crystal electron mobility, l is the distance between electrodes. It can be seen that the gas-sensing mechanism depends on both the width and the height of the contact potential barriers (Sysoev et al., 2009, Rothschild&Komem, 2004). Thus, the sensor resistance due to surface depletion layer and potential barrier is represented by
From Eq. (12), (8) and using
From this equation, it can be seen that the sensor response depend not only on the potential barrier between wires but also on the size of nanowire.
Under D≤2w
In this case, the depletion layer has effect only on the electron density in the wires and can be regarded as fully depleted cylinders. The fully depleted cylinders are occurred when the Fermi level is totally controlled by surface states under nearly flat energy bands and so potential barrier can be neglected. Therefore, the sensor resistance is controlled only by the surface depletion in this case.
The MOS nanowires have been synthesized by thermal oxidation technique. This technique has been successfully used for synthesizing ZnO or CuO by simply heating pure Zn and Cu material source, respectively. The process is usually conducted in a cylindrical furnace. For the synthesis of ZnO nanowire as shown in Fig. 5, Zn thin films or thick films were screened or evaporated on alumina substrate. Then, they were sintered at temperature in ranging of 500-700ºC to form the nanostructure. For the synthesis of CuO nanowire, the commercial grade copper plate with thickness of 0.1 mm was cut and cleaned by alcohol in an ultrasonic bath for 2 min and dried at room temperature. The copper plate was loaded into a center of a tube furnace at 600°C at normal atmosphere for oxidation reaction.
Schematic diagram of the synthesis of ZnO nanowire on alumina substrate by thermal oxidation technique.
The sensors were fabricated by putting gold paste as inter-digital electrodes on the top of the sensors surface and putting a heater underneath the alumina substrate as shown in Fig 6. The heater for the sensor was made from nickel-chromium which could control temperature in the range 280-380 ºC. The operating temperature was measured by a thermocouple placed on the middle of the sensor.
Schematic diagram of the fabricated sensor structures.
A set up for the ethanol sensing characteristic measurement was shown in Fig. 7. The sensing response and recovery characteristics of MOS sensors were studied in a gas flow chamber under a dynamic equilibrium. Electrical measurements were performed using a volt-amperometric technique. A constant bias voltage of 5 V was applied to the sensor. Another voltage was applied to the heater coil used for heating the sensor and maintaining at a desired operating temperature. A thermocouple was employed to monitor the sensor temperature. The ammeter, voltmeter, and thermocouple signals were monitored and recorded via an interfaced personal computer. The ethanol sensing properties of the device were observed by the resistance change under an ethanol vapor atmosphere at different operating temperatures. Since our goal was to apply as an alcohol breath analyzer, the ethanol vapor at various concentrations was generated from ethanol solutions using alcohol simulator (GUTH Laboratories, Inc., Harrisburg, PA). The function of this alcohol simulator was to simulate alcohol concentration at conditions similar to exhaled human breath, being varied for ethanol concentration of 50–1,000 ppm for this experiment. A set up for the ethanol sensing characteristic measurement was illustrated in Fig. 7. The sensor sensitivity is defined by the ratio of the electrical resistance of the sensor in air and the electrical resistance of the sensor in ethanol vapor.
Schematic diagram of a set up for the ethanol sensing characteristic measurement.
For the synthesis of ZnO nanowires, it was found that the nanowires exhibit the belt-like or wire-like structures with sharp tip. The diameter and length were in the range of 100-500 nm and 2-7 μm, respectively. For the synthesis of CuO nanowires, the nanowires having a diameter of 100–400 nm and the length of around several micrometers were observed. The different morphologies of ZnO and CuO nanowires were shown in Fig 8. It can be seen that Fig 8 (a) and (b) were for the thick film morphologies. No nanowires were observed in this case representing as the bulk case. Fig 8 (d) and (f) were for vertical aligned and non-vertical aligned ZnO nanowires, respectively. The vertical aligned ZnO nanowires were prepared by zinc screening technique but non-vertical alignment of ZnO nanowires were prepared by zinc evaporation technique. And finally Fig 8 (g) was for the CuO nanowires (Raksa et al., 2005).
FE-SEM images of bulk ZnO (a, b), ZnO nanowires (c-f), and CuO nanowires (g).
The resistance response and recovery characteristics of ZnO and CuO gas sensor that exposed to ethanol concentration in range of 50-1,000 ppm at the optimum operating are shown in Fig. 9 (a) and (b), respectively. At the beginning, the measured resistance is steady in air atmosphere and then, the resistance of ZnO sensor drops sharply in ethanol atmosphere and recovers to the initial value after removing ethanol vapor. While the resistance of CuO sensor rapidly rises in ethanol atmosphere and falls back after removing ethanol. The decrease and increase of resistance under the ethanol atmosphere is due to the n-type and p-type conducting of ZnO and CuO, respectively as discussed earlier.
The sensitivity of ZnO sensors with different sizes and morphologies at different ethanol concentration are summarized in Table 2. The sensitivity of sensor is defined as Ra/Rg (reverse for CuO case) when Ra was the resistance of sensor in air and Rg was the steady resistance of sensor in ethanol. The sensor sensitivity strongly depends on size and morphology of the sensors. This size and morphology dependence will be discussed in a later section.
The response and recovery curve of n-type and p-type MOS sensor for ZnO nanowires (a) and CuO nanowires (Raksa et al., 2005) (b), respectively.
\n\t\t\t\t\n\t\t\t\t\tMorphology\n\t\t\t\t\n\t\t\t | \n\t\t\t\n\t\t\t\t\n\t\t\t\t\tDiameter (nm)\n\t\t\t\t\n\t\t\t | \n\t\t\tSensitivity(50 ppm) | \n\t\t\tSensitivity(100 ppm) | \n\t\t\tSensitivity(500 ppm) | \n\t\t\tSensitivity(1000 ppm) | \n\t\t
\n\t\t\t\t\n\t\t\t\t\tbulk\n\t\t\t\t\n\t\t\t | \n\t\t\t- | \n\t\t\t1.3 | \n\t\t\t1.6 | \n\t\t\t2.0 | \n\t\t\t2.2 | \n\t\t
\n\t\t\t\t\n\t\t\t\t\tNanowire (screening)\n\t\t\t\t\n\t\t\t | \n\t\t\t100-500 | \n\t\t\t3.1 | \n\t\t\t3.9 | \n\t\t\t6.4 | \n\t\t\t8.7 | \n\t\t
\n\t\t\t\tNanowire(evaporation)\n\t\t\t | \n\t\t\t11-104 | \n\t\t\t17 | \n\t\t\t24 | \n\t\t\t30 | \n\t\t\t40 | \n\t\t
Sensor sensitivity of sensor with different ZnO sizes and morphologies.
Sometimes, a compact form of the sensitivity relation on gas concentration can be rewritten as
where a is a controllable parameter and X is a concentration of gas. At the optimum operating temperature condition, the relation between the sensitivity and gas concentration can be rewritten as:
It can be seen that log(Sg-1) has a linear relation with log X having a slope of b value. Thus, b value which represents oxygen ion species on the surface of MOS sensors can be obtained from a slope of a plot between log(Sg-1) and log X.The value of the constant b is normally around either 0.5or 1, depending on the charge state of the surface ion. The adsorbed oxygen ion is O2-for b of 0.5, the adsorbed oxygen ion is O¯ for b of 1.
The plots between log (Sg-1) and log Χ of some works as listed in Table 1 was displayed in Fig 10. It was found that the value b of all sensors is close to 0.5 suggesting that the adsorbed surface oxygen species on ZnO sensor is O2-. In addition, this suggests that the oxygen adsorption species on the surface is independent on the size and morphology of ZnO regardless of bulk, microstructure or nanostructure.
Plot of sensor response (Sg-1) and ethanol concentration in log scale for ethanol sensor based on different ZnO morphologies. The linear line in the graph has a slope of 0.5.
In the section 2 we have explained the sensing formula for n-type and p-type MOS sensor. In this section, we will explain the sensing parameters for understanding in the mechanism of resistance change under air atmosphere and gas atmosphere and will discuss in term of the size and morphology dependence on the sensor sensitivity.
Sensor sensitivity for different ZnO sizes and morphologies with ethanol concentration of 1,000 ppm.
Let consider a sensitivity of MOS gas sensor based on the different sizes and morphologies as seen in Fig. 11, it can be divided into three cases of MOS ethanol gas sensor.
From Table 2, the sensitivity of a bulk ZnO sensor shows the lowest value compare with that of nanostructures. It can be simply explained by using Eq. (8). The sensing parameter of the surface-to-volume ratio is low for the bulk sensor and thus, the oxygen ion surface density is low resulting in low sensitivity.
From Table 2, it can be seen that the sensitivity of MOS sensor based on vertical aligned nanowires (zinc screening nanowires) is higher than that of bulk. The sensitivity is 8.7 for vertical aligned nanowires sensor at 1,000 ppm of ethanol compared to that of about 2 for bulk ZnO gas sensor. The higher sensitivity of MOS sensor based on vertical aligned nanowires can be explained in terms of surface-to-volume ratio parameter (Φ) by using Eq. (11) or (15). Since Φ is proportional to sensitivity, the larger Φ due to nanostructure gives the higher sensitivity for the case of vertical aligned nanowires even though the nanowires are not aligned along the conducting direction.
It can be seen in Table 2 that the sensitivity of MOS sensor based on non-vertical aligned nanowires (zinc evaporation nanowires) is even higher than that of zinc screening nanowires (the sensitivity increases from 8.7 to 40). This is due to the combination effects of the surface-to-volume ratio and the depletion layer and can be explained by using Eq. (15). The non-vertical aligned nanowires exhibit smaller diameter (11-104 nm) indicating higher surface-to-volume ratio. Also, the diameter of nanowires is comparable to the depletion layer width (two times of Debye length; about 10 nm for ZnO) indicating strong effect of the depletion layer. Thus, the surface-to-volume ratio parameters (Φ) increases and the difference between diameter and the depletion layer width (D-2Ld) decreases resulting in the increase of the sensor sensitivity as indicated in Eq. (15).
In addition, the sensor sensitivity can be further enhanced up to several folds by using adding novel metal technique.There have been several reports on sensitivity enhancement due to metal doping or metal adding effect. We have also reported on the sensitivity enhancement due to gold nanoparticles (AuNPs) on the surface of ZnO (Wongrat et al., 2012).As shown in Fig 12, the sensitivity of ZnO:AuNPs exhibits maximum value of 478 at ethanol concentration of 1,000 ppm while the sensitivity of pure ZnO nanostructure sensor is about 40.
Ultra high sensitivity of ZnO sensor withAuNPs on the surface at ethanol concentration of 1,000 ppm (Wongrat et al., 2012).
The metal adding effect can be simply explained in our model by using Eq. (15), (17) and (26). It can be seen that the sensitivity is proportional to the reaction rate constant, kgas and kOxy, through the oxygen density. Basically, the reaction rate constant can be affected by noble metals (such as Au, Pd, Pt etc.) in MOS sensors due to the catalytic effect. Thus, metal adding causes an increasing of reaction rate constant and resulting in enhancement of the sensor sensitivity.
The evidence for having higher kgas can be observed from the sensor resistance in the ethanol ambient. The sensor resistance under ethanol ambient of ZnO:AuNPs sensor is about 200 kΩ which is less than of pure ZnO nanostructure sensor(500 kΩ) suggesting higher kgas. In addition, the evidence for having higher kOxy, can be observed from the sensor resistance in air. The highest resistance in air of ZnO:AuNPs sensor is about 100 MΩ which is more than of resistance of pure ZnO nanostructure sensor (20 MΩ).The increase of resistance in air suggests that the gold metal catalytically activates the dissociation of molecular oxygen due to higher reaction rate that results in increasing an amount of the oxygen adsorption molecules. Therefore, electrons in ZnO nanowire are captured by oxygen adsorption to form oxygen ion and hence ZnO nanowire loses more electrons and causes the larger depletion layer at ZnO surface resulting in higher resistance.
Therefore, the sensitivity enhancement of ZnO sensors with noble metal is due to catalytic effect in both ethanol adsorption reaction kgas and oxygen adsorption reaction kOxy through the oxygen density. In the other words, the ultra-high sensitivity of ZnO sensors with noble metal can be explained by an increase of both parameters of kgas and w (depletion layer width) as described in Eq. (26).
The MOS nanostructures, especially nanowires have been demonstrated to be an excellent candidate as a gas sensing device. The gas sensors based on MOS nanowires are promising due to feasibility for ultrahigh sensitive sensors or ppb-level sensors. The simple and low-cost technique of thermal oxidation technique is effectively used to prepare the MOSs nanowires. The sensing characteristics of the MOS sensors strongly depend on sizes and morphologies of ZnO nanostructures. The sensitivity formulas have been developed in order to explain all circumstances of gas sensors based on MOS nanowires. The size and morphology dependences on the sensitivity have been explained in terms of the two important parameters including surface-to-volume ratio and depletion layer width. The experimental sensing characteristics of ZnO sensors are in good accordance to the developed formulas. This suggests that the sensing formulas are a powerful tool in sensor design and also can be applied for sensors based on other MOSs such as SnO2, TiO2, MoO3 or WO3, etc. In addition, the sensor sensitivity can be further enhanced up to several folds by using adding novel metal technique and can be simply used the developed sensitivity formula for explanation in term of the depletion layer parameter.
k Reaction rate
Χ Density, Concentration, of X
n, n0 Electron carrier density
Γ Time constant
Ra Resistance in air
Rg Resistance in active gas
Sg Sensitivity
Φ Surface to volume ratio
σ, σ0 Oxygen ion surface density
Vm Volume of material
Vs Volume of system
Cg Ethanol concentration
Ld Debye length
ε Static dielectric constant
q Electrical charge of carrier
kB Boltzmann constant
T Temperature (K)
Hydatid disease is a worldwide parasitic infection created by larval phase of Echinococcus [1]. Human infection is frequently seen in Europe, Middle East, some places of Canada, Russia, Japan, China, Australia and New Zealand [2].
In the life period, E. granulosus stands in the small bowel of its definitive host; carnivores, which are generally dogs and wolves [3]. Then, eggs passed into the feces are ingested with the intermediate host, which is generally sheep [4]. Larval stage occurs in the intermediate host; i.e., ingested eggs outgrows in the small intestine and lets out oncosphere, which invades the intestinal mucosa and come in the lungs, liver or other organs (metacestode larvae). Eggs can survive up to 1 year in the environment. On the next step, definitive host digests the infected organs of the intermediate host. Protoscolices invades the intestinal mucosa and grow up to adult worms [3]. Human being can be more commonly infected by indirect ingestion of contaminated water and food or directly from contact with dogs [4].
Fluid filled cyst is covered with three layers; pericyst, ectocyst and endocyst [5]. Pericyst is created by the protective reaction of the host tissue; the middle laminated layer called ectocyst lets for the transition of nutrients and the germinal layer inside called endocyst generates cyst fluid, blood capsules, scolices and also provides the constitution of ectocyst [5, 6]. Many daughter vesicles remain in the hydatid cysts [6].
Liver is the most commonly affected organ, second one is the lung. Other organs are less commonly affected. Heart is rarely affected, but it’s fatal if it’s affected. Left ventricule is more commonly affected than the right ventricle possibly due to its richer blood supply. Additionally, huger myocardial mass in left ventricle supplies better circumstances for parasite’s growth. Hydatid cysts of left ventricle are generally located in the subepicardium. Rupture into the pericardial space is seldom. However, habitation in the right ventricle is subendocardial, rupture is more common which results with anaphylaxis, pulmonary embolisation and death [7].
Most common way for myocardial invasion is coronary circulation. Second most common route is pulmonary venous drainage with the rupture of pulmonary cysts. Heart may also be involved with direct contact [7].
Hydatid disease has an evolutionary period; first, cysts grow slowly; then, a differentiation period starts which the parasite dies and forms calcified, solidified cyst behind [7].
The lungs are the most common organ in pediatric patients and the second most common organ for adults. Due to the negative pressure inside the lungs, cysts grow three times faster compared to the growth in the liver [6].
E. granulosus has a broad genetic diversity. Molecular gene analysis has defined 10 genotypes, which are aggregated into four different types: E. granulosus sensu strict [G1-G3 complex], Echinococcus equinus [G4], Echinococcus ortleppi [G5] and Echinococcus canadensis [G6-G10 complex]. G1 genotype of E. granulosus is reported to infect humans more frequently compared to other subtypes. Genotyping of human CE can help to plan the controlling methods for human hydatidosis. Genetic subtyping also clarifies the diversity in development, antigenicity and response to chemotherapeutic agents [3].
The disease is asymptomatic in the inception and can remain asymptomatic for long years even though the cysts become very huge [1]. For symptomatic patients, symptoms appertain to localization of the cyst. Cough, dyspnea or chest pain can be seen if the cysts are in the lung. Abdominal pain, hepatomegaly, sensibility, fever and icterus are the symptoms for liver cysts. With the rupture of the cyst due to the surgical intervention to the cyst or mechanical trauma, patients are prone to go into anaphylactic shock [1]. Cyst rupture can realise throughout the bronchus and patients can present with cough and sputum with hydatid sand and membrane fragments. If the cyst rupture realises throughout the pleural cavity, patients can present with pneumothorax, effusion and emphysema [6]. If the cyst rupture through vena cava, patient can present with recurrent pulmonary embolism [6].
Cysts and cyst like hypodense lesions carry diagnostic debate on computed tomography (CT) in some cases. Tumors with cystic degeneration, inauspicious lesions like necrotic lung cancer, metastases and infections like tuberculosis can imitate hydatid cyst [8].
Diagnosis is quite elementary for hydatid cyst (HC) if typical findings like crescent sign, onion peel, combo sign or folded membranes are present. However, atypical findings like solid or more hypodense semblance of ruptured, collapsed or infected cysts are more complicated as they resemble infections like tuberculosis or neoplastic lesions. MRI may help for diagnosis in these conditions [8]. Ultrasound can help to diagnose peripheral lesions and to achieve pleura [6].
Imaging tools for hydatid disease are computed tomography (CT), ultrasonography (USG), magnetic resonance imaging (MRI), radiography and urography.
Radiograph is the primary method for imaging in bone and lung disease. An uncomplicated hydatid cyst looks like a well-limited homogenous radio-opacity on chest X-ray (Figure 1A). Cysts quietly resemble carom balls in posteroanterior X-ray and to rugger balls in lateral X-ray [6]. Cysts may look like a strange shaped mass due to pressure of mediastinum, bronchovascular components. Multiple large cysts are also pathognomonic for echinococcosis (Figure 1B) [1]. Cysts can present with bilobed appearance due to nicking inside the cysts [6]. The loss of a round shape with a small depressed view points out bronchial rupture, so called “slit sign”.
(A) Posteroanterior view of chest X-ray presenting uncomplicated hydatid cyst of left lower lung and (B) posteroanterior view of chest X-ray presenting multiple, large, circular and well limited masses in both hemithoraces.
Atelectatic and reactive reactions can result with the loss of well limited borders, thus imitating carcinoma or pneumonia [6].
A radiolucent frame may be seen with the entry of air between pericyst and endocyst due to disruption of bronchus, so called “crescent sign” (Figure 2). This sign is not pathognomonic for hydatid cysts and may also be seen in carcinoma, blood clots, mycetoma, and Rasmussen aneurysm. If the entry of air increases, endocyst minimizes and ruptures; an air fluid level is observed in the endocyst, so-called “double curve sign”. The natant membranes in the cyst fluid compose “water-lily sign” if there is furthermore collapse of the endocyst. Daughter cysts may look like circular radio-opacities at deep part of the cysts, so-called “rising sun” image. Pericyst can become empty if the membranes are extracted with cough, air-filled cysts can be seen on X-ray, so-called “dry cyst sign”. In cases of infection added to the disorder, lung abscess can be imitated (Figure 3).
(A) Chest X-ray showing pulmonary meniscus sign (arrow) indicating crescent shaped containment of air and (B) chest X-ray presenting a well limited lesion (arrow) in the right lower lobe of the lung with air fluid level, indicating a superimposed infection.
(A) Abdominal X-ray showing round calcified mass in the right hypochondrium and (B) chest radiograph showing hydatid cyst in the liver.
X-rays for abdomen may present with hepatomegaly, elevation of right hemidiaphragm and cyst wall calcification. During healing period of the cyst, all the structures in the cyst calcify and plain radiograph presents a dense calcified mass [5].
Cysts don’t always present classical signs above. Obstacles about diagnosis can be overlapped with the help of CT in required cases [6]. CT is a significant diagnostic tool in detecting cyst wall or septal calcification, osseous lesions, cystic component localized posterior to calcification, evaluating complications and in cases which USG is not enough (abdominal wall deformities, excessive bowel gases, obesity and previous surgery) [4].
US is easily accessible and lacks radiation. It’s sensitivity is about 100% acquiring it the priority as a screening method for abdominal hydatidosis. USG and MRI are both successful to show hydatid sand, daughter cysts, natant membranes and vesicles inside the cyst (Figure 4) [1, 4].
Transverse ultrasound of the retroperitoneum showing unilocular anechoic cyst (type CL according to WHO classification).
Mobile hydatid sand which points out to the splitted capsules and scolices that moves in the cyst cavity may be presented in a “snowstorm” appearance (Figure 5). Most commonly used classifications related to sonographic appearance are classifications of Gharbi et al. (Table 2) and the World Health Organisation Informal Working Group classification on echinococcosis (WHO-IWGE) (Table 3) [5].
Longitudinal ultrasound of a liver hydatid cyst in a 8 years old girl presenting the “snowstorm appearance”.
Gharbi type 1 is the most common subtype and it’s presented as a pure cystic lesion with or without the entity of hydatid sand (Figures 4 and 5). Gharbi type II cysts grows out after trauma, cyst degeneration, host response or drug therapy. Decrease in the intracystic pressure results with splitting of the endocyst and pericyst; natant membranes may be seen in the cyst cavity. Complete splitting of the membranes is called as “water-lily” sign due to its morphological appearance (Figure 6). Gharbi type III cysts are multivesicular cysts which septae presenting the neighbour borders of daughter cysts composes a “honeycomb” image (Figure 7). “Spoke wheel” appearance may be seen when daughter cysts are splitted with hydatid matrix. Gharbi type IV cysts are composed of an internal echogenic matrix giving them a solid appearance (Figure 8). For differential diagnosis, daughter cysts or membranes should be searched to externalize a solid mass. Gharbi type V cysts involve wall calcification and dense distal acoustic shadowing (Figure 9). A densely calcified cyst can be supposed to be dead. However, a partially calcified cyst should still be regarded as an alive cyst [5].
Ultrasonographic view of Gharbi type II hydatid cysts: (A) “Split wall” sign from splitting of pericyst and endocyst and (B) “water-lily” sign resulting from complete splitting of the membranes.
Transverse ultrasound of Gharbi type III hydatid cyst of liver multiple daughter cysts in an echogenic matrix results in a “honeycomb” image.
Ultrasonographic appearance of Gharbi type IV hydatid cyst of the liver.
Ultrasonographic appearance of Gharbi type V hydatid cyst.
Imaging findings for hydatid cyst differentiate from cystic lesions to solid appearing lesions. The cyst may look like a well identified fluid accumulation. There may be the appearance of natant membranes due to cleavage of endocyst from pericyst. Ring like calcification of the cyst can lead to complete calcification during differentiation of the cyst [2].
Specific findings of imaging are visualization of daughter cysts, calcification of the cyst wall and membrane detachment. Diagnosis in early stage is hard [1].
Appearance of hydatid disease may be classified into four subtypes.
Type I is simple cyst with no internal tectonic. On ultrasound, type 1 hydatid cysts seem as well identified unilocular anechoic lesions (Figure 10). On CT, they seem as fluid accumulated lesions. MRI demonstrates a fluid accumulated cystic lesion with a T1 isointense and T2 hypointense peripheral border (rim sign) enclosing the homogenous high signal cyst ingredients [2].
Type 1 hydatid cyst: (A) axial contrast CT image of a 15 years old female presents a well identified fluid accumulated simple cystic lesion in the liver and (B) oblique sonogram in a 45 years old male demonstrates type 1 hydatid cyst in the liver.
Type II hydatid cysts are cysts with daughter cysts and matrix. They include cleaved natant membranes or daughter cysts (Figure 11). Attenuation of the daughter cyst is hypodense/hypointense to maternal matrix on CT and MRI, respectively. If there are multiple cysts, they are covered with a single capsule presenting with a “truckle spoke” appearance [2].
Type 2 hydatid cyst: (A) contrast enhanced computed tomography demonstrates multiple daughter cysts with irregular borders covering almost all of the volume of the mother cyst-so called “rosette appearance” and (B) oblique ultrasonogram in a 39 years old male demonstrates type 2 hydatid cyst.
Type II HC are classified to three subtypes according to the age, quantity and setting of the daughter cysts.
Type IIa contain involve daughter cysts organized at the periphery.
Type IIb involve bigger daughter cysts with irregular borders that covers almost all of the capacity of the mother cyst.
Type IIc contains high attenuation round or oval masses with sprinkled calcifications and daughter cysts, demonstrating attrition of the old cyst.
Type III cysts are dead calcified cysts (Figure 12).
Type 3 hydatid cyst: (A) contrast enhanced computed tomography presents type 3 hydatid cyst in the right lobe of the liver and (B) oblique ultrasonogram shows anechoic lesion with membranes floating on the cyst fluid.
Type IV hydatid cysts are complicated cysts (Figure 13). Most common complications of echinococcosis are rupture and superinfection. Degeneration of parasitic membranes causes the rupture of the cyst (Figures 14–18).
Type 4 hydatid cyst: (A) sagittal contrast enhanced CT images of thorax show ruptured type 4 hydatid cyst in the lower lobe of the right lung with wrinkled floating endocyst-so called “lily sign” and (B) oblique ultrasonogram shows type 4 hydatid cyst.
Various secondary complications possibly happen according to site of rupture in the body. Secondary complications of echinococcosis according to different locations are listed in Table 1.
Gharbi et al. classification of hydatid cysts related to ultrasonographic features [5].
Gharbi et al. preferred classification for differentiation of subtypes of hydatid cysts on ultrasonogram of the liver (Table 1) [5].
Another global classification used for sonographic imaging of hydatid cysts wad presented by World Health Organization Informal Working Group (Table 2) [5].
Types of hydatid cysts observed on ultrasound examination of liver [5].
MRI is better to show cyst wall defect, biliary and neurological involvement. Cysts are hyperintense on T2W images and are covered by a low signal frame possibly because of the collagen rich pericyst [1]. If available, daughter cysts are hypointense compared to the intracystic fluid on T1 weighted imaging and hyperintense on T2-weighted images [5]. DW MRI makes the differentiation of CE1 hydatid cysts from other simple cysts with their hyperintense image. Apparent diffusion coefficient (ADC) of the hydatid cyst is lower compared to ADC of simple cyst because of internal viscous contents [1]. Also, ADC values of simple cysts and type I to III hydatid cysts are higher than ADC values of abscesses because diffusion of protons throughout thin fluid is limited. ADC values of type IV hydatid cysts and abscesses present no considerable statistical difference [5].
MRI demonstrates the degree of cyst degeneration with secession of the wall, collapsed membranes are observed as bent linear compositions inside the cyst. Wall calcification is demonstrated better on MRI compared to CT, besides MRI is more successful than CT to represent irregularities of borders that points out inchoative segregation of membranes [5].
MRI is also better to differentiate liver hydatid cysts from other simple cysts [4] (Figures 14–18).
MRI showing hydatid cyst in the liver of a 45 years old male: (A) coronal T1 weighted image, (B) coronal T2 weighted scan and (C) axial T2 weighted scan.
(A) Axial T2 weighted MRI showing splenic hydatid cyst and (B) coronal T2 weighted scan of hydatid disease in L4-5 vertebra.
MRI showing hydatid cyst in the lower pole of the kidney: (A) coronal T1 weighted scan and (B) axial T2 weighted scan.
MRI showing hydatid cyst in the cyst hydatid in the mesosalpinx adjacent to the left ovary: (A) axial T2 weighted image and (B) coronal T2 weighted image.
In cardiac cystic echinococcosis, trans-thoracic echocardiography, CT and MRI can demonstrate the cystic structure of the lesion and it’s correlation with the cardiac chamber [8] (Figure 18).
Case of cardiac cyst hydatid: (A) computed tomographic image, (B) magnetic resonance imaging of transverse section, and (C) magnetic resonance imaging of longitudinal section showing daughter cysts.
ERCP and MRCP show cystobiliary relationship, daughter vesicles & germinative membranes of cysts in bile ducts, dilated bile ducts. However, because of high intracystic pressure, communication of cyst with bile ducts can’t be shown via ERCP& MRCP effectively [1].
Complications like rupture into the peritoneal cavity, biliary cavity and the pleura are presented in Figure 19. Incidence and location specific complications of hydatid disease is presented in Table 3 [2].
(A) CT image of rupture of hydatid cyst in the lung, (B) CT scan of intrabiliary rupture of hydatid cyst. (C) CT scan showing intraperitoneal cyst rupture with diffuse peritoneal effusion.
Frequency and location specific complications of hydatid disease [2].
Echinococcosis is a disorder of larval incursion by echinococcus tapeworm, prevalent in various continents in the world. Lungs and liver are the most commonly affected organs. Imaging has a significant role to implement the right treatment techniques. US is easily accessible and lacks radiation. MRI, CT and ERCP are also used for complicated cases.
No contribution by any other author or no funding declared.
The authors declare no conflict of interest.
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