State of homogeneity of dispersed hc-SWCNTs and SWCNTs with crystal defects.
\r\n\tReduction of inefficiencies, cost, and environmental impact are the main topics of energy engineering. Improving the individual technologies becomes more challenging from year to year as thermodynamic inefficiencies approach unavoidable levels. The chapters to be presented in the book aim to cover a wide range of: processes from low-temperature processes associated with air separation of liquefaction of gases to the high-temperature processes of combustion; from micro thermodynamic processes associated with the structure of materials to the macro thermodynamic processes associated with complex energy-conversion and chemical energy-intensive plants; application of new concepts such energy analysis; combination of thermodynamics and environmental sciences, and many other interdisciplinary concepts including modern applied thermodynamics; evaluation criteria based on the availability of primary energy resources, the efficiency of available energy technologies, as well as their economic and environmental methods to ensure that the scientifically-based evaluation and optimization methods are adequate and comprehensive.
",isbn:null,printIsbn:null,pdfIsbn:null,doi:null,price:0,priceEur:null,priceUsd:null,slug:null,numberOfPages:0,isOpenForSubmission:!1,hash:"a8122d2875513b75741cacfd07cf65fb",bookSignature:"Prof. Tatiana Morosuk",publishedDate:null,coverURL:"https://cdn.intechopen.com/books/images_new/8365.jpg",keywords:"Applied Thermodynamics, Energy Resources, Energy Analysis, Entropy Analysis, Exergy Analysis, Energy Engineering, Energy-Conversion System, Economic Analysis, Ecological Analysis, Optimization",numberOfDownloads:null,numberOfWosCitations:0,numberOfCrossrefCitations:0,numberOfDimensionsCitations:null,numberOfTotalCitations:null,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"May 28th 2018",dateEndSecondStepPublish:"June 18th 2018",dateEndThirdStepPublish:"August 17th 2018",dateEndFourthStepPublish:"November 5th 2018",dateEndFifthStepPublish:"January 4th 2019",remainingDaysToSecondStep:"3 years",secondStepPassed:!0,currentStepOfPublishingProcess:5,editedByType:null,kuFlag:!1,biosketch:null,coeditorOneBiosketch:null,coeditorTwoBiosketch:null,coeditorThreeBiosketch:null,coeditorFourBiosketch:null,coeditorFiveBiosketch:null,editors:[{id:"193888",title:"Prof.",name:"Tatiana",middleName:null,surname:"Morosuk",slug:"tatiana-morosuk",fullName:"Tatiana Morosuk",profilePictureURL:"https://mts.intechopen.com/storage/users/193888/images/system/193888.jpeg",biography:"Professor Tatiana Morosuk (Tetyana Morozyuk) is the Head of the Department “Energy-Based Methods for Refrigeration Systems” at the Technische Universität Berlin, Germany. She studied refrigeration engineering in the Odessa State Academy of Refrigeration, Ukraine, and received her diploma in 1990. She received her Ph.D. in 1994 and Professorship in 2001, all in the Ukraine.\nProfessor Morosuk has over twenty years teaching experience in the fields of refrigeration, energy engineering, and applied thermodynamics. She is associated with several scientific organizations as well as many international energy-related conferences and recognized international journals. She serves as an associate editor for the following international journals: “International Journal of Energy and Environmental Engineering” (Springer), “International Journal of Natural Gas Science and Engineering” (Elsevier), “International Journal of Energy Research” (Wiley), “Energies” (MDPI), “Entropy” (MDPI), and “Journal of Energy Resources Technology” (ASME).\nProfessor Morosuk’s areas of scientific activities include the application of energy-based methods to the improvement of the thermodynamic, economic, environmental performance of different power generation systems, refrigeration/cryogenic systems and chemical plants. Particular attention is given to hydrogen economy, systems associated with the liquefaction of natural gas and the regasification of LNG, alternative refrigeration processes for sustainable industrial and commercial applications, and smart energy supply and use in industrial parks, including innovative concepts of liquid air energy storage. She is the author or co-author of 7 books and 12 book chapters as well as more than 300 publications and 10 patents. Fourteen Ph.D. theses and more than 100 master theses have been successfully completed under her supervision/co-supervision. Prof. Morosuk has vast administrative experience being the study dean of four international master’s programs in Germany, and the Head of the Energy Engineering Department at TU Berlin Campus El Gouna. Tatiana Morosuk is professor of Technische Universität Berlin, Germany. She studied refrigeration engineering in the Odessa State Academy of Refrigeration (Diploma in 1990), Ph.D. in 1994 and Professorship in 2001, all in Ukraine. The main objective of her research is to increase the sustainability of energy conversion systems from the thermodynamic, economic and ecological viewpoints. These activities in research and teaching cover a wide range of applications from power plants to refrigeration/cryogenic processes, and energy-intensive chemical plants. This includes smart energy supply and use in industrial parks, implementation of renewable energy, and innovative concepts of CO2 technologies. She is the author/co-author of 7 books and approximately 400 publications. Professor Morosuk is the director of the Institute for Energy Engineering at TU Berlin and the study dean of the four international master programs.",institutionString:"Technical University of Berlin",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"4",totalChapterViews:"0",totalEditedBooks:"1",institution:{name:"Technical University of Berlin",institutionURL:null,country:{name:"Germany"}}}],coeditorOne:null,coeditorTwo:null,coeditorThree:null,coeditorFour:null,coeditorFive:null,topics:[{id:"11",title:"Engineering",slug:"engineering"}],chapters:null,productType:{id:"1",title:"Edited Volume",chapterContentType:"chapter",authoredCaption:"Edited by"},personalPublishingAssistant:{id:"194667",firstName:"Marijana",lastName:"Francetic",middleName:null,title:"Ms.",imageUrl:"https://mts.intechopen.com/storage/users/194667/images/4752_n.jpg",email:"marijana@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. Whether that be identifying an exceptional author and proposing an editorship collaboration, or contacting researchers who would like the opportunity to work with IntechOpen, I establish and help manage author and editor acquisition and contact."}},relatedBooks:[{type:"book",id:"8394",title:"Low-temperature Technologies",subtitle:null,isOpenForSubmission:!1,hash:"be68d10255b1c1c72aef7caddf946e34",slug:"low-temperature-technologies",bookSignature:"Tatiana Morosuk and Muhammad Sultan",coverURL:"https://cdn.intechopen.com/books/images_new/8394.jpg",editedByType:"Edited by",editors:[{id:"193888",title:"Prof.",name:"Tatiana",surname:"Morosuk",slug:"tatiana-morosuk",fullName:"Tatiana Morosuk"}],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"}},{type:"book",id:"3161",title:"Frontiers in Guided Wave Optics and Optoelectronics",subtitle:null,isOpenForSubmission:!1,hash:"deb44e9c99f82bbce1083abea743146c",slug:"frontiers-in-guided-wave-optics-and-optoelectronics",bookSignature:"Bishnu Pal",coverURL:"https://cdn.intechopen.com/books/images_new/3161.jpg",editedByType:"Edited by",editors:[{id:"4782",title:"Prof.",name:"Bishnu",surname:"Pal",slug:"bishnu-pal",fullName:"Bishnu Pal"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"72",title:"Ionic Liquids",subtitle:"Theory, Properties, New Approaches",isOpenForSubmission:!1,hash:"d94ffa3cfa10505e3b1d676d46fcd3f5",slug:"ionic-liquids-theory-properties-new-approaches",bookSignature:"Alexander Kokorin",coverURL:"https://cdn.intechopen.com/books/images_new/72.jpg",editedByType:"Edited by",editors:[{id:"19816",title:"Prof.",name:"Alexander",surname:"Kokorin",slug:"alexander-kokorin",fullName:"Alexander Kokorin"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"1373",title:"Ionic Liquids",subtitle:"Applications and Perspectives",isOpenForSubmission:!1,hash:"5e9ae5ae9167cde4b344e499a792c41c",slug:"ionic-liquids-applications-and-perspectives",bookSignature:"Alexander Kokorin",coverURL:"https://cdn.intechopen.com/books/images_new/1373.jpg",editedByType:"Edited by",editors:[{id:"19816",title:"Prof.",name:"Alexander",surname:"Kokorin",slug:"alexander-kokorin",fullName:"Alexander Kokorin"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"57",title:"Physics and Applications of Graphene",subtitle:"Experiments",isOpenForSubmission:!1,hash:"0e6622a71cf4f02f45bfdd5691e1189a",slug:"physics-and-applications-of-graphene-experiments",bookSignature:"Sergey Mikhailov",coverURL:"https://cdn.intechopen.com/books/images_new/57.jpg",editedByType:"Edited by",editors:[{id:"16042",title:"Dr.",name:"Sergey",surname:"Mikhailov",slug:"sergey-mikhailov",fullName:"Sergey Mikhailov"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"371",title:"Abiotic Stress in Plants",subtitle:"Mechanisms and Adaptations",isOpenForSubmission:!1,hash:"588466f487e307619849d72389178a74",slug:"abiotic-stress-in-plants-mechanisms-and-adaptations",bookSignature:"Arun Shanker and B. Venkateswarlu",coverURL:"https://cdn.intechopen.com/books/images_new/371.jpg",editedByType:"Edited by",editors:[{id:"58592",title:"Dr.",name:"Arun",surname:"Shanker",slug:"arun-shanker",fullName:"Arun Shanker"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"878",title:"Phytochemicals",subtitle:"A Global Perspective of Their Role in Nutrition and Health",isOpenForSubmission:!1,hash:"ec77671f63975ef2d16192897deb6835",slug:"phytochemicals-a-global-perspective-of-their-role-in-nutrition-and-health",bookSignature:"Venketeshwer Rao",coverURL:"https://cdn.intechopen.com/books/images_new/878.jpg",editedByType:"Edited by",editors:[{id:"82663",title:"Dr.",name:"Venketeshwer",surname:"Rao",slug:"venketeshwer-rao",fullName:"Venketeshwer Rao"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"4816",title:"Face Recognition",subtitle:null,isOpenForSubmission:!1,hash:"146063b5359146b7718ea86bad47c8eb",slug:"face_recognition",bookSignature:"Kresimir Delac and Mislav Grgic",coverURL:"https://cdn.intechopen.com/books/images_new/4816.jpg",editedByType:"Edited by",editors:[{id:"528",title:"Dr.",name:"Kresimir",surname:"Delac",slug:"kresimir-delac",fullName:"Kresimir Delac"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}}]},chapter:{item:{type:"chapter",id:"65995",title:"Conductive Effect of Increased Crystallinity of Single-Walled Carbon Nanotubes as Field Emitter",doi:"10.5772/intechopen.84854",slug:"conductive-effect-of-increased-crystallinity-of-single-walled-carbon-nanotubes-as-field-emitter",body:'In the development regime of electronic devices, carbon nanotubes (CNTs) are expected to represent a promising material because of their unique physicochemical properties—nanoscale needle shape, high chemical stability, thermal conductivity, and mechanical strength—which represent advantages for the fabrication of field emitters. The utilization of single-walled CNTs (SWCNTs) relies on their electronic properties because they can be either metallic or semimetallic, depending on the geometry of how a graphene sheet is rolled into a tube (i.e., diameter and chiral angle) [1, 2, 3]. This controllability is considered to be effective for developing electronic devices based on SWCNTs [3, 4, 5]. SWCNTs also exhibit one-dimensional confinement effects and can be used as coherent quantum wires [6, 7, 8], and the Young’s modulus of SWCNTs is especially high when compared to that of other CNTs [9]. Owing to these properties, SWCNTs have been used in a wide range of applications including field emitters [10], probes in scanning microscopes [11], gas-storage materials [12], and electrode materials for secondary batteries [13], and they have been studied in a wide range of applied research fields.
However, synthesized CNTs, including SWCNTs, have crystal defects in the carbon network, and the unstable physicochemical properties make it difficult to use CNTs in electronic devices which require high reliability. Tohji et al. improved the purity and crystallinity of SWCNTs synthesized by arc discharge, and they succeeded in obtaining highly pure SWCNTs [14]. Together with Iwata and coworkers, they established a method to analyze, with high resolution, the crystallinity of highly crystalline SWCNTs (hc-SWCNTs) [15]. Based on these developments, a process for synthesizing hc-CNTs has been gradually established; however, a technique to control the crystallinity of hc-SWCNTs has yet to be demonstrated.
The application of hc-SWCNTs as field emitters is industrially promising and is approaching practical utilization. We have carried out basic research to develop field-emission (FE) devices using hc-SWCNTs [16] and succeeded, for the first time in recorded history, in employing SWCNT field emitters as the cathode of a planar lighting device [17]. These results suggest that hc-SWCNTs will be indispensable for decreasing the driving voltage for FE, increasing the emission lifetime, and improving the homogeneity of planar emission of planar lighting devices [17].
In the chapter reported here, the effect of the increased crystallinity of SWCNTs on their electrical properties was examined by comparing hc-SWCNTs and SWCNTs with crystal defects. In addition, field emitters were prepared from these SWCNTs, and the effects of the increased crystallinity of hc-SWCNTs on their electrical conductivity and FE current fluctuations were theoretically analyzed by determining their FE properties.
The Fowler-Nordheim (F-N) tunneling model shown in Figure 1 is an electron tunneling model represented by Eq. (1). The F-N tunneling model is valid only when electrons in the field emitter are passing into an energy barrier quantum mechanically. We assume that electrons emit from SWCNTs to the outside in case of the FE model discussed in this chapter, and we constructed an FE model including F-N tunneling model by combining the model of inelastic and elastic tunneling electrons passing through the inside of SWCNTs to the outside.
Schematic diagram of Fowler-Nordheim (F-N) tunneling.
In the quantum electron-tunneling model, the states of the electrons before and after tunneling through an energy barrier can be estimated by considering the energy transfer. According to Laks and Mills [18], the current density
where
When an electron exists in a sphere Ω,
When
When
where e is the electric charge. The quantum-mechanical tunneling-current operator
where Tkq is the tunneling matrix element between state k of an electron in the SWCNT and state q of an electron in the vacuum through a tunneling energy barrier, and
where m* is the effective mass of the electron in the tunneling barrier, and
In Eqs. (8) and (9),
By substituting Eqs. (6)–(9) into Eq. (11), we can finally obtain the following expression for the power spectrum of the field-emission current fluctuations:
where A is the area of the field-emission site of the SWCNTs on a cathode, and m is the effective mass of the electron that moves parallel to the emission site in the source electrode from which tunneling electrons are injected into the barrier.
Ballistic electrons are considered to pass through CNTs without crystal defects. However, when electrons pass through CNTs with crystal defects, the ballistic property is lost; an energy barrier is believed to inhibit the conduction of these electrons. In accordance with the works of Fransen et al. [22] and Nilsson et al. [23] on the electron tunneling model, we adopted an inelastic tunneling model through an energy barrier having a rectangular waveform.
In the inelastic tunneling model, the energy states of electrons passing through an energy barrier can be estimated by the energy transfer before and after electron tunneling. The power spectrum with the flow of FE current for the inelastic tunneling model was proposed by Kirtley et al. [24], Bardeen [25], and Watanabe et al. [26] based on Eqs. (12) and (13):
where ρ(E) is the state density of electrons in one-dimensional space, and nih (h = l (for left region) or r (for right region)) is the occupation number of electrons within state i (i = k or q).
We attempted to obtain the direct-current (DC) component of the power spectrum of the inelastic electron tunneling model using a rectangular potential barrier and Eq. (13). As mentioned above, the electrons passing through the CNTs without crystal defects are ballistic [5]. The CNTs with crystal defects are reported to have an energy bandgap that depends on the position of the defects, and electrons rarely pass through CNTs without energy loss. In order to analyze the electrical conductivity of SWCNTs, we attempted to obtain the tunneling matrix Mkq and the power spectrum of inelastic electron tunneling when electrons inelastically pass through the local area corresponding to crystal defects. The conductivity of electrons passing into SWCNTs with crystal defects was explained employing the electron tunneling model below.
For Mkq of an energy barrier having a rectangular waveform, the state of wave function transfers that in the right region (r) to the left region (l) of the energy barrier or vice versa, φrq is the wave function having wavenumber q localized in the right region of the barrier called as wave-B, and φlk is the wave function having wavenumber k localized in the left region of the barrier called as wave-A. The Fermi level of an SWCNT is represented by EF. When electrons pass through the rectangular potential barrier from the left region to the right region, the wave function shifts from state k to state q, and the tunneling matrix Mkq is given by:
where V(z) is the potential height of the energy barrier having a rectangular distribution on the z axis shown in Figure 2, and m is the effective mass of an electron.
Image of a rectangular energy barrier having a potential height V(z).
The wave functions φk and φq localized in the left region (wave-A) and in the right region (wave-B) are represented by:
where S is the area in which electrons pass through an SWCNT; and k||, q||, and x|| are the components, along the direction perpendicular to the z axis, of the wavenumber k, wavenumber q, and position x, respectively. The wave functions χk and χq have coefficients An, Bn and Cn, Dn, respectively, and are defined as:
The energy transfer between waves-A and -B, ħω, is included with the wavenumber in Eq. (16), and it corresponds to the energy loss of an electron passing through the energy barrier from the left region to the right region:
Using Eqs. (16) and (17), Mkq can be rewritten as:
The power spectrum of inelastic electron tunneling, |Iin(ω)|2, is obtained from Eqs. (13)–(18). The power spectrum at ω = 0 represents the magnitude of the direct current of the power spectrum |Iin(ω)|2.
The thickness of the rectangular energy barrier and the energy transfer which means the energy difference between the left region and the right region are important factors in this simulation. Results of research on tunnel junction devices indicate that the thickness of the rectangular potential barrier for inelastic electron tunneling is only ∼3 nm [20]. The energy loss caused by the tunneling of electrons through the energy barrier depends on the bandgap associated with the crystal defects [27]. The theoretical value of difference in the energy between waves A and B is calculated by fitting to be 0.027 eV, which corresponds to a temperature of 313 K for the energy loss observed when the electrons pass through SWCNTs with crystal defects.
Eq. (12) should be transformed into a more suitable form for a field-emission cathode using metallic SWCNTs. Field-emission measurements were carried out in the F-N tunneling regime, and a further simplified form is expressed as follows:
where
where
Original model of field emission using an SWCNT emitter in F-N tunneling.
In this study, the SWCNTs synthesized by arc discharge were annealed at a high temperature of approximately 1200 K in a low pressure of 10−6 Pa to obtain hc-SWCNTs. Figure 4 shows transmission electron microscope (TEM) images of the SWCNTs before and after annealing. As shown in Figure 4(a), we could find that the crystallinity of the SWCNTs after annealing was significantly improved.
TEM images with annealed and unannealed SWCNTs: (a) annealed hc-SWCNTs; (b) nonannealed SWCNTs with crystal defects.
The SWCNTs obtained before and after annealing were dispersed in a liquid medium with solvent including, to control the viscosity of the solution, surfactant and an ITO precursor solution, to prepare a coating film. The agitated mixture was sprayed on a silicon substrate to form an ITO film and sintered at approximately 700 K in a vacuum to remove any components in the organic solvents. In addition, to facilitate FE, the ITO film with SWCNTs was scratched with a thin needle to activate the film [16].
A diode structure fixed to the distance of 1.2 mm between a cathode of the ITO film having SWCNTs and an anode of a phosphor plate was prepared for the FE measurements; Figure 5 shows a schematic of the FE-measurement system.
Schematic diagram of the FE-measurement system with a diode structure.
The sample was set in a vacuum chamber of approx. 10−4 Pa. A supplied voltage with a frequency of 60 Hz was applied across the cathode and the anode to measure the FE characteristics.
Tunneling electron microscopy and scanning electron microscopy were used to obtain images of the dispersed hc-SWCNT bundles and the ITO film which was subjected to activation treatment. As one can clearly see in the TEM image in Figure 6(a), the hc-SWCNT bundles were well dispersed in the liquid medium. Meanwhile, the SWCNT bundles shown in the SEM image in Figure 6(b) were exposed in the scratched grooves on the activated ITO film and marked within the white circles; the dispersed SWCNTs in a scratched area are also illustrated with the red circles indicating the ends of the SWCNT bundles on the right. The number of dispersed and exposed SWCNTs per unit area could be controlled via the density of the SWCNTs. Table 1 shows the summary of the state of the exposed SWCNTs in terms of (1) the number of SWCNTs protruding from the grooved walls of the scratched ITO film per unit area, (2) the mean diameter of the exposed SWCNT bundles, and (3) the mean distance between neighboring SWCNT bundles for two types of SWCNTs, i.e., SWCNTs with crystal defects and hc-SWCNTs. The states of exposure of the two types of SWCNTs fabricated by our wet-coating process were similar, and they were homogeneously dispersed in the films.
(a) TEM image of dispersed hc-SWCNT bundles. (b) Left: SEM image of scratched ITO film having SWCNTs, where the white circles show the SWCNT bundles protruding from the grooved walls of the ITO film; right: schematic diagram of scratched area including dispersed SWCNTs, where the red circles show the tops of the exposed SWCNTs in the scratched area.
hc-SWCNTs | SWCNTs with crystal defects | |
---|---|---|
Number of SWCNTs exposed at grooved walls of ITO film after activation | Approx. 21 per 100 × 100 μm2 | Approx. 26 |
Average diameter of bundled SWCNTs (nm) | Approx. 9 | Approx. 10 |
Average distance between neighboring bundled SWCNTs (μm) | Approx. 27 | Approx. 21 |
State of homogeneity of dispersed hc-SWCNTs and SWCNTs with crystal defects.
Figure 7 shows the relationship between the current density and electric field for the SWCNTs, obtained using the system for FE measurements (Figure 5). The threshold field decreased from 2.01 V μm−1 for the SWCNTs with crystal defects to 1.07 V μm−1 for the hc-SWCNTs. As shown in Table 1, the dispersion density of SWCNTs and the mean diameter of SWCNT bundles in the films were similar for the two types of the SWCNTs. It means that the probability densities of SWCNTs that induced FE were similar for the two types of SWCNTs. Therefore, it can be discussed and assumed that the above improvement in electrical properties was caused by the increase in crystallinity of the SWCNTs.
Semilog plot of current density versus electric field for hc-SWCNTs and SWCNTs with crystal defects.
Figure 8 shows the distribution of bright spots in the hc-SWCNTs and SWCNTs with crystal defects. As can be seen in Figure 7, the threshold and the driving field depended on the crystallinity of the SWCNTs. When the applied field was controlled so that the current density was uniform, the densities of the high- and low-brightness spots on the measured area were almost the same between the hc-SWCNTs and the SWCNTs with crystal defects, respectively. Previous reports showed that in the SWCNTs synthesized by arc discharge, SWCNTs with metallic and semiconductive properties coexisted [31]. Therefore, the high-brightness spots can be attributed to the FE from metallic SWCNTs, and the low-brightness spots can be attributed to the FE from semiconductive SWCNTs; these phenomena and their origins are not discussed in this chapter. When the crystallinity of SWCNTs increased, the chirality of the carbon sheets making up the SWCNTs did not change, and the mixed ratio of metallic to semiconductive SWCNTs remained unchanged [32, 33, 34, 35, 36, 37].
Homogeneity of emission sites homogeneity in (a) hc-SWCNTs and (b) SWCNTs with crystal defects. The panels on the left show planar lighting, and the enlarged view of the circled regions in the panels on the right show the distribution of spots of cathodes employing hc-SWCNTs and SWCNTs with crystal defects.
The results in Figure 6 and Table 1 indicate that the diameter, protruded length, and dispersion density of the SWCNT bundles protruding from the grooved ITO film were similar for the two types of the SWCNTs as FE electron sources. However, the difference in the plots of current density versus electric field of Figure 7 is impossible to be analyzed only by the exposed uniformity of the dispersed SWCNTs on the activated ITO film. Therefore, we surmised that the difference in the crystallinity of SWCNTs caused the difference in electric properties of SWCNTs. Fransen et al. and Nilsson et al. find that the interruption of carbon network of an SWCNT with crystal defects originates a local energy band that affects the electrical conductivity by scanning tunneling microscopy (STM) [22, 23]. On the basis of the above results, an electric-physical model in an SWCNT was developed from the inelastic electron tunneling model. Therefore, the energy difference originated by the energy bandgap yielding from the interruption of carbon network in an SWCNT with crystal defects is surmised to become an energy barrier which impedes the electrons pass through the SWCNT.
Figure 9 shows the FE properties obtained by experiment in Figure 7 and simulation. For the hc-SWCNTs, the results obtained by the experiment are represented by red circles and those obtained by simulation using Eq. (12) at ω = 0 of the F-N tunneling model without inelastic tunneling model are represented by the yellow dashed line. Moreover, the experimental results of the SWCNTs with crystal defects are represented by blue circles and those obtained by the following method are represented by the dark-red dashed line. We can find the fitting between experiment and simulation is in good agreement. The simulation results represented by the dark-red dashed line were obtained by combining the F-N tunneling model of electrons emitted from the end of the SWCNT with the power spectrum with inelastic tunneling model given by Eqs. (7)–(12) at ω = 0. Table 2 shows the summary of the parameters employed in the theoretical calculations on the basis of F-N tunneling and inelastic electron tunneling. The total electron emission site area (α) and the field-enhancement factor (β) for FE are important parameters in evaluating the FE characteristics. These two parameters were the same for the two types of the SWCNTs.
Fitting of simulation results to experimental current density-electrical field characteristics.
hc-SWCNTs | SWCNTs with crystal defects | |
---|---|---|
Electron-emission site (α) | 1.95 × 10−9 | |
Field-enhancement factor (β) | 259,500 | |
Effective mass of electron (m) | 1.00m0 (m0 = 9.11 × 10−31 kg) | |
Thickness of rectangular inelastic barrier | — | 2.9 nm |
Energy bandgap after passing into the barrier | — | 0.148 eV |
Energy difference between wave A and wave B | — | 0.025 eV |
Homogeneity of dispersed hc-SWCNTs and SWCNTs with crystal defects.
The inelastic electron tunneling through the SWCNTs with crystal defects, as shown in Figure 10, is a phenomenon based on the energy loss associated with the electron transfer in the SWCNTs. Although many researchers have reported that CNTs exhibit ballistic electrical conductivity, such property has not been demonstrated in any experiment that we know of. We can express successfully the first report of the development using an inelastic electron tunneling model for an SWCNT with crystal defects based on the evaluation of FE properties. The hc-SWCNTs are suitable materials for electronic devices to save energy because the energy loss associated with electron transfer in the SWCNT is suppressed.
Schematic of field-emission property of SWCNTs with crystal defects modeled as convoluted FN-tunneling with inelastic tunneling.
Figure 11 shows the relationship between the current density and electric field for the SWCNTs obtained using the FE-measurement system shown in Figure 5. The threshold field of the metallic SWCNTs was 4.1 V μm−1 at a line-current density of 0.1 mA cm−2, as shown in Figure 11. Moreover, the planar lighting observed at 2 mA cm−2 was homogeneous, as shown in the inset in Figure 11.
Current density-electric field characteristics of metallic SWCNTs; the inset shows the case of planar emission.
Figure 12(a) shows the stability of the FE current of metallic SWCNTs when different values of DC voltage were supplied for 50 s; Figure 12(b) shows the power spectrum of the frequency based on the FE current fluctuations by Fourier transform calculation. The current density obtained from the sample biased using the DC power supply was measured as 1.2 mA cm−2 at 6 kV, 2.0 mA cm−2 at 6.6 kV, 4.6 mA cm−2 at 7.1 kV, and 10 mA cm−2 at 7.6 kV. The FE current fluctuations were observed to be stable owing to the desorption of gases from the SWCNT surface caused by annealing before the FE measurements. Some damped current distributions in the FE current were expected if the annealing of the sample was insufficient. However, Figure 12(a) shows no damping, and the SWCNT surfaces were expected to be clean for the FE measurements. The spectrum of each FE current in Figure 12(a) is normalized by the peak at 0 Hz, and it indicates that periodic fluctuations were recorded. A peak appears at 50 Hz, as shown in Figure 12(b), and it originated from the noise of the DC power supply, which represents the frequency of the commercial power supply in the eastern region in Japan. It can be seen that the stable DC current had alternating values, especially in the low-frequency domain of <100 Hz. Moreover, the spectrum distribution depends on the FE current, and the contents of each spectrum increased with the DC power.
(a) FE current fluctuations and (b) power spectra of FE-current fluctuations obtained by Fourier transform.
When the experimental results and the theoretical predictions explained in the previous theoretical section are compared, the parameters that determined the tunneling characteristics of the metallic hc-SWCNTs used as field emitters are listed in Table 3. The enhanced field E in Eq. (20) was determined from the surface potential calculations with an SWCNT model. The area of the field-emission site, A, at the SWCNT surface was calculated from the analysis that determined the FE properties. Each SWCNT model protruded from the ITO wall, which included the minimum area for calculating the electric field using the surface-charge method. The potential parameter ϕB was estimated as the work function value of bulk carbon.
e (elementary charge) | 1.60 × 10−19 C |
A (area of field-emission site) | 6.48 × 10−24 m2 |
ϕB (work function of bulk carbon) | 4.3 eV |
6.58 × 10−16 eV s | |
β (enhancement factor) | 2.56 × 103 |
m (free electron mass) | 9.11 × 10−31 kg |
Parameters used in the theoretical calculations.
A and β were obtained from the simulation reported in Ref. [28].
The power spectrum |I(ω)|2 obtained from Eq. (19) simplified by the WKB approximation shows the dependence of the applied field on a cathode using hc-SWCNTs, as shown in Figure 13. Each calculated spectrum was normalized, and it can be seen that |I(ω)|2 increased with the applied voltage at low frequency. For the metallic hc-SWCNTs, the experimental results are shown in Figure 12, and those obtained by simulation are shown in Figure 13; the two sets of results are in good agreement. From the above comment, the experimental results could be fitted well by the composition of the inelastic tunneling model and the F-N tunneling model employing the power spectrum of current fluctuation represented by Eq. (19). These results shown in Figures 12 and 13 indicate that the electrons passing into a barrier in the F-N model exhibited the electron flow fluctuation in the inelastic tunneling model, and the shape of the power spectrum depended on the increased component of current fluctuation obtained from FE.
Power spectrum obtained by simulation showing the dependence on applied voltage; E0 represents the original supplied electric field between the cathode and anode.
Field emission using metallic SWCNTs was modeled as a phenomenon based on inelastic electron tunneling, and the calculated power spectra are shown in Figure 13. Although many researchers have reported that field emitters exhibit F-N tunneling with elastic electrical conductivity, the phenomenon has not been demonstrated in any reported experimental work. This chapter presents successfully the first report of the development of an inelastic electron-tunneling model with WKB approximation for SWCNTs from the FE properties. Moreover, the FE current from electron sources like SWCNTs contains time-depended fluctuations, and the I-V characteristics of the FE electron sources were expressed as the power spectrum at ω = 0, which gives the magnitude of the current originating from the electrons passing through the SWCNTs, in accordance with the inelastic electron-tunneling model.
In this chapter, the author explained the conductive model of electrons flowing in the vicinity of a crystal defect that acts as a rectangular energy barrier based on inelastic electron tunneling model and the current fluctuation model for FE with hc-SWCNTs employing the F-N tunneling phenomenon.
The author could succeed in developing a model of the flow of electrons through the inside of an SWCNT to the outside using the fluctuations of the tunneling current. The electron flow model for an SWCNT with crystal defects was obtained by combining the F-N tunneling model with the power spectrum obtained using the tunneling matrix. From the previous mentioned comment, we could give a brief explanation of the effect of the increased crystallinity of SWCNTs on their electrical conductivity and describe the development of an electron flow model through the crystal defects of an SWCNT. Therefore, we expect that the hc-SWCNTs are used as field emitters with stable emission and low power consumption for saving energy.
The author kindly appreciates to support and give helpful discussions and suggestions by DOWA Holdings Co. Ltd., Japan.
Given the impact of invasive species on native biodiversity, it is important to increase the knowledge about factors influencing invasion processes to establish conservation and restoration strategies [1, 2, 3]. Invasion by exotic plant species has been related to biotic (native vegetation and herbivory) as well as abiotic (e.g. climate and soil) factors [3, 4, 5, 6, 7]. Among biotic factors, native vegetation has received more attention. Native vegetation may negatively affect invasion of exotic plants through competitive interactions as native species use resources that exotic species also require (space, light, nutrients, etc.) [2, 7, 8]. However, positive effects and facilitation of native species on exotic plants have also been observed [9]. Amelioration of abiotic stress by native vegetation may facilitate recruitment and/or establishment of exotic species, especially under more stressful conditions [10, 11, 12]. As a consequence of these negative or positive interactions, different relationships between native vegetation variables, such as species richness and cover, and invasibility may be expected. For instance, richer communities should reduce niche opportunities for establishing exotic species and hence resist invasion better than poorer communities, and in this case, a negative relationship between native and exotic richness may be expected [2, 7, 13, 14]. This pattern should occur in the absence of covarying extrinsic biotic or abiotic factors [15], which would mainly occur at small spatial scales or within community types [7]. Instead, positive relationships between exotic and native species richness should occur when competition is less important than facilitation [16, 17] or when both, native and exotic species, respond similarly to external environmental factors, which would mainly occur in large spatial scales often including different communities and climates [7]. Empirical evidence shows different results: negative and positive as well as absence of significant relationships have been documented [18, 19, 20, 21, 22, 23, 24, 25, 26] although negative relationships have mainly been observed in local scales while positive relationships at larger spatial scales.
Similarly, reductions in native species cover (e.g. by disturbance) would increase plant invasion through depletion of competitive interactions [13, 27]. Many studies have documented that more disturbed habitats, where cover of native plants has been eliminated or strongly reduced, present higher plant invasion [4, 5, 18, 19, 20, 25, 28, 29, 30, 31]. Nonetheless, it is less clear if within forest habitats, sites with lower cover of native species (e.g. triggered by some natural or anthropogenic disturbance) but without complete elimination of the forest canopy are related to an increase in plant invasion. Alternatively, when facilitative interactions are stronger than competition, positive associations between native and exotic species are more frequent [11], and positive relationships between native species cover and plant invasion may be expected. Moreover, some studies have recently documented invasion in closed-canopy forests by some shade-tolerant exotic plant species [32], and hence for some of these exotic species, greater cover of native species may even be necessary.
On the other hand, the effect of native vegetation on plant invasion may be related to other variables. An attribute of native vegetation, which may affect plant invasion, is the foliage periodicity of dominant tree species (e.g. evergreen and deciduous) [33]. Forest communities dominated by deciduous species receive more light than evergreen forests, at least during a period of time within a year, and thus, evergreen forests may produce greater competitive resistance against plant invasion. However, the role of this factor in plant invasion has been very few times evaluated. Only Ibáñez et al. [33] addressed this issue and documented greater exotic species richness in deciduous forests than evergreen forests in a region of eastern North America.
Plant-plant interactions may strongly be modulated by abiotic conditions [34], and hence, the effect of native vegetation on plant invasion may be influenced by climate or habitat conditions. Specifically, positive interactions should be more frequent under more stressing conditions, while competition under more productive or favourable conditions for plants, which is known as the stress-gradient hypothesis [34]. Although some evidence for this hypothesis has been documented through experimental approaches in the context of plant invasions [10, 11, 12, 17], these studies have only been performed at local scales and for particular exotic species. Thus, it is less known that the pattern of relationship between native vegetation variables, such as cover and species richness, and exotic invasion varies between different climatic or habitat conditions according to the stress-gradient hypothesis (but see [25]). Based on the stress-gradient hypothesis, plant invasion should be positively related to cover and richness of native species under more stressing conditions (e.g. arid and semiarid climates), while negatively in more favourable conditions (e.g. temperate climates). Likewise, plant invasion should be greater in deciduous forests than evergreen forests under more favourable conditions.
In this study, we compiled data on exotic species richness at a plot scale in different forest types of Chile and assessed how exotic species richness is correlated to cover and richness of native species, as well as the type of periodicity of foliage of dominant trees in forests distributed through the Mediterranean-type and temperate regions of the country.
We compiled several published and unpublished studies on Chilean vegetation, from which we obtained data on exotic and native species composition and abundance at a plot scale from different types of forest communities (Table 1). Each one of these communities corresponded to a particular phytosociological unit, most of them at the association level, with homogeneous climate and soil conditions. However, due to differences in geographical distribution among forest types, these had different climatic regimes (Mediterranean-type and temperate climates) and are dominated by species with different periodicity of foliage (deciduous or evergreen). We considered only studies in which species composition and abundance (percentage of cover) per plot were published (e.g. phytosociological tables), from which we obtained values of exotic and native species richness and cover. Within every forest type, selected plots for the analyses had the same size, although the size of plots varied between some forest types. In addition, the distance between plots varied between forest types, from 300 m in some forest types to some kilometres in others. Also, forest types included in the analyses did not show significant evidence (indicated in the publication) of strong anthropogenic disturbances (massive logging of trees or recent fires). This entailed that all plots within each forest types were at least partially covered by a tree canopy. However, forest types could present slight perturbations such as herbivory by exotic livestock and rabbits, tourism impacts (e.g. tracks) and/or reduced past forest logging. This produced a gradient of native species cover and richness within all forests. According to these criteria, we found eight forest types including Mediterranean as well as temperate forests of Chile (Table 1).
Forest type | Lat. | Long. | Plot (m2) | N° plots | Region | Foliage | % herbs | % shrubs | % trees |
---|---|---|---|---|---|---|---|---|---|
Sclerophyllous forest (Sc) | 32°17′ | 71°11′ | 100 | 18 | M | E | 100 | 0.0 | 0.0 |
Mediterranean montane deciduous forest (Mm) | 35–36° | 71–72° | 100 | 21 | M | D | 28.6 | 42.9 | 28.6 |
Mediterranean Subantarctic Andean forest (Sa) | 35°35′ | 71°02′ | 100 | 26 | M | D | 83.3 | 16.7 | 0.0 |
Temperate montane deciduous forest (Tm) | 38°26′ | 71°31′ | 100 | 20 | T | E | 95.0 | 5.0 | 0.0 |
Lowland deciduous forest (Ld) | 39–40° | 72–73° | 140 | 35 | T | D | 88.0 | 12.0 | 0.0 |
Swamp evergreen forest (Se) | 39–41° | 72–73° | 100 | 27 | T | E | 85.7 | 7.1 | 7.1 |
Swamp deciduous forest (Sd) | 40°30′ | 72°30′ | 200 | 10 | T | D | 90.0 | 10.0 | 0.0 |
Lowland evergreen forest (Le) | 41°00′ | 73°00′ | 200 | 10 | T | E | 90.5 | 9.5 | 0.0 |
Characteristics of the studied forest ecosystems: geographical location or range in which each forest was sampled (latitude and longitude), size of sampling plots, number of plots used, climatic region (M: Mediterranean; T: temperate), foliage periodicity of dominant species (E: evergreen; D: deciduous) and percentages of herb, shrub and tree species in the exotic flora in each forest.
Forest types selected for this study were distributed between 33 and 41°S of Chile, covering both Mediterranean and temperate climates (Table 1 and Figure 1). The most septentrional forest used in this study is a sclerophyllous forest (Becerra, unpublished data), which is an evergreen forest distributed in the coastal range of the semi-arid Mediterranean zone, dominated by the species Cryptocarya alba and Schinus velutina. The Mediterranean montane deciduous forest [35] is dominated by the deciduous species Nothofagus glauca and is distributed in coastal as well as pre-Andean foothills of the Mediterranean region. The Mediterranean Subantarctic Andean forest [36] is dominated by the deciduous species Nothofagus pumilio and is distributed along the Andean timberline within the humid Mediterranean region of Chile. The temperate montane deciduous forest [37] is dominated by the deciduous species Nothofagus alpina and N. obliqua and is distributed on the foothills of the Andean range. The swamp deciduous forest [38] is dominated by the deciduous species Nothofagus antarctica and is distributed on swamp soils in the central valley of the temperate region. The lowland evergreen forest [38] is dominated by the evergreen species Eucryphia cordifolia and Nothofagus dombeyi and is distributed on the foothills of the Andean range of the temperate region. The lowland deciduous forest [39] is dominated by the deciduous species Nothofagus obliqua and is distributed in the central valley of the temperate region. Finally, the swamp evergreen forest [40] is dominated by the evergreen species Myrceugenia exsucca and Blepharocalyx cruckshanksii and is distributed on the lowlands of the temperate region of Chile occupying mainly riverine habitats.
Geographical distribution (only referential location) of forest types included in the study. Different studies covered different surfaces. Nomenclature of forest types is indicated in Table 1.
Climate of forests included in this study varied from approximately 350 mm of annual precipitation and an annual mean temperature of 14°C in the sclerophyllous forest, to near 2500 mm of annual precipitation and an annual mean temperature of 10.5°C in the lowland evergreen forest [41].
We performed two types of analyses: first, we analysed together all data from all forest types, in order to examine the contribution of every variable to the variation in exotic species richness. Thus, in the same model, we evaluated the independent effects of the climatic region (Mediterranean vs. temperate), foliage periodicity of forests (deciduous vs. evergreen), native species richness and native species cover, as well as the statistical interactions between the climatic region and each native vegetation variable. Although the areas of plots were in general quite similar between forests (Table 1), the size of plots differed between some of them (Table 1), and preliminary log(10) area-log (N° species) correlations were significant for all forest types. Hence, to compare exotic and native species richness at a plot scale among all forest types, we controlled the size of plots by dividing values of exotic species richness as well as native species richness by the log(10) of the area of each plot. On the other hand, cover values of native species per plot were quantified by the sum of cover among all native species per plot. However, due to larger plots that may have more species and therefore more components for this sum, to use native species cover in the analyses, we controlled the differences in the species number by dividing the sum of cover by the number of native species per plot. Thus, we obtained a variable representing a mean cover of native species per plot.
Finally, we assessed the relationships between exotic species richness and native species richness and cover separately for each forest type with the aim to evaluate if these intra-forest relationships are generalised among different forest types in central-south Chile. In these cases, because within each forest type the size of plots was equal among plots, we did not control the area of them and used the absolute number of exotic and native species as well as the sum of native species cover directly.
All statistical analyses were carried out using SPSS 15.0 by generalised linear models (GLMs).
Among the eight forest types, we recorded 56 exotic species corresponding to three trees (5.4%), four shrubs (7.1%) and 49 herbs (87.5%). The most common species were Rumex acetosella and Rosa rubiginosa present in six forest types; Hypochaeris radicata, Prunella vulgaris and Veronica serpyllifolia present in five forest types; and Anthoxanthum odoratum, Holcus lanatus, Leontodon taraxacoides, Lotus uliginosus, Plantago lanceolata, Trifolium repens and Rubus constrictus present in four forest types. In general, exotic species were mostly herbs in all forests with percentages greater than 80%, except in the Mediterranean deciduous forest (Table 1). Species composition per forest-type is shown in Table 2.
Exotic species | Sc | Mm | Sa | Tm | Sd | Le | Ld | Se |
---|---|---|---|---|---|---|---|---|
Achillea millefolium | 1 | |||||||
Agrostis capillaris | 1 | 1 | 1 | |||||
Agrostis castellana | 1 | 1 | ||||||
Agrostis tenuis | 1 | |||||||
Anagallis arvensis | 1 | |||||||
Anthoxanthum odoratum | 1 | 1 | 1 | 1 | ||||
Aster vahlii | 1 | |||||||
Bellardia trixago | 1 | 1 | ||||||
Bromus hordeaceus | 1 | |||||||
Capsella bursa-pastoris | 1 | |||||||
Cirsium vulgare | 1 | 1 | ||||||
Crataegus monogyna | 1 | |||||||
Crepis capillaris | 1 | |||||||
Cynosurus echinatus | 1 | 1 | ||||||
Cytisus striatus | 1 | |||||||
Chrysanthemum sp. | 1 | |||||||
Dactylis glomerata | 1 | 1 | 1 | |||||
Digitalis purpurea | 1 | 1 | 1 | |||||
Erodium cicutarium | 1 | |||||||
Fumaria officinalis | 1 | |||||||
Galium aparine | 1 | |||||||
Gastridium ventricosum | 1 | |||||||
Holcus lanatus | 1 | 1 | 1 | 1 | ||||
Hypochoeris radicata | 1 | 1 | 1 | 1 | 1 | |||
Lapsana communis | 1 | |||||||
Leontodon taraxacoides | 1 | 1 | 1 | 1 | ||||
Leucanthemum vulgare | 1 | 1 | ||||||
Lolium multiflorum | 1 | |||||||
Lolium perenne | 1 | 1 | ||||||
Lotus uliginosus | 1 | 1 | 1 | 1 | ||||
Medicago polymorpha | 1 | |||||||
Mentha pulegium | 1 | |||||||
Panicum capillare | 1 | |||||||
Phleum pratense | 1 | |||||||
Pinus radiata | 1 | |||||||
Plantago lanceolata | 1 | 1 | 1 | 1 | ||||
Poa pratensis | 1 | |||||||
Poa trivialis | 1 | |||||||
Prunella vulgaris | 1 | 1 | 1 | 1 | 1 | |||
Ranunculus repens | 1 | 1 | ||||||
Rosa rubiginosa | 1 | 1 | 1 | 1 | 1 | 1 | ||
Rubus constrictus | 1 | 1 | 1 | 1 | ||||
Rubus ulmifolius | 1 | |||||||
Rumex acetosella | 1 | 1 | 1 | 1 | 1 | 1 | ||
Salix viminalis | 1 | |||||||
Sonchus asper | 1 | |||||||
Stellaria media | 1 | 1 | ||||||
Taraxacum officinale | 1 | 1 | 1 | |||||
Teline monspessulana | 1 | 1 | ||||||
Trifolium dubium | 1 | 1 | ||||||
Trifolium pratense | 1 | 1 | 1 | |||||
Trifolium repens | 1 | 1 | 1 | 1 | ||||
Urtica dioica | 1 | |||||||
Verbascum thapsus | 1 | |||||||
Veronica scutellata | 1 | |||||||
Veronica serpyllifolia | 1 | 1 | 1 | 1 | 1 |
Exotic species recorded in each forest type. Nomenclature of forests is in Table 1.
Regarding all forests, exotic species richness varied between 0 and 20 species per plot. After controlling the area of plots, exotic species richness was significantly greater in temperate forests than in Mediterranean forests along all gradients of cover and richness of native species and for each type of forest canopy (deciduous or evergreen) (Table 3 and Figures 2–4). Exotic species richness was negatively and significantly related to the native species cover (Table 3 and Figure 2). This pattern seems to occur in both Mediterranean and temperate forests as we found no significant interaction between the climatic region and native species cover (Table 3). However, the slope of this relationship in plots from the temperate region was greater than in plots from the Mediterranean-type climate region (Figure 2). In contrast, exotic species richness was not significantly related to the native species richness when all plots were analysed together or in each climatic region separately (Table 3 and Figure 3). On the other hand, exotic species richness was significantly greater in deciduous forests than evergreen forests (Table 3 and Figure 4). Yet, the interaction between region and foliage periodicity was significant (Table 3), indicating that higher exotic species richness in deciduous forests than evergreen forests occurred only in temperate forests (Figure 4).
Source of variation | Chi2 | P |
---|---|---|
Climatic region | 54.999 | <0.001 |
Foliage periodicity | 8.377 | 0.004 |
Native cover | 5.201 | 0.023 |
Native richness | 2.241 | 0.134 |
Climatic region × foliage | 17.278 | <0.001 |
Climatic region × native cover | 0.029 | 0.864 |
Climatic region × native richness | 0.066 | 0.798 |
Statistical results (generalised lineal models) for the effect of climatic region (Mediterranean vs. Temperate), foliage periodicity (evergreen vs. deciduous), native species cover and native species richness on exotic species richness (N = 167 plots).
Relationship between exotic species richness and native species cover per climatic region. Exotic species richness per plot was divided by the logarithm (10) of the area of plots to control the differences of area between plots. Native species cover per plot was divided by the number of native species in the plot to control the differences of richness between plots.
Relationship between exotic species richness and native species richness per climatic region. Exotic species richness and native species richness per plot were divided by the logarithm (10) of the area of plots to control the differences of area between plots.
Exotic species richness per climatic region and foliage periodicity type (mean ± 1 S.E.) (N = 167 plots). Different letters indicate significant statistical differences between each combination of region and foliage periodicity (P < 0.05).
When analysing data separately for each forest type, they showed different relationships between native vegetation variables and exotic species richness. A significant negative relationship between native species cover and exotic species richness was observed in four forest types, representing 50% of studied forest types, two forests from the Mediterranean-type climate region and two from the temperate region (Table 4 and Figure 5). There was no positive relationship between native species cover and exotic species richness. In turn, a significant relationship between native species richness and exotic species richness was observed only in three forest types, representing 38% of forests included in this study, all of them corresponding to temperate forests (Table 4 and Figure 6). However, in this case, in two forests the relationship was negative while in one forest type (Swamp deciduous forest) the relationship was positive (Figure 6).
Forest type | Native species richness | Total native cover | ||
---|---|---|---|---|
Chi2 | P | Chi2 | P | |
Sclerophyllous forest (Sc) | 1.901 | 0.168 | 0.626 | 0.429 |
Mediterranean Subantarctic Andean forest (Sa) | 1.217 | 0.270 | 7.337 | 0.007 |
Mediterranean montane deciduous forest (Mm) | 1.043 | 0.307 | 8.109 | 0.004 |
Lowland deciduous forest (Ld) | 11.351 | 0.001 | 0.012 | 0.913 |
Swamp deciduous forest (Sd) | 7.781 | 0.005 | 0.550 | 0.458 |
Lowland evergreen forest (Le) | 0.074 | 0.786 | 0.058 | 0.810 |
Temperate montane deciduous forest (Tm) | 4.526 | 0.033 | 11.450 | 0.001 |
Swamp evergreen forest (Se) | 0.004 | 0.951 | 6.160 | 0.013 |
Statistical results (generalised linear models, ordinal multinomial distribution of data and logit function link) of analyses per forest type for the effect of native species richness and native species cover on exotic species richness. Significant relationships in bold.
Relationships between exotic species richness and native species cover in every forest type. Curves are shown only for significant relationships.
Relationships between exotic species richness and native species richness in every forest type. Curves are shown only for significant relationships.
In this study, we document that exotic species richness is related to variation in native species cover, foliage periodicity and, at a less extent, native species richness. Additionally, these relationships depend on climate and/or forest type in forest communities of Chile.
The significant negative relationships between exotic species richness and native species cover pooling all forests as well as within some forest types suggest competitive effects of native vegetation on invasion of exotic plants [27]. Variability of native cover within forests may be produced by natural causes (including natural disturbances) as well as anthropogenic disturbances. Regardless of the cause determining this variability, lower native cover entails more resources for invasive species [13, 14, 27]. Therefore, our results suggest a high importance of competition in invasion processes of exotic species in these forest communities. Similarly, other observational studies performed within forest ecosystems [19, 28, 31, 42] as well as an increasing number of experimental studies have demonstrated the importance of resource availability and competition liberation for plant invasion [8, 12, 21, 23, 43]. Therefore, although many exotic plant species may also invade closed-canopy forests, as documented by Martin et al. [32], our results suggest that more covered sites within or between native forests may better resist plant invasion.
Globally within the study area, we observed no significant relationship between exotic and native species richness. Instead, when every forest was separately analysed, two of them showed a significant negative relationship, which is consistent with the idea that negative relationships between exotic and native species richness would only occur when other factors are controlled (i.e. within each forest type) [3, 7, 15, 21]. This result suggests that, at least in these two forest types, exotic and native species may be competing by resources. However, our results did not agree to Shea and Chesson [7] and some empirical studies [6, 19, 22, 25, 44, 45], which proposed that in geographical comparisons (in our case in the analysis pooling data from all forests), positive relationships between exotic and native species richness should emerge. In particular, the absence of a positive correlation between native and exotic species richness when all forests were analysed together contrasts to Fuentes et al. [26], who found similar geographical tendencies between native and exotic species richness along Chile, although in this case, using much larger scales to measure species richness. Davies et al. [46] proposed that positive relationships between exotic and native species richness would mainly occur when richness is quantified at large spatial scales [26]. This would occur because greater environmental heterogeneity within large quadrants would favour both exotic and native species. Instead, this would not occur at small spatial scales such as a plot-scale (this study), even though plots are compared at a geographical scale [46]. However, Souza et al. [47] found that native and exotic species richness may be positively correlated both at local and landscape scales. Consistent to Souza et al. [47], we observed a positive relationship between exotic and native species richness occurring within a forest type (at a local scale). This positive correlation could be produced by a similar response of native and exotic species to environmental factors [7, 47], or because native species are facilitating exotic species [16, 47]. In the forest type in which this positive relationship was observed (swamp deciduous forest), soil conditions are extreme, with soils permanently saturated with water and low soil oxygen [38]. Therefore, it is probable that within this community, only in microsites (at a scale of 100 m2 or less) where soil conditions are a little more favourable, more species, exotics as well as natives, can coexist. Nevertheless, it is not possible to rule out facilitative effects of native on exotic species in this case either.
We observed that in the temperate region, deciduous forests presented greater exotic species richness than evergreen forests, which suggests that the seasonal increase in light conditions in deciduous forests may be a factor contributing to an increase of invasion probability in temperate forests. Higher light requirement of exotic species has been proposed as an important life history attribute favouring the invasion in low-cover sites [14, 43], for instance, ruderal habitats. In fact, most of the exotic species of central-south of Chile have been documented as shade-intolerant species [48]. Although the relationship between foliage periodicity and plant invasion has scarcely been evaluated, our results agree to Ibáñez et al. [33] who documented greater exotic species richness in deciduous forests than evergreen forests in eastern North America. Thus, this factor may be an important driver of plant invasion in forest ecosystems although more studies are needed to assess the generality of this relationship.
On the other hand, our results show that under the same conditions of cover, richness and foliage periodicity of native species, forests from the temperate climate region were richer in exotic species than forests from the Mediterranean-type climate region. This suggests that the Mediterranean-type semiarid region of Chile represents a more stressful condition than the temperate region for exotic species invading forest ecosystems, which agrees to several studies documenting that greater exotic species richness seems to establish mainly in more productive climates [6, 20, 26, 33]. For instance, Lonsdale [6] found a lower number of exotic species in deserts and savannas than in forest habitats around the world, and Stohlgren et al. [20] found a positive relationship between productivity and exotic species richness within North America. Ibáñez et al. [33] documented higher exotic species richness in areas with warmer temperatures and higher summer precipitation in a region of eastern North America. Finally, in the same country, Chile, Fuentes et al. [26] observed greater exotic species richness at a regional scale (10 × 10 km) within Mediterranean and temperate regions than in deserts or colder areas. Nevertheless, in contrast to our results, Fuentes et al. [26] observed higher exotic species richness in the Mediterranean region than the temperate region although, in this case, using larger scales to measure exotic species richness.
If more xeric climates such as in the Mediterranean region of Chile entail more stressful conditions for exotic species (as suggested by the greater exotic species richness in the temperate climate), based on the stress-gradient hypothesis [34], in the Mediterranean region, facilitative interactions and positive relationships may be expected between native vegetation and exotic species richness, while competitive and negative relationships in temperate forests. Thus, the fact that the relationship between native cover and plant invasion was observed in both climatic regions only partially supports the stress-gradient hypothesis [34]. However, the slope of this relationship was steeper in the temperate region than in the Mediterranean-type climate region, suggesting that competitive effects of native vegetation on exotic species were stronger in the less stressful climatic region, which agrees to the stress-gradient hypothesis [11, 34]. Additionally, we did not find a significant negative relationship between native cover and exotic species richness in the most xeric forest included in this study (sclerophyllous forest), which again suggests that under more stressing conditions in terms of water availability, competition would be weaker, or that facilitative effects of native vegetation on exotic species counteracted any competitive interaction (e.g. [10, 12, 17]). Furthermore, two among five temperate forests presented negative relationships between native cover and exotic richness, and in the other temperate forest (lowland deciduous forest), a negative relationship between native and exotic species richness was observed. These results suggest that in temperate forests negative relationships between native vegetation and exotic species are more frequent than in Mediterranean forests, which agree with the stress-gradient hypothesis. On the other hand, the fact that deciduous forests presented greater exotic richness than evergreen forests only in the temperate region suggests that in more humid regions the light conditions may be a more important limiting factor for exotic species than in Mediterranean-type climates. This result may also be consistent with the stress-gradient hypothesis since competition by light would be stronger under less stressful abiotic conditions (temperate region). In consequence, our results suggest that the stress-gradient hypothesis may be useful to predict patterns of relationship between exotic species richness and native vegetation when species richness is analysed at small spatial scales. Other studies [11] have also found support for this hypothesis in the context of interactions between native and exotic species.
Finally, our results suggest that maintaining or increasing native species cover may help to control or reduce plant invasion, at least in terms of exotic species richness. This may be a successful management strategy for the control of invasion mainly in temperate forests as well as in some Mediterranean-type climate forests. Instead, in more xeric Mediterranean forests (e.g. sclerophyllous forest), an increase in cover of native species does not seem to be enough to reduce exotic species richness, and other actions are needed to control plant invasion.
We thank the Chilean phytosociologists who have greatly contributed to knowledge of Chilean plant communities and have published original tables of species which allowed performing this study. This work was supported by a doctoral fellowship from CONICYT to PIB and by ICM-P05-002. PIB thanks FB 0002-2014.
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