Properties of ZnO [1].
\\n\\n
Released this past November, the list is based on data collected from the Web of Science and highlights some of the world’s most influential scientific minds by naming the researchers whose publications over the previous decade have included a high number of Highly Cited Papers placing them among the top 1% most-cited.
\\n\\nWe wish to congratulate all of the researchers named and especially our authors on this amazing accomplishment! We are happy and proud to share in their success!
Note: Edited in March 2021
\\n"}]',published:!0,mainMedia:{caption:"Highly Cited",originalUrl:"/media/original/117"}},components:[{type:"htmlEditorComponent",content:'IntechOpen is proud to announce that 191 of our authors have made the Clarivate™ Highly Cited Researchers List for 2020, ranking them among the top 1% most-cited.
\n\nThroughout the years, the list has named a total of 261 IntechOpen authors as Highly Cited. Of those researchers, 69 have been featured on the list multiple times.
\n\n\n\nReleased this past November, the list is based on data collected from the Web of Science and highlights some of the world’s most influential scientific minds by naming the researchers whose publications over the previous decade have included a high number of Highly Cited Papers placing them among the top 1% most-cited.
\n\nWe wish to congratulate all of the researchers named and especially our authors on this amazing accomplishment! We are happy and proud to share in their success!
Note: Edited in March 2021
\n'}],latestNews:[{slug:"webinar-introduction-to-open-science-wednesday-18-may-1-pm-cest-20220518",title:"Webinar: Introduction to Open Science | Wednesday 18 May, 1 PM CEST"},{slug:"step-in-the-right-direction-intechopen-launches-a-portfolio-of-open-science-journals-20220414",title:"Step in the Right Direction: IntechOpen Launches a Portfolio of Open Science Journals"},{slug:"let-s-meet-at-london-book-fair-5-7-april-2022-olympia-london-20220321",title:"Let’s meet at London Book Fair, 5-7 April 2022, Olympia London"},{slug:"50-books-published-as-part-of-intechopen-and-knowledge-unlatched-ku-collaboration-20220316",title:"50 Books published as part of IntechOpen and Knowledge Unlatched (KU) Collaboration"},{slug:"intechopen-joins-the-united-nations-sustainable-development-goals-publishers-compact-20221702",title:"IntechOpen joins the United Nations Sustainable Development Goals Publishers Compact"},{slug:"intechopen-signs-exclusive-representation-agreement-with-lsr-libros-servicios-y-representaciones-s-a-de-c-v-20211123",title:"IntechOpen Signs Exclusive Representation Agreement with LSR Libros Servicios y Representaciones S.A. de C.V"},{slug:"intechopen-expands-partnership-with-research4life-20211110",title:"IntechOpen Expands Partnership with Research4Life"},{slug:"introducing-intechopen-book-series-a-new-publishing-format-for-oa-books-20210915",title:"Introducing IntechOpen Book Series - A New Publishing Format for OA Books"}]},book:{item:{type:"book",id:"3545",leadTitle:null,fullTitle:"Autophagy - A Double-Edged Sword - Cell Survival or Death?",title:"Autophagy - A Double-Edged Sword",subtitle:"Cell Survival or Death?",reviewType:"peer-reviewed",abstract:"The chapters in this book review the latest advances in the molecular mechanisms of autophagy, highlighting some of the most challenging research topics. The focus is mainly on how this basic cell defense mechanism comes into play in various pathologies, including liver diseases, myopathies, infectious diseases, cancers and neurodegenerative diseases. In these diseases, the contradictory autophagy roles of cell survival versus cell death emphasize the necessity of taking into account this double-edged nature in future development of already promising, autophagy- modulating, therapies.",isbn:null,printIsbn:"978-953-51-1062-0",pdfIsbn:"978-953-51-5366-5",doi:"10.5772/50855",price:159,priceEur:175,priceUsd:205,slug:"autophagy-a-double-edged-sword-cell-survival-or-death-",numberOfPages:524,isOpenForSubmission:!1,isInWos:null,isInBkci:!1,hash:"62f2a3697cfbfa51f5d78b86b07140aa",bookSignature:"Yannick Bailly",publishedDate:"April 17th 2013",coverURL:"https://cdn.intechopen.com/books/images_new/3545.jpg",numberOfDownloads:59885,numberOfWosCitations:67,numberOfCrossrefCitations:31,numberOfCrossrefCitationsByBook:3,numberOfDimensionsCitations:88,numberOfDimensionsCitationsByBook:4,hasAltmetrics:1,numberOfTotalCitations:186,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"June 20th 2012",dateEndSecondStepPublish:"July 11th 2012",dateEndThirdStepPublish:"October 15th 2012",dateEndFourthStepPublish:"January 13th 2013",dateEndFifthStepPublish:"February 12th 2013",currentStepOfPublishingProcess:5,indexedIn:"1,2,3,4,5,6",editedByType:"Edited by",kuFlag:!1,featuredMarkup:null,editors:[{id:"164577",title:"Dr.",name:"Yannick",middleName:null,surname:"Bailly",slug:"yannick-bailly",fullName:"Yannick Bailly",profilePictureURL:"https://mts.intechopen.com/storage/users/164577/images/system/164577.jfif",biography:"Yannick Bailly was born in 1956. 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Since 1994, after returning to Strasbourg as a CNRS Research Director, his laboratory has become renowned for its expertise in ultrastructural neuroanatomy. \r\nYannick Bailly has made major contributions concerning the synaptic localization of cardinal molecules involved in neurodegenerative diseases, such as amyloid precursor proteins and presenilins in Alzheimer’s disease and prion protein. \r\nHis research group has provided valuable insight into neuronal death mechanisms involved in brain pathologies, in particular in prion diseases.",institutionString:"University of Strasbourg",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"1",totalChapterViews:"0",totalEditedBooks:"1",institution:{name:"University of Strasbourg",institutionURL:null,country:{name:"France"}}}],equalEditorOne:null,equalEditorTwo:null,equalEditorThree:null,coeditorOne:null,coeditorTwo:null,coeditorThree:null,coeditorFour:null,coeditorFive:null,topics:[{id:"414",title:"Cytology",slug:"cytology"}],chapters:[{id:"44093",title:"Role of Human WIPIs in Macroautophagy",doi:"10.5772/54601",slug:"role-of-human-wipis-in-macroautophagy",totalDownloads:2225,totalCrossrefCites:0,totalDimensionsCites:0,hasAltmetrics:0,abstract:null,signatures:"Tassula Proikas-Cezanne and Daniela Bakula",downloadPdfUrl:"/chapter/pdf-download/44093",previewPdfUrl:"/chapter/pdf-preview/44093",authors:[{id:"164152",title:"Prof.",name:"Tassula",surname:"Proikas-Cezanne",slug:"tassula-proikas-cezanne",fullName:"Tassula Proikas-Cezanne"},{id:"164170",title:"MSc.",name:"Daniela",surname:"Bakula",slug:"daniela-bakula",fullName:"Daniela Bakula"}],corrections:null},{id:"44094",title:"Atg8 Family Proteins — Autophagy and Beyond",doi:"10.5772/55647",slug:"atg8-family-proteins-autophagy-and-beyond",totalDownloads:2758,totalCrossrefCites:1,totalDimensionsCites:7,hasAltmetrics:0,abstract:null,signatures:"Oliver H. 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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:"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:"314",title:"Regenerative Medicine and Tissue Engineering",subtitle:"Cells and Biomaterials",isOpenForSubmission:!1,hash:"bb67e80e480c86bb8315458012d65686",slug:"regenerative-medicine-and-tissue-engineering-cells-and-biomaterials",bookSignature:"Daniel Eberli",coverURL:"https://cdn.intechopen.com/books/images_new/314.jpg",editedByType:"Edited by",editors:[{id:"6495",title:"Dr.",name:"Daniel",surname:"Eberli",slug:"daniel-eberli",fullName:"Daniel Eberli"}],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:"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:"2270",title:"Fourier Transform",subtitle:"Materials Analysis",isOpenForSubmission:!1,hash:"5e094b066da527193e878e160b4772af",slug:"fourier-transform-materials-analysis",bookSignature:"Salih Mohammed Salih",coverURL:"https://cdn.intechopen.com/books/images_new/2270.jpg",editedByType:"Edited by",editors:[{id:"111691",title:"Dr.Ing.",name:"Salih",surname:"Salih",slug:"salih-salih",fullName:"Salih Salih"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}}]},chapter:{item:{type:"chapter",id:"60151",title:"Fabrication of ZnO Thin Film through Chemical Preparations",doi:"10.5772/intechopen.74985",slug:"fabrication-of-zno-thin-film-through-chemical-preparations",body:'\nZinc oxide (ZnO) is a II-VI semiconductor group which has a wurtzite as the most stable compound structure and has unique physical and chemical properties. In physical properties, ZnO has a high thermal stability, which starts to melt and boil at 1975°C; in optical properties, it has a high transparency and a direct band gap at 3.4 eV, which can be tuned by doping several elements such as Al, Ga, or In [1]. ZnO also has a low resistivity, which is about 1–2 × 10−4 Ωcm [2], a high thermal stability, a high electrochemical coupling coefficient, and a high bonding energy (60 meV) [1]. Due to all these unique properties, ZnO becomes a promising material, which can be applied in many fields as a sensor, converter, catalyst, and even as an important part in solar cells. This study aims to review ZnO as a transparent conductive oxide (TCO) in solar cells.
\nIn solar cells, ZnO plays important roles in collecting the energy from sunlight in various solar cells such as silicone-based solar cell (first-generation solar cell), thin film (second-generation), organic, multijunction, dye-sensitized (third-generation), hybrid and perovskite solar cells (fourth generation). In the first to the third generation of solar cell, ZnO plays a role as transparent conductive oxide (TCO), except in organic solar cell in which ZnO acts as a junction for exciton separation [3].
\nTransparent conductive oxide (TCO) is very important for harvesting electricity from sunlight and can improve solar cell efficiency. This layer is used to place on top of thin film solar cells and has a high transmittance (greater than 80% in the visible spectrum area) but has a low resistivity (less than 10−4 Ωcm). These properties will minimize the probability of the received photon absorbed by the layers before the absorber layer or reflected back. Table 1 shows several properties of ZnO as TCO on solar cells.
\nProperties of ZnO [1].
In addition, TCO should have a higher band gap than the absorber layer and the buffer layer, approximately 3.2 eV. If all of the layers are stacked together, they will make a gradation of band gap energy from low band gap energy (absorber layer) to the high energy (the top contact). This gradation can help electrons of the absorbed photons in the absorber layer to move past the other layers to the top layer. On the other hand, the holes move to the back-contact as a hole summation in solar cells. Since the electrons and holes move to the opposite side, this makes a difference potential on either side and produces electricity. If the band gap gradation is not sequentially arranged, it will disturb electron and hole movement. As a consequence, the electricity will not appear. Figure 1 shows illustrations of electrons and holes, movement through several layers with different band gaps in the CIGSe (CuInGeSe4) solar cell.
\nA schematic layer structure of a classical CIGSe solar cell [
Besides its physical properties, ZnO is a common material as TCO for thin film solar cell because this material is non-toxic and abundant. However, ZnO still lacks in optical and electrical (opto-electrical) properties. Thus, some of elements or molecules have been successfully developed to improve its optoelectrical properties such as Al, Ga, B, In, Y, Sc, F, V, Si, Ge, Ti, Zr, Hf, In2O3 and SnO2 [6]. Some of elements provide a significant change in optical and electrical properties of ZnO. Table 2 shows some changes of ZnO optical and electrical properties as TCO after being doped by some elements.
\nDopants | \nOptimum content in target (%) | \nThickness (nm) | \nResistivity (Ωcm) | \nTransmittance (%) | \nReferences | \n
---|---|---|---|---|---|
Al | \n2 | \n500 | \n4.5 × 10−4 | \n88 | \n[7] | \n
Ga | \n5 | \n200 | \n8.12 × 10−4 | \n>90 | \n[8] | \n
In | \n40 | \n>1000 | \n4.02 × 10−4 | \n>85 | \n[9] | \n
F | \n2 | \n200 | \n4.83 × 10−4 | \n>90 | \n[10] | \n
Si | \n2 | \n∼150 | \n6.2 × 10−4 | \n∼80 | \n[11] | \n
Properties of ZnO films with different dopants.
ZnO thin film could be prepared by physical or vacuum methods such as radio frequency (RF) magnetron sputtering or direct current (DC) sputtering, pulsed laser deposition (PLD), and e-beam evaporation [12, 13, 14, 15]. However, all of these methods need particular vacuum equipments and investment. Contrary from physical or vacuum methods, chemical methods are well known as a low-cost method because it does not require particular equipment or expensive investment. Thus, chemical process becomes a promising and low-cost process.
\nThere are several processes for depositing ZnO by using chemical process, such as chemical bath deposition (CBD)/dip coating, chemical vapor deposition (CVD)/spray pyrolysis, sol-gel spin coating, doctor blade coating, printing deposition, and electrochemical deposition. Even though there are various deposition techniques, the steps of each technique are the same. The first step is preparing the precursor which can be in a solution, sol-gel, colloidal, or even in a dispersion precursor form. The second step is depositing using various techniques, and the last step is drying or heat treatment to remove the solvent and to develop the ZnO thin film. Common steps in the preparation of ZnO by chemical process are shown in Figure 2.
\nA common preparation step to fabricate ZnO thin film by chemical processes.
In the chemical preparation process, to adjust ZnO thin films into p or n semiconductor, it is done by adding some particular element of salt such as aluminum salt or boron salt into the precursor mixture.
\nSome of experiments only need a single step of heat treatment to develop the ZnO thin film, but in spin-coating method, several repetition steps of coating and heat treatment are required in order to get the desired thickness, and this repetition step is called as preheat treatment. Contrary with the spin coating, chemical vapor deposition (CVD) or spray pyrolysis method may not have specific drying or heat treatment steps because in this method, the heat treatment is done simultaneously with deposition. To adjust the thickness in CVD or spray pyrolysis, it is adjusted by the deposition time.
\nChemical bath deposition (CBD) or dip coating is the simplest and low-cost deposition method because this method does not need expensive and special equipment. In addition, it also has a simple deposition principle. The arrangement of equipment is shown in Figure 3.
\nThe arrangement of CBD equipment [
At the precursor preparation, zinc oxide is prepared from zinc-salt compound such as zinc acetate dihydrate, zinc nitrate, zinc chloride, and zinc sulfate [17, 18, 19, 20, 21]. After these kinds of zinc salts were dissolved in the solution, zinc in the salt becomes a cation which can react with anion from basic compound, as well as form a seed of nuclei which adhere on the substrate. Besides that, zinc cation also reacts with other compounds in the precursor mixture such as surfactants which act as a binder and form zinc complex compound or in order to get desire properties of the mixture such as viscosity or homogeneity. Table 3 shows various zinc salts and other compounds as precursor mixture.
\nZinc salt | \nOther additive compounds | \nReferences | \n
---|---|---|
Zn(CH3COO)2 | \n2-methoxyethanol, mono-ethanolamine | \n[17] | \n
Zn(NO3)2 | \nNaOH, sodium n-dodecyl sulfate, triethanolamine | \n[18] | \n
ZnCl2 | \nNH4OH, hexadecyl(trimethyl)azanium bromide | \n[19] | \n
ZnSO4 | \nNH4OH, NH4HCO3 | \n[20] | \n
Various zinc salts and other compounds as precursor mixture.
Further, this seed of nuclei will develop as zinc-salt precipitation which adheres on the substrate, and after drying or heat treatment under various atmospheres, it becomes oxidized and forms a zinc oxide as thin film. The schematic of this preparation is shown in Figure 4.
\nMechanism of ZnO thin film growth [
This is the reaction mechanism of ZnO thin film fabrication.
\nAt drying or heat treatment step, the heat treatment can be done at various temperatures and atmospheres. These various processes have the effect to the shape, morphology, optical, and electrical properties of zinc oxide thin film [22]. Table 4 shows various annealing temperatures and atmospheres or heat treatment step.
\nTemperature (°C) | \nDuration (hour) | \nAtmosphere | \nReferences | \n
---|---|---|---|
100 | \n1 | \nAir | \n[23] | \n
300 | \n0.5 | \nOxygen | \n[24] | \n
300–600 | \n1 | \nAir | \n[25] | \n
400–800 | \n1 | \nAir | \n[26] | \n
Various annealing temperatures and atmospheres/heat treatment step.
In addition to these, the concentration of precursor of zinc salt as zinc source and other additive concentrations also give significant role to ZnO thin film [22]. The effect of zinc and surfactant concentrations can be seen in Figure 4. The increase of zinc and surfactant concentration shows an increase of ZnO thin film crystallinity. Besides crystallinity, the effect of the increase of the concentration also affects the reaction rate of nucleation between zinc and anion, in which it becomes faster. However, besides concentration, the reaction rate is also affected by the temperature reaction.
\nThe preparation of chemical vapor deposition (CVD) or spray pyrolysis is similar with CBD. The zinc precursor must be solved in a solution and has to be evaporated. Evaporation of precursor can be done by several ways. First, zinc precursor must be easy to evaporate or in other words it should be a volatile precursor. Second, by using high temperature, the zinc ingot as precursor can evaporate, and the last step is by using devices such as an atomizer or an ultrasonic transducer that can atomize the precursor or make a mist of it. The arrangement of CVD equipment is shown in Figure 5.
\nCVD using the ultrasonic transducer to produce a precursor mist [
In Figure 5, zinc precursor solution has changed into mist by ultrasonic apparatus and carried by inert gas into the heat furnace chamber with a substrate placed inside the chamber as a target to develop the ZnO thin film. The temperatures of CVD in several experiments are shown in Table 5.
\nTemperature (°C) | \nZinc source | \nAtmosphere | \nReferences | \n
---|---|---|---|
90 | \nZinc acetate | \nO2, N2O, H2O | \n[28] | \n
135–235 | \nDiethylzinc | \nHe-Diborane 2% | \n[29] | \n
120 | \nDimethylzinc | \nO2 | \n[30] | \n
300–375 | \nZinc acetate | \nN2, O3 | \n[31] | \n
Several ZnO thin film CVD condition.
After the precursor mist or vapor is carried and arrived at the heater chamber, some of the zinc precursor particles undergo a reaction with a molecule that contains oxygen in the chamber and forms a larger molecule. Then, this molecule is attached on to the substrate. Due to the high temperature or enough energy, this molecule decomposes into zinc that reacts with the oxygen and then forms a zinc oxide behind. The solvent is evaporated and leaves the chamber with the carrier gas, and at the same time, zinc oxide gets developed as zinc oxide thin film. Or the reaction mechanism could undergo another possibility, when zinc precursor is arrived at the chamber, and it will attach on the substrate and then undergo a reaction or bonding with another molecule which contains oxygen. Due to the high temperature and enough energy to decompose, the zinc precursor molecule and oxygen containing molecule react to the zinc oxide and release some decomposed solvents, which get carried out with gas, and finally the zinc oxide molecule becomes zinc oxide thin film. This schematic is shown in Figure 6.
\nZnO thin film fabrication. Mechanism with CVD [
Spin-coating method uses the energy of the substrate rotation to remove excess or unattached precursor and flatten the thin film. While the precursor drops on the substrate, it will attach on the substrate but the spread is uneven. When the substrate starts to spin, the precursor will spread along the substrate surface due to the centripetal force. A high spin velocity means a high centripetal force to remove the excess of precursor from the substrate. The amount of precursor in the substrate depends on the spin velocity and the precursor’s ability to adhere or attach on the substrate, which is usually called as adhesivity or wet ability. It makes the precursor to attach strongly on the substrate. Besides that, the viscosity also has a role on it. If the precursor has a high viscosity, it will slowly move due to the centripetal force. Consequently, it takes a longer spinning time or a higher spin velocity. The schematic of the spin coater is shown in Figure 7.
\nSchematic representation of a home-built spin coater (a) and details of the rotor (b) [
After the precursor is attached on the substrate, the next stage is drying stage or evaporating the solvent. One thing that should be considered is that the evaporation of the solvent is affected by the viscosity of the precursor. Thus, it is really important to find out the optimum viscosity of the precursor. A high viscosity means difficult to spread well on the substrate surface, and it means that there is a high surface tension which makes it evaporate slowly. The evaporation of the precursor’s solvent is called as preheat treatment. Once the solvent evaporates, it will leave the zinc particle on the substrate and makes the layer thinner. In this method, the desired thickness cannot be achieved by a single process. It should be done in several preheat treatment stages to get the desired thickness. After the preheat treatment, the next stage is to fabricate the zinc oxide from the attached zinc on the substrate by oxidizing heating process. The schematic of alignment process on spin coating is shown in Figure 8.
\nSchematic of the four stages of spin coating (a) Deposition, (b) Spin up, (c) Spin off, (d) Drying [
The precursor solution in spin-coating method is different from the chemical bath deposition and chemical vapor deposition. Precursor preparation in spin coating is more varied. It is not only a solution precursor but also a sol–gel or a colloidal form. Additionally, in this method, the quality on the thin film is affected not only by the concentration of zinc source and other additives but also by the rotation speed, time of spin coating, viscosity, and adhesivity of the precursor solution as mentioned earlier. Table 6 shows several conditions of ZnO spin coating.
\nPrecursor’s form | \nZinc source | \nOther compounds | \nMixture condition | \nReferences | \n
---|---|---|---|---|
Sol-gel | \nZinc acetate dihydrate | \n2-methoxyethanol, monoethanolamine | \nStirring for 30 min at 60°C, aged for 72 h at room temperature | \n[35] | \n
Solution | \nZinc acetate dihydrate | \n2-methoxyethanol, monoethanolamine | \nStirred at 65°C for 90 min | \n[36] | \n
Solution | \nZinc acetate dihydrate | \nEthanol, NH4OH | \npH 10, room temperature | \n[37] | \n
Solution | \nZinc acetate dihydrate | \nEthanol, acetylacetone | \nRoom temperature | \n[38] | \n
Precursor conditions.
Besides that, another thing that brings this method unique lies on the preheat treatment step. The function of this step is to make the coated film dried and attached on the substrate. The repetition of this step is to get a desired thickness. Table 7 shows the condition of several preheat treatments and heat treatments.
\nSpin condition | \nPreheat condition | \nHeat treatment condition | \nAtmosphere | \nReferences | \n
---|---|---|---|---|
2000 rpm for 30 s | \n200°C, 10 s | \n400°C for 1 h | \n— | \n[35] | \n
3000 rpm for 30 s | \n260°C, 10 min | \n400°C for 3 h | \nOxygen | \n[36] | \n
700 rpm for 10 s | \n100°C for 10 min | \n500°C for 2 h | \nAir | \n[37] | \n
2000 rpm for 10 s | \nRoom temperature, 3 min | \n500°C for 2 h | \nOxygen | \n[38] | \n
Heat treatment condition.
In the thin film solar cells, zinc oxide (ZnO) layer acts as a transparent conductive oxide (TCO), which is an important part of solar cells. This thin film can be fabricated by various chemical processes as alternative of vacuum process, where the production is economically cost-effective but still has the same function and properties as vacuum methods.
\nTitanium dioxide (TiO2) is an inorganic substance that is used extensively as a white pigment. Compared with many other inorganic pigments, TiO2 has the advantages of high stability, being non-toxic, and low cost. TiO2 have three polymorphs: anatase, rutile and brookite, but only anatase and rutile crystal forms have been useful as pigment. Both anatase and rutile crystals have very high refractive indices, and their particles can scatter visible light almost completely [1]. The optimum particle size of TiO2 for pigment applications is around 250 nm. In the early application of TiO2 as pigment, it was found that paint faded more rapidly than others when painted films were exposed to the Sun and ultraviolet (UV) light. Coating with inorganic compounds such as alumina or silica suppressed the catalytic activity on the surface and improve the weather resistance, leading titanium dioxide in wide applications as white pigment. Global titanium dioxide pigment sales were about 6 million tons in 2017 and the growth trend of global titanium dioxide pigment sales is continuing over the recent years [2].
In the 60s of the last century, scientists studied the photo-induced phenomena on the solids of TiO2 and ZnO under UV light irradiation [3, 4, 5]. In the early 1970s, research on photocatalysis by TiO2 got wide attention due to the historic discovery of the electrochemical water splitting by use of TiO2 [6]. In the 1990s, photocatalytic research of TiO2 had made progress in the practical applications of TiO2 in the decomposition of harmful organic materials [7, 8]. A function of super hydrophilicity of TiO2 was also discovered [9]. Since the beginning of this century, nano-structured TiO2 has attracted extensive interests. When the particle sizes of TiO2 are reduced down to the nano-meter scale (generally in 1–100 nm), the surface characteristics and surface areas of TiO2 have changed dramatically. The new or enhanced physical and chemical properties of nano-structured TiO2 begin to emerge. The photocatalytic property of nano-structured TiO2 has been greatly enhanced because of the changes in the surface characteristics and surface areas. Quantum effects of nano-structured TiO2 can also have a role to play, affecting its photocatalytic, optical or electronic properties. As the results of academic and industrial research in recent years, enormous progresses have been made in the preparation, characterization, and scientific understandings of nano-structured TiO2. Nano-structured TiO2 have begun to find applications in a wide range of areas including electronic materials, energy, environment, health & medicine, sensors, catalysts, etc.
TiO2 pigment is industrially produced from titanium containing ores by using a Chloride or Sulfate process [1, 10]. Nano-structured TiO2 are made in the different ways, depending on the material characteristics required for the specific applications. A number of innovative fabrication methods of nano-structured TiO2 materials have been developed and are used for different applications. These methods can be broadly classified as the liquid phase or the gas phase methods. Nano-particles, nano-wires, nano-tubes, two or three-dimensional nano-structured TiO2 materials can also be fabricated for different applications [11, 12, 13, 14, 15, 16, 17, 18].
This chapter will discuss and highlight the recent development of applications of titanium dioxide as pigment and as functional materials in the areas of energy, environment, catalyst, and biomedicine.
The main use of titanium dioxide is white pigment, because it absorbs almost no incident light in the visible region of the spectrum (380–700 nm). Titanium dioxide has a strong light scattering power, and scatters incident light in three ways: surface reflection, refraction and diffraction in the crystal [1]. When the refractive index difference between titanium dioxide and medium increases, the reflected light increases and complies with Eq. (1):
np and nm are the refractive index of pigment and medium, respectively [1]. Titanium dioxide has a high refractive index (refractive index of rutile and anatase titanium dioxide is 2.70 and 2.55 respectively) [19]. These high refractive index values enable the rutile and anatase TiO2 pigments to have much greater hiding power in coatings or in plastics, making TiO2 to be a much better pigment than the other chemical substances. Therefore, under the same conditions, only less titanium dioxide is needed to form a coating, which is white and opaque. Studies have shown that the optical properties of titanium dioxide pigments are related to their particle size, and the optimum of particle size of pigmentary titanium dioxide is around 250 nm [1].
Pigmentary TiO2 is inert, non-toxic, stable and less costly. Over 50 percent of all TiO2 pigment produced is consumed by the coatings industry, and approximately a quarter by the paper industry. Eleven per cent goes into plastics; remaining a few percent into inks and other end-uses [20]. Titanium dioxide particles optimized with particle size and surface treatments have excellent hiding power, brightness, and other important features such as resistance to chemical degradation. Rutile pigment is more resistant to UV light than anatase, and is preferred for paints, plastics, especially for the applications in outdoor conditions. Anatase pigment is less abrasive and is used mainly in indoor paints and in paper manufacture. TiO2 is surface treated with one or more inorganic oxides such as alumina, silica, zirconia or a combination of these inorganic oxides, and organic compounds such as polyhydric alcohol to have the required properties of dispersion, photoactivity, and opacity required for a specific application [21].
In coating applications, a relatively high quantity of TiO2 pigment must be used to achieve desirable hiding effect on the coating subtracts, because coatings of titanium dioxide are usually in the form of very thin layers. The pigment volume concentration (PVC) is practically used to specify the amount of TiO2 in a coating. Different types of paints containing TiO2 pigment will have different levels of PVC, depending on different coating applications. TiO2 coatings are used to cover a wide range of surfaces, including indoor and outdoor building, wood products, metal objects, domestic and industrial equipment [21].
In plastics applications, titanium dioxide pigment is used to opacify plastic materials. In some applications, TiO2 is used to improve photodurability. The requirements for TiO2 in plastics are good dispersibility in a polymer system and good heat stability. Hydrophobic organic surface treatments on the pigments are utilized to facilitate their dispersion in the viscous molten plastic resin. These are often silicone oils and other organic compounds for specialized uses. In many plastics applications, a blue undertone is also desirable to mask an intrinsic yellowness in the color of the resin or a slight degradation that occurs during the high-temperature processing. For this reason, plastics pigments often have a smaller crystal size than those for coatings applications [19].
The amount of titanium dioxide used in paper industry is the third largest after coating and plastic industries [20]. Although other white pigments can be used in paper industry, the production of high quality papers must use titanium dioxide as pigment. Titanium dioxide imparts desirable brightness and opacity to high-quality papers. Papers containing titanium dioxide pigment have high strength and have appearance to be white, shiny, thin and smooth. Because photochemical stability is not as critical in paper as in paint, both anatase and rutile pigments are widely be used in paper industry.
In inks applications, performance requirements for TiO2 pigment are different from coatings, plastics and paper. Inks are usually applied to produce a much thinner film on a surface than a general coating. It is very important to choose titanium dioxide particles with good shape, suitable size and size-distribution, smooth surface and non-angular. The type of TiO2 can also affect the rheology, abrasiveness, gloss and redispersibility for ink products and applications.
TiO2 is also widely used as a pigment for coloring of different products in pharmaceuticals and cosmetics industries. The characteristics of titanium dioxide provide interesting colors and allow new properties to pharmaceuticals with very small amounts of pigments. There are many products in this field that contain titanium dioxide, including: shampoos, creams, sunscreens, toothpaste, etc. [10].
With the special physical and chemical properties, nano-structured titanium dioxide has shown a number of promising application prospects in energy generation and storage. These include: solar cells, hydrogen production, and lithium battery [22, 23, 24].
The solar energy is a clean, abundant and renewable energy [25]. The current technology for the conversion of sunlight to electrical power is predominately silicon-based solid state solar cells. In recent years, the new semiconducting material-based solar cells have emerged to offer the possible alternative photovoltaic technology with prospect of cheap fabrication and flexibility [26, 27, 28]. Nano-structured TiO2 has been the main semiconducting material for this new generation of solar cells. In this technology, an electron sensitizer absorbing in the visible is used to inject charge carriers across the semiconductor-electrolyte junction into TiO2 to enhance the conversion efficiency from solar energy, because TiO2 with its band gap of 3.2 electronvolt (eV) absorbs only the ultraviolet part of the solar energy. This type of solar cells is therefore called dye-sensitized solar cells (DSSCs). The dye-sensitized solar cells (DSSCs) have exhibited high performance and have the potential to be low-cost [29, 30, 31, 32, 33].
Figure 1 illustrates the working principle of a dye-sensitized solar cell. The dye-sensitized solar cell consists of two electrodes, a dye-sensitized nano-structured TiO2 mesoporous layer, and a liquid electrolyte containing redox system (
Working principle of a dye-sensitized solar cell.
The nano-structured TiO2 mesoporous layer in a dye-sensitized solar cell has a much larger surface area available for the dye-chemisorptions. The kinetic processes occurring in a dye-sensitized solar cell have been profoundly changed as a result of using nano-structured TiO2. Solar energy-to-electricity conversion efficiencies of DSSCs have been increased. The record for the highest certified single cell and DSSCs module efficiencies are 11.9% and 8.8%, respectively [34].
More recently, TiO2 is used in a new type of solar device so-called pervoskite solar cells. As in DSSCs, TiO2 is used as a mesoporous layer. However, instead of using organic dye in DSSCs, organic lead complex (for example, CH3NH2PbI3) is used to inject electrons into the conduction band of TiO2. In a short period of the recent few years, the reported efficiency of pervoskite solar cells was 9.7% initially, and then 12.0% [35, 36]. Further progress was made with efficiencies above 15.0% [37]. The record for the highest certified single cell and minimodule efficiencies are 20.9% and 16.0%, respectively [34].
In 1972, Fujishima and Honda discovered the phenomenon of photocatalytic splitting of water on a TiO2 electrode under UV light [6, 38, 39]. Compared with other photocatalysts, TiO2 is much more promising as it is stable, non-corrosive, environmentally friendly, abundant and cost effective. Figure 2 illustrates the mechanism of the photocatalytic hydrogen production by TiO2 semiconducting materials. When excited by photons which have energy equal to or higher than their band gap (
Illustration of mechanism of photocatalytic hydrogen production by TiO2.
The photo-generated (e−) and (h+) in TiO2 can recombine, releasing energy in the form of heat or photons. The photo-generated (e−) and (h+) that migrate to the surface of TiO2 without recombination can reduce and oxidize H2O molecules adsorbed on the surface of TiO2 to generate H2 and O2.
As can be seen in Figure 2, the conduction band level of TiO2 is more negative than the hydrogen production level (
Despite many advantages of using TiO2 for photocatalytic hydrogen production, the efficiency using solar energy for water-splitting by TiO2 is still low, and is currently not been used for industrial scale of hydrogen production. The low energy conversion efficiency of TiO2 in water-splitting is believed to be caused by the wasteful recombination of electron/hole pairs, backward reaction of combining hydrogen and oxygen into water, and limitations for TiO2 to utilize visible light due to its large band gap. Research has been carried out to produce nano-structured TiO2 with a narrower band gap in order to utilize visible-light energy more efficiently. Progresses have been made in modifying the band gap of nano-structured TiO2 by means of metal loading, ion doping, metal ion-implantation, dye sensitization and composite TiO2. Noble metals, such as Pt, Au, Pd, and Ag, have been reported to be very effective in enhancing TiO2 photocatalysis [40, 41, 42, 43]. Carbon-doped nano-structured TiO2 have showed much more efficient water splitting under visible-light illumination [44]. A study using a dye sensitizer for photocatalytic hydrogen production was investigated [45]. A visible light absorber, C3N4, has been coupled to many wide-band gap semiconductors to improve solar harvesting. A 50 wt % C3N4/TiO2 junction was found to double H2 evolution compared to pure C3N4 under visible irradiation [46].
Lithium-ion batteries are a type of rechargeable batteries commonly used in consumer electronics. Lithium ion battery system and technology has been a revolutionary change in the field of power supply battery. Anode materials based on titanium oxides are the promising candidates as alternative materials to carbonaceous anodes due to advantages in terms of cost, safety and toxicity [47, 48]. TiO2 also exhibits excellent structural stability, high discharge voltage plateau (more than 1.7 V versus Li+/Li), and excellent cycling stability [49, 50].
Typically the Li+ insertion–extraction reaction for TiO2 polymorphs occurs according to reaction (3):
x can range between 0 and 1, depending strongly on the polymorph, particle size, and morphology of TiO2. The maximum theoretical capacity is 335 mAh g−1 which corresponds to x = 1. This makes TiO2 a highly competitive alternative to graphite anodes having a theoretical capacity of 372 mAh g−1 [51, 52, 53]. However, TiO2 has limitations, such as low capacity, low electrical conductivity, and poor rate capability. Strategies have been developed to address the issues of TiO2-based anodes. These include the use of multi-dimensional nanostructured TiO2, composite and coating materials, and element doping.
One dimensional anatase TiO2 nanofiber anodes were used as an anode active material in Li ion batteries and exhibited a high lithium storage capacity, a stable cycle life, and good rate capability [54]. Two dimensional TiO2 nanosheets have been shown to exhibit the superior capacities, improved cycling stability and rate capabilities, owing to unique exposed facets, shortened path, and reserved porous structures [55, 56, 57]. Nanostructured TiO2 is a low voltage insertion host for Li and a fast Li insertion/extraction host [58, 59]. These characteristics provide nanostructured TiO2 a potential anode material for high-power Li-ion batteries. Studies on the use of nanostructured TiO2 as anode with LiCoO2 cathode demonstrated specific capacity of 169 mAh g−1 [60]. Xu, et al. investigated electrochemical performance of TiO2-coated LiCoO2 and LiMn2O4 in different potential regions [61]. Mechanically blended composite of nanosized TiO2 and carbon nanotubes (CNTs) has been used as potential anode materials for Li-ion batteries. It was found that the TiO2/CNTs nanocomposites exhibited an improved cycling stability and higher reversible capacity than CNTs [62, 63]. Metal oxide coatings containing TiO2 can efficiently improve the capacitive performance of the materials through synergistic effects in an electrode system [64, 65, 66, 67].
Excitation of TiO2 with UV light with energy greater than the band gap (>3.2 eV) promotes electrons from valence band into the conduction band and generates electron/hole pairs [68, 69]. Figure 3 illustrates the mechanism of generating reactive radicals from TiO2 under irradiation of UV light. The conduction band electrons e− can reduce molecular oxygen to generate (O2•−) superoxide radicals, and valance band holes h+ is positive enough to generate (OH•) radicals from H2O or OH− on TiO2 surface. OH• radicals have the strongest oxidation potential. Superoxide radicals (O2•−) have moderate oxidation potentials, but their diffusion distances can reach up to hundreds of micrometers [70]. Both radicals are very reactive, and they attack the organic matter present or near the surface of TiO2 to degrade toxic and bio-resistant compounds or species into CO2, H2O, etc. [69, 71].
Mechanism of generating reactive radicals (OH•) and superoxide (O2•−) from TiO2 under irradiation of UV light.
The generation of reactive radicals (OH•) and (O2•−) is affected by the crystalline state, and properties such as surface area and particle size. Although anatase and rutile have the similar band gaps, anatase has shown to have more rapid rate in photo-degradation of organic or bio-resistant compound than rutile [72, 73]. Therefore, nano-structured anatase TiO2 is often used as a catalyst in photo-degradation applications.
One application, which is commercially successful, is the nano-structured TiO2 material for self-clean and antibacterial uses [68, 74, 75]. Many nano-structured TiO2 material based products have been used as construction materials [76, 77, 78, 79, 80, 81, 82]. Self-clean application is based on the actions of sunlight, rainwater, and photocatalytic properties of TiO2. Under the irradiation of sunlight, adsorbed organic materials like oil can be decomposed by hydroxyl radicals on the surface of TiO2. Because of the hydrophilic property of TiO2 surface, contaminates and dust can be washed away off by rainwater. Tiles containing nano-structured TiO2 have been used to construct photocatalytic surface to decompose bacteria and viruses on the surface or bacteria floating in the air as they come in contact with surface.
Studies have shown that the photocatalytic properties of TiO2 can sometimes be enhanced by doping TiO2 with different elements. For example, TiO2 nano-particles containing Ag+ have been widely used in antibacterial plastics and coatings [83, 84, 85]. Fe or Sb-doped TiO2 have been used to make coatings with high antibacterial property [79, 80].
Nano-structured self-clean glass is now an important commercial product. Pilkington Glass has developed the first self-cleaning windows. The window glass is coated with a very thin and transparent TiO2 layer to have the properties of photocatalysis and hydrophilicity on the glass surface. Photocatalysis of TiO2 break down the organic dirt adsorbed onto the window in sunlight, and the decomposed organic species is washed away efficiently by rain or other water in the form of thin layer instead of droplets [86].
Another important application of nano-structured TiO2 is in the water-treatment, utilizing its photocatalytic properties [87, 88, 89, 90, 91, 92]. Research of using nano-structured TiO2 for water-treatment has been very active in recent years. TiO2 has been used in the photocatalytic decomposition of organic dyes in waste water, and organic pollutants such as pesticides, dyes and pharmaceuticals in other contaminated water [93, 94]. The photocatalytic decomposition of organic matters in water are all based on the mechanism of the generation of highly reactive radicals (OH•) and superoxide ions (O2•−) in TiO2 under UV irradiation, as illustrated in Figure 3. TiO2 has been considered to be the best choice to be used as photo-catalysts, as TiO2 is chemically inert, and cheap to manufacture and to apply.
The complete separation and recycling of TiO2 fine particles is important for the practical applications. A number of innovative methods have been developed for this purpose. For example, fixing TiO2 nano-particles on supports such as glass plates, aluminum sheets, and activated carbon are investigated to recycle the catalyst [95], or developing TiO2 catalyst system which can be separated from reaction liquid by applying external magnetic field [96, 97].
Because TiO2 and many other semiconductors have the large band gaps, the application of photocatalytic water treatment using TiO2 is limited by its relatively low efficiency. To improve photocatalytic efficiency of TiO2 for water treatment, as well as other photocatalytic applications, Enormous research has been carried out to extend the photocatalytic response of TiO2 into the visible range [98]. One of the strategies for improving photocatalytic efficiency for water treatment is to modify the band gap of TiO2 by incorporation of other ions into TiO2 structure, through metal and non-metal doping, metal implantation, noble metal loading, and others [99, 100, 101, 102, 103, 104].
TiO2-based composite materials have been widely used as catalysts [105, 106, 107]. TiO2 is used as support in commercial V2O5-WO3/TiO2 catalysts for the selective catalytic reduction (SCR) of NOx. In SCR technology, highly undesirable NOx acid gas emissions from various industrial sources are reduced to harmless N2 and H2O. The V2O5-WO3/TiO2 catalysts are widely used in commercial applications because of their excellent thermal stability and lower oxidation activity for the conversion of SO2 to SO3 [108, 109]. The V2O5-WO3/TiO2 catalysts have become the most widely used industrial catalysts for these SCR applications since the introduction of this technology in the early of 1970s [110].
TiO2 has the potential to induce the reductive chemical transformation. The reductive photocatalysis of ethyne and ethene have been reported [111, 112, 113]. TiO2 have been used as a useful catalyst for the reduction of carbonyl compounds such as aldehydes or ketones, nitro compounds, imines and for the some of the chemical transformations involving redox processes. Photocatalysis on TiO2 is a light-driven redox reaction. Redox reactions can be induced by electrons (e−) generated in conduction band (CB) and holes (h+) simultaneously generated in valance band (VB) under the irradiation of light. The electrons in the conduction band are readily available for transferring while the holes in the valence band are open for donations [114]. The photocatalytic reduction of an electron acceptor can be carried out in the presence of a large excess amount of electron donors such as alcohols or amines, which are used to scavenge (h+). Oxygen (O2) is a competitive electron acceptor, and can influence the reduction reaction. Therefore, the reductive chemical transformation should be generally performed in an O2 free environment. Under these conditions, a photocatalytic reduction proceeds through transferring electrons (e−) in CB or trapped at surface defects of TiO2 into the organic molecules adsorbed on TiO2 surface. The photocatalytic reduction of aldehydes, nitro compounds, and imines have been reported. Aromatic aldehydes and ketones were reduced to the corresponding alcohols using TiO2 as a photocatalyst [115, 116]. Aromatic and aliphatic nitro compounds were reduced to corresponding amines using TiO2 as catalyst [117]. The direct reduction of imines to corresponding secondary amines was studied [118].
The sunlight reaching the earth’s surface contains UV, visible and infrared wavelength. The Sun releases ultraviolet (UV) radiation in three different wavelengths, and all are harmful in different ways. These wavelengths in sunlight are called UVA (315–400 nm), UVB (280–315 nm) and UVC (100–280 nm) [119]. Because the earth’s atmosphere blocks most UVC rays, UVC does not generally reach the earth’s surface to a significant degree. Therefore, they are not thought to be important contributors to the biological effects on human skin [120]. UVA wavelength penetrates more deeply into the skin causing photo-aging and the formation of skin cancer. UVB is shorter, and damages the surface of the skin. The damage from UVB can cause sunburn and cancer [121, 122, 123, 124].
TiO2 is a semiconducting material with very high refractive index. The high refractive index is what allows the substance to scatter visible light. The current method of preventive treatment again harmful UV radiation involves suspending a substance that either absorbs or scatters UV radiation in a thick emulsion, called sunscreen. Titanium dioxide (TiO2) is an ingredient in sunscreens where its loading is frequently 2–15%. Sunscreen typically contain chemical filters that are organic compounds that absorb strongly the UV (most often UVB) and physical filters such as TiO2 and ZnO that block UVA and UVB sunlight through absorption, reflection and scattering.
In biomedicine, TiO2 nanoparticles with their extraordinary stability, exceptional photo-reactivity, and biocompatibility have a special place in biomedical solutions. The therapeutic potential of TiO2 lies in the ability of these particles in response to light to produce reactive oxygen species (ROS). Production of ROS is the main factor in causing detrimental effects on cells. This effect was first applied by Cai
In both photodynamic therapy (PDT) and sonodynamic therapy (SDT), nano-structured titanium dioxide is used as an agent to produce reactive oxygen species (ROS). Photodynamic therapy (PDT) is an anti-tumor method in which photosensitive agent is applied and target area is illuminated for the activation of the agent. TiO2 is normally a photocatalyst that produces oxidizing radicals by reacting with water during UV exposure and can damage nearby cells [127, 128]. Titanium dioxide and zinc oxide are two of the most effective photosensitizers for PDT applications. In sonodynamic therapy, TiO2 acts as a sonocatalyst. Studies have shown that TiO2 particles can promote the production of hydroxyl (OH•) radicals by ultrasound irradiation even in dark conditions [129, 130]. Ultrasound technology has been already used for some cancer therapies, either by generating localized heating using high intensity ultrasound or by activating a drug release using low intensity ultrasound. Ultrasound can penetrate inches below the skin. Therefore, it can be used to activate TiO2 nanoparticles deep below the skin surface.
TiO2 has been considered to be a good material for the design of drug carriers, for the reasons that the shape and size of TiO2 nanoparticles can be engineered to control their electronic and chemical properties, and the surface of TiO2 nanoparticles can be functionalized with various drug molecules [131, 132]. These capabilities bring new opportunities for more efficient site-selective chemistry of TiO2, and form the vehicles for drug delivery applications.
Titanium dioxide is a stable, non-toxic inorganic material with very high refractive index, and can scatter visible light almost completely. The particle sizes for pigmentary TiO2 are generally engineered to be around 250 nm to have optimized light scattering property. After coating with inorganic compounds such as alumina or silica, the catalytic activity on the surface of TiO2 particles is suppressed and the weather resistance is improved. Because of the superior optical properties and chemical stability, TiO2 has been developed and used as white pigment over several decades. Pigmentary titanium dioxide has excellent ability to impart brightness and opacity. Titanium dioxide has now been a well established inorganic white pigment and is widely applied in the coatings, plastics, paper manufacturing, and in many common products. Global sales of titanium dioxide pigment were about 6 million tons in 2017 and the growth trend of global titanium dioxide pigment sales is continuing over the recent years.
Titanium dioxide is also a semiconducting material which is characterized by a filled valence band and an empty conduction band. When excited by photons which have energy equal to or higher than their band gap, electrons (e−) in valence band of TiO2 are promoted to the conduction band and holes (h+) are created in the valence band of TiO2. Because of the discovery of photocatalytic properties of titanium dioxide, and the ability to engineer TiO2 nanomaterials for controlling their electronic and chemical properties, the applications of titanium dioxide as functional materials have become the focus of enormous research and development in the recent years. The applications of nano-structured TiO2 can now be found in a wide range of areas including electronic materials, energy, environment, health & medicine, and catalysts. A number of materials containing nano-structured TiO2 have become the important commercial products. Further research is continuing to modify the electronic and chemical properties, as well as surface characteristics of TiO2 for the creation of more efficient TiO2 functional materials in more specific application areas.
This work was financially supported by the Pangang Group under a Basic Research Grant.
The authors declare no conflict of interest.
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Saleh and Amal I. Hassan",coverURL:"https://cdn.intechopen.com/books/images_new/11120.jpg",editedByType:"Edited by",publishedDate:"June 23rd 2022",editors:[{id:"144691",title:"Prof.",name:"Hosam M.",middleName:null,surname:"Saleh",slug:"hosam-m.-saleh",fullName:"Hosam M. Saleh"}],equalEditorOne:null,equalEditorTwo:null,equalEditorThree:null,productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"10696",title:"Applications of Calorimetry",subtitle:null,isOpenForSubmission:!1,hash:"8c87f7e2199db33b5dd7181f56973a97",slug:"applications-of-calorimetry",bookSignature:"José Luis Rivera Armenta and Cynthia Graciela Flores Hernández",coverURL:"https://cdn.intechopen.com/books/images_new/10696.jpg",editedByType:"Edited by",publishedDate:"June 23rd 2022",editors:[{id:"107855",title:"Dr.",name:"Jose Luis",middleName:null,surname:"Rivera Armenta",slug:"jose-luis-rivera-armenta",fullName:"Jose Luis Rivera Armenta"}],equalEditorOne:null,equalEditorTwo:null,equalEditorThree:null,productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}}]},subject:{topic:{id:"135",title:"Environmental Studies",slug:"environmental-studies",parent:{id:"12",title:"Environmental Sciences",slug:"environmental-sciences"},numberOfBooks:5,numberOfSeries:0,numberOfAuthorsAndEditors:177,numberOfWosCitations:193,numberOfCrossrefCitations:130,numberOfDimensionsCitations:338,videoUrl:null,fallbackUrl:null,description:null},booksByTopicFilter:{topicId:"135",sort:"-publishedDate",limit:12,offset:0},booksByTopicCollection:[{type:"book",id:"8969",title:"Deserts and Desertification",subtitle:null,isOpenForSubmission:!1,hash:"4df95c7f295de7f6003e635d9a309fe9",slug:"deserts-and-desertification",bookSignature:"Yajuan Zhu, Qinghong Luo and Yuguo Liu",coverURL:"https://cdn.intechopen.com/books/images_new/8969.jpg",editedByType:"Edited by",editors:[{id:"180427",title:"Dr.",name:"Yajuan",middleName:null,surname:"Zhu",slug:"yajuan-zhu",fullName:"Yajuan Zhu"}],equalEditorOne:null,equalEditorTwo:null,equalEditorThree:null,productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"6706",title:"Environmental Risks",subtitle:null,isOpenForSubmission:!1,hash:"ea444f5d9f74628b340b2d9514bca236",slug:"environmental-risks",bookSignature:"Florin-Constantin Mihai and Adrian Grozavu",coverURL:"https://cdn.intechopen.com/books/images_new/6706.jpg",editedByType:"Edited by",editors:[{id:"175726",title:"Dr.",name:"Florin-Constantin",middleName:null,surname:"Mihai",slug:"florin-constantin-mihai",fullName:"Florin-Constantin Mihai"}],equalEditorOne:null,equalEditorTwo:null,equalEditorThree:null,productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"5995",title:"Mediterranean Identities",subtitle:"Environment, Society, Culture",isOpenForSubmission:!1,hash:"5254b511e85984b9457a09ddc2758a1c",slug:"mediterranean-identities-environment-society-culture",bookSignature:"Borna Fuerst-Bjelis",coverURL:"https://cdn.intechopen.com/books/images_new/5995.jpg",editedByType:"Edited by",editors:[{id:"138475",title:"Prof.",name:"Borna",middleName:null,surname:"Fuerst-Bjeliš",slug:"borna-fuerst-bjelis",fullName:"Borna Fuerst-Bjeliš"}],equalEditorOne:null,equalEditorTwo:null,equalEditorThree:null,productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"1011",title:"International Perspectives on Global Environmental Change",subtitle:null,isOpenForSubmission:!1,hash:"aaa208c16030078cdca711a1867ca7ff",slug:"international-perspectives-on-global-environmental-change",bookSignature:"Stephen S. Young and Steven E. Silvern",coverURL:"https://cdn.intechopen.com/books/images_new/1011.jpg",editedByType:"Edited by",editors:[{id:"96190",title:"Dr.",name:"Stephen",middleName:null,surname:"Young",slug:"stephen-young",fullName:"Stephen Young"}],equalEditorOne:null,equalEditorTwo:null,equalEditorThree:null,productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}},{type:"book",id:"2110",title:"Relevant Perspectives in Global Environmental Change",subtitle:null,isOpenForSubmission:!1,hash:"a531a19888ec539192408b7a229fdbf9",slug:"relevant-perspectives-in-global-environmental-change",bookSignature:"Julius Ibukun Agboola",coverURL:"https://cdn.intechopen.com/books/images_new/2110.jpg",editedByType:"Edited by",editors:[{id:"107567",title:"Dr.",name:"Julius",middleName:"Ibukun",surname:"Agboola",slug:"julius-agboola",fullName:"Julius Agboola"}],equalEditorOne:null,equalEditorTwo:null,equalEditorThree:null,productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}}],booksByTopicTotal:5,seriesByTopicCollection:[],seriesByTopicTotal:0,mostCitedChapters:[{id:"27194",doi:"10.5772/29375",title:"Using Fuzzy Cognitive Mapping in Environmental Decision Making and Management: A Methodological Primer and an Application",slug:"using-fuzzy-cognitive-mapping-in-environmental-decision-making-and-management-a-methodological-prime",totalDownloads:4654,totalCrossrefCites:41,totalDimensionsCites:89,abstract:null,book:{id:"1011",slug:"international-perspectives-on-global-environmental-change",title:"International Perspectives on Global Environmental Change",fullTitle:"International Perspectives on Global Environmental Change"},signatures:"Elpiniki Papageorgiou and Areti Kontogianni",authors:[{id:"6011",title:"Dr.",name:"Elpiniki",middleName:null,surname:"Papageorgiou",slug:"elpiniki-papageorgiou",fullName:"Elpiniki Papageorgiou"},{id:"71620",title:"Prof.",name:"Areti",middleName:"D.",surname:"Kontogianni",slug:"areti-kontogianni",fullName:"Areti Kontogianni"}]},{id:"27184",doi:"10.5772/26954",title:"Effect of Environmental Change on Secondary Metabolite Production in Lichen-Forming Fungi",slug:"effect-of-environmental-change-on-secondary-metabolite-production-in-lichen-forming-fungi",totalDownloads:7066,totalCrossrefCites:14,totalDimensionsCites:29,abstract:null,book:{id:"1011",slug:"international-perspectives-on-global-environmental-change",title:"International Perspectives on Global Environmental Change",fullTitle:"International Perspectives on Global Environmental Change"},signatures:"Christopher Deduke, Brinda Timsina and Michele D. Piercey-Normore",authors:[{id:"68386",title:"Dr.",name:"Michele",middleName:null,surname:"Piercey-Normore",slug:"michele-piercey-normore",fullName:"Michele Piercey-Normore"},{id:"68390",title:"BSc.",name:"Chris",middleName:null,surname:"Deduke",slug:"chris-deduke",fullName:"Chris Deduke"},{id:"102711",title:"Ms.",name:"Brinda",middleName:null,surname:"Timsina",slug:"brinda-timsina",fullName:"Brinda Timsina"}]},{id:"27182",doi:"10.5772/26536",title:"Primary Succession in Glacier Forelands: How Small Animals Conquer New Land Around Melting Glaciers",slug:"primary-succession-in-glacier-forelands-how-small-animals-conquer-new-land-around-melting-glaciers",totalDownloads:4996,totalCrossrefCites:8,totalDimensionsCites:28,abstract:null,book:{id:"1011",slug:"international-perspectives-on-global-environmental-change",title:"International Perspectives on Global Environmental Change",fullTitle:"International Perspectives on Global Environmental Change"},signatures:"Sigmund Hågvar",authors:[{id:"66992",title:"Prof.",name:"Sigmund",middleName:null,surname:"Hågvar",slug:"sigmund-hagvar",fullName:"Sigmund Hågvar"}]},{id:"55867",doi:"10.5772/intechopen.69214",title:"The Marine Biodiversity of the Mediterranean Sea in a Changing Climate: The Impact of Biological Invasions",slug:"the-marine-biodiversity-of-the-mediterranean-sea-in-a-changing-climate-the-impact-of-biological-inva",totalDownloads:2351,totalCrossrefCites:9,totalDimensionsCites:19,abstract:"The Mediterranean Sea, one of the most complex marine ecosystems, is inhabited by a rich and diverse biota which is disproportionate to its dimensions. It is currently affected by different pressures, mainly driven by human activities such as climate change and bioinvasions. This Sea, also due to its geographic position (wedged between the temperate climate of central Europe and the arid climate of northern Africa), seems to be one of the regions most susceptible to global climate change. The increased rates of introduction and spread of marine alien species may represent a supplementary stress factor to Mediterranean marine native biota already challenged by climatic abnormalities. The Suez Canal is considered to be the main vector of introduction of non‐indigenous marine species into the Mediterranean Sea. Due to the dramatically accelerating rate of such introductions and due to the sheer magnitude of shipping traffic, the Mediterranean Sea may be considered as a true hotspot of marine bioinvasions. The complexity of interactions between native and invasive species and the associated resulting impacts make environmental management of such an issue particularly difficult. A collaboration between researchers, resource management agencies and policy makers is called for to bolster the effectiveness of invasive species management procedures.",book:{id:"5995",slug:"mediterranean-identities-environment-society-culture",title:"Mediterranean Identities",fullTitle:"Mediterranean Identities - Environment, Society, Culture"},signatures:"Anna M. Mannino, Paolo Balistreri and Alan Deidun",authors:[{id:"202075",title:"Prof.",name:"Alan",middleName:null,surname:"Deidun",slug:"alan-deidun",fullName:"Alan Deidun"},{id:"203773",title:"Dr.",name:"Anna Maria",middleName:null,surname:"Mannino",slug:"anna-maria-mannino",fullName:"Anna Maria Mannino"},{id:"203777",title:"Dr.",name:"Paolo",middleName:null,surname:"Balistreri",slug:"paolo-balistreri",fullName:"Paolo Balistreri"}]},{id:"55996",doi:"10.5772/intechopen.69410",title:"The Fire in the Mediterranean Region: A Case Study of Forest Fires in Portugal",slug:"the-fire-in-the-mediterranean-region-a-case-study-of-forest-fires-in-portugal",totalDownloads:2079,totalCrossrefCites:8,totalDimensionsCites:19,abstract:"Forest fires are a common disturbance in many forest systems in the world and in particular in the Mediterranean region. Their origins can be either natural or anthropogenic. The effects in regard to the time trends, vegetation, and soil will be reflected in the species distribution, forest composition, and soil potential productivity. In general, it can be said that the larger the fire and the shorter the time between two consecutive occurrences, the higher the probability to originate shifts in vegetation and soil degradation. In the Mediterranean region, the number of fire ignitions does not reflect the burnt area due to the occurrence of very large fires. The latter occur in a very small proportion of the number of ignitions, but result in very large burnt areas. Also there seems to be an increasing trend toward larger fires in the Mediterranean region due mainly to climatic and land use changes. This case study highlights the importance of vegetation regrowth a short time after the fire to maintain both forest systems and soil conservation.",book:{id:"5995",slug:"mediterranean-identities-environment-society-culture",title:"Mediterranean Identities",fullTitle:"Mediterranean Identities - Environment, Society, Culture"},signatures:"Ana Cristina Gonçalves and Adélia M.O. Sousa",authors:[{id:"187880",title:"Prof.",name:"Adélia",middleName:null,surname:"Sousa",slug:"adelia-sousa",fullName:"Adélia Sousa"},{id:"194484",title:"Prof.",name:"Ana Cristina",middleName:null,surname:"Gonçalves",slug:"ana-cristina-goncalves",fullName:"Ana Cristina Gonçalves"}]}],mostDownloadedChaptersLast30Days:[{id:"77362",title:"Role of Eco-Village Initiatives in Mitigating Desertification in Semi-Arid Areas of Tanzania",slug:"role-of-eco-village-initiatives-in-mitigating-desertification-in-semi-arid-areas-of-tanzania",totalDownloads:112,totalCrossrefCites:0,totalDimensionsCites:0,abstract:"Climate change adaptation actions for mitigating desertification and improving community livelihood in developing countries have attracted numerous scholarly works. However, there have been insufficient findings on the adaptation regarding the eco-village practices in semi-arid areas in particular. This inspired a study to assess the role of eco-village practices in strengthening climate change adaptive capacity and mitigating desertification in semi-arid areas of Chololo village, Dodoma region in central Tanzania. Data were collected using mixed methods, that is, household survey (92), focus group discussions (21), key informants interviews (6), field observation and documentary review. Statistical Package for Social Sciences (SPSS) and content analysis were used in analyzing quantitative and qualitative data respectively. The study found a relatively high level of community awareness on the eco-village initiative; the initiative rehabilitated village forest reserve; improved land productivity for sorghum and pearl millet; increased number of planted trees; and strengthening communities’ adaptation to climate change through improved households’ nutrition, income and reduced water stress.",book:{id:"8969",slug:"deserts-and-desertification",title:"Deserts and Desertification",fullTitle:"Deserts and Desertification"},signatures:"Fredy S. Mswima and Abiud L. Kaswamila",authors:[{id:"115390",title:"Prof.",name:"Abiud L.",middleName:"Lucas",surname:"Kaswamila",slug:"abiud-l.-kaswamila",fullName:"Abiud L. Kaswamila"},{id:"415117",title:"Dr.",name:"Fredy S.",middleName:null,surname:"Mswima",slug:"fredy-s.-mswima",fullName:"Fredy S. Mswima"}]},{id:"77741",title:"Characteristic on the Stability of Haloxylon ammodendron Plantation in the Southern Fringe of Gurbantunggut Desert, Northwest China",slug:"characteristic-on-the-stability-of-em-haloxylon-ammodendron-em-plantation-in-the-southern-fringe-of-",totalDownloads:165,totalCrossrefCites:0,totalDimensionsCites:0,abstract:"Using chronosequence theory and method, the characteristics of vegetation-soil coupling and structure stability of Haloxylon ammodendron plantations in the southern fringe of Gurbantunggut Desert were analyzed. The results showed, the canopy storey of H. ammodendron plantation experienced three stages, rapid growth (the age of 7 to 20), then slow growth (the age of 20 to 28) and last decline (over the age of 28). The best natural regeneration started from 17-yr-old plantation. Vegetation-soil system coupling degree (C) and coupling coordinative degree (D) of plantations with different age were not one-to-one correspondence. The system of H. ammodendron plantations always stayed in disorder recession, vegetation and soil were prone to loss type during the process of sand-fixation. Five principal components evaluated that the first rank was 42-yr-old plantation. It was inferred that the trend of the vegetation and soil system was from senescence to harmonious development. So the trend of coordinated development between vegetation and soil would be promoted, if the artificial tending and management measures strengthened.",book:{id:"8969",slug:"deserts-and-desertification",title:"Deserts and Desertification",fullTitle:"Deserts and Desertification"},signatures:"Qinghong Luo, Qimin Chen, Miao He and Na Li",authors:[{id:"340564",title:"Dr.",name:"Qinghong",middleName:null,surname:"Luo",slug:"qinghong-luo",fullName:"Qinghong Luo"},{id:"347848",title:"Mr.",name:"Qimin",middleName:null,surname:"Chen",slug:"qimin-chen",fullName:"Qimin Chen"},{id:"348214",title:"Associate Prof.",name:"Miao",middleName:null,surname:"He",slug:"miao-he",fullName:"Miao He"},{id:"348215",title:"Associate Prof.",name:"Na",middleName:null,surname:"Li",slug:"na-li",fullName:"Na Li"}]},{id:"77086",title:"Bowing Sand, Dust, and Dunes, Then and Now–A North American Perspective",slug:"bowing-sand-dust-and-dunes-then-and-now-a-north-american-perspective",totalDownloads:94,totalCrossrefCites:0,totalDimensionsCites:0,abstract:"Dune fields of the present day, the Dust Bowl disaster of the 1930s U.S. Great Plains, and contemporary efforts to forecast, simulate, and understand dust storms have a striking, uniform commonality. What these apparently diverse phenomena have in common is that they all result from blowing sand and dust. This review paper unifies these three disparate but related phenomena. Its over-arching goal is to clearly explain these manifestations of windblown sand and dust. First, for contemporary dune fields, we offer reviews of two technical papers that explain the eolian formation and the continuing development of two major dune fields in southeastern California and northwestern Sonora, Mexico: the Algodones Dunes and the Gran Desierto de Altar. Second, historical, geological, meteorological, and socioeconomic aspects of the 1930s Great Plains Dust Bowl are discussed. Third, and last, we return to the present day to summarize two lengthy reports on dust storms and to review two technical papers that concern their forecasting and simulation. The intent of this review is to acquaint the interested reader with how eolian transport of sand and dust affects the formation of present-day dune fields, human agricultural enterprises, and efforts to better forecast and simulate dust storms. Implications: Blowing sand and dust have drastically affected the geological landscape and continue to shape the formation of dune fields today. Nearly a century ago the U.S. Great Plains suffered through the Dust Bowl, yet another consequence of blowing sand and dust brought on by drought and mismanagement of agricultural lands. Today, this phenomenon adversely affects landscapes, transportation, and human respiratory health. A more complete understanding of this phenomenon could (and has) led to more effective mitigation of dust sources, as well as to a more accurate predictive system by which the public can be forewarned.",book:{id:"8969",slug:"deserts-and-desertification",title:"Deserts and Desertification",fullTitle:"Deserts and Desertification"},signatures:"Peter Hyde and Alex Mahalov",authors:[{id:"348247",title:"Dr.",name:"Peter",middleName:null,surname:"Hyde",slug:"peter-hyde",fullName:"Peter Hyde"},{id:"419631",title:"Dr.",name:"Alex",middleName:null,surname:"Mahalov",slug:"alex-mahalov",fullName:"Alex Mahalov"}]},{id:"61738",title:"Assessment of the Riparian Vegetation Changes Downstream of Selected Dams in Vhembe District, Limpopo Province on Based on Historical Aerial Photography",slug:"assessment-of-the-riparian-vegetation-changes-downstream-of-selected-dams-in-vhembe-district-limpopo",totalDownloads:1571,totalCrossrefCites:0,totalDimensionsCites:2,abstract:"Dams have been associated with various impacts on downstream river ecosystems, including a decrease in stream flow, species biodiversity, water quality, altered hydrology and colonisation of the area by invasive alien plant species. The impacts normally interfere with the ecosystem functioning of riparian and aquatic environments, thereby leading to decreased biodiversity. This study aims to assess the impacts of dams on downstream river ecosystems, using data from aerial photographs and orthophotos, supplemented by field work. Five dams in Limpopo Province, South Africa, were selected (Albasini, Damani, Mambedi, Nandoni and Vondo), and photographs from different years were used. The area devoid of trees of certain species both downstream and upstream of the dams was calculated using grids of predetermined square sizes on each available photograph. Aerial photographs and orthophoto data were supplemented by field work. The nearest-individual method was used in the field to determine tree density of particular tree species. The environments downstream of the dams show a loss of obligate riparian vegetation and an increase of obligate terrestrial vegetation (Acacia Karroo, Acacia Ataxacantha and Bauhinia galpinii). Treeless area increased in all cases, especially in the case of Mambedi and Vondo dams, indicating lower resilience and higher fragility there.",book:{id:"6706",slug:"environmental-risks",title:"Environmental Risks",fullTitle:"Environmental Risks"},signatures:"John M. Mokgoebo, Tibangayuka A. Kabanda and Jabulani R.\nGumbo",authors:[{id:"224099",title:"Prof.",name:"Jabulani",middleName:null,surname:"Gumbo",slug:"jabulani-gumbo",fullName:"Jabulani Gumbo"},{id:"250766",title:"Mr.",name:"M.J.",middleName:null,surname:"Mokgoebo",slug:"m.j.-mokgoebo",fullName:"M.J. Mokgoebo"},{id:"250767",title:"Prof.",name:"T.A.",middleName:null,surname:"Kabanda",slug:"t.a.-kabanda",fullName:"T.A. Kabanda"}]},{id:"78428",title:"Jojoba - The Gold of Desert",slug:"jojoba-the-gold-of-desert",totalDownloads:247,totalCrossrefCites:0,totalDimensionsCites:0,abstract:"Jojoba [Simmondsia chinensis (Link) Schneider] is evergreen, perennial and drought resistant shrub belongs to the family of Simmondsiaceae. It is a multipurpose oil seed crop mainly grown in desert regions of world. This plant has unique oil among plant kingdom which is chemically a liquid-wax. The liquid-wax is made up of an ester of long chain fatty acids and alcohols. The liquid-wax is unique in nature because have no traces of glycerine and easily modified via hydrolysis, hydrogenation, halogenation, sulfurization, phosphosulfurization and ozonization techniques. The main uses of liquid-wax in various industries like cosmetics, pharmaceuticals, petrochemicals and lubricants. It is a potential seed oil crop for desert region so it is well known as the gold of desert. The main purpose of this chapter is to review the complete information about this plant so that it can produce and utilized maximally. 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He obtained a Master’s degree in Public Health and PhD in Public Health and Epidemiology. He has a background in Clinical Medicine and has taken courses at higher diploma levels in public health from University of Transkei, Republic of South Africa, and African Medical and Research Foundation (AMREF) in Nairobi, Kenya. Dr. Kasenga worked in different places in and outside Malawi, and has held various positions, such as Licensed Medical Officer, HIV/AIDS Programme Officer, HIV/AIDS resource person in the International Department of Diakonhjemet College, Oslo, Norway. He also managed an Integrated HIV/AIDS Prevention programme for over 5 years. He is currently working as a Director for the Health Ministries Department of Malawi Union of the Seventh Day Adventist Church. Dr. Kasenga has published over 5 articles on HIV/AIDS issues focusing on Prevention of Mother to Child Transmission of HIV (PMTCT), including a book chapter on HIV testing counseling (currently in press). 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