Tolerance factors for the perovskite structures
\r\n\t
",isbn:"978-1-83968-571-2",printIsbn:"978-1-83968-570-5",pdfIsbn:"978-1-83968-599-6",doi:null,price:0,priceEur:0,priceUsd:0,slug:null,numberOfPages:0,isOpenForSubmission:!0,hash:"dd81bc60e806fddc63d1ae22da1c779a",bookSignature:"Dr. Sebahattin Demirkan and Dr. Irem Demirkan",publishedDate:null,coverURL:"https://cdn.intechopen.com/books/images_new/10818.jpg",keywords:"Decision Making, Blockchain, Accounting, Earnings Management, Strategic Alliances, Innovation, Performance, Corporate Governance, Accounting Quality, Digital Assets, Internationalization, MNCs",numberOfDownloads:null,numberOfWosCitations:0,numberOfCrossrefCitations:null,numberOfDimensionsCitations:null,numberOfTotalCitations:null,isAvailableForWebshopOrdering:!0,dateEndFirstStepPublish:"January 28th 2021",dateEndSecondStepPublish:"February 25th 2021",dateEndThirdStepPublish:"April 26th 2021",dateEndFourthStepPublish:"July 15th 2021",dateEndFifthStepPublish:"September 13th 2021",remainingDaysToSecondStep:"6 hours",secondStepPassed:!1,currentStepOfPublishingProcess:2,editedByType:null,kuFlag:!1,biosketch:"Academician in the area of accounting who believes in the impact of interdisciplinary research. Dr. Sebahattin Demirkan's research interests are in the areas of financial accounting, capital markets, auditing, corporate governance, strategic alliances, taxation, CSR, and data analytics.",coeditorOneBiosketch:"Researcher of strategic management, corporate entrepreneurship, and international business; specific interests include innovation, the ambidexterity framework, inter-organizational relationships, and networks. Experienced in teaching graduate and undergraduate courses in strategy, entrepreneurship, and international business and management areas.",coeditorTwoBiosketch:null,coeditorThreeBiosketch:null,coeditorFourBiosketch:null,coeditorFiveBiosketch:null,editors:[{id:"336397",title:"Dr.",name:"Sebahattin",middleName:null,surname:"Demirkan",slug:"sebahattin-demirkan",fullName:"Sebahattin Demirkan",profilePictureURL:"https://mts.intechopen.com/storage/users/336397/images/system/336397.jpg",biography:"Dr. Sebahattin Demirkan is a Professor of Accounting. He earned his Ph.D. in Accounting/Management Science at Jindal School of Management of the University of Texas at Dallas where he got his MS in Accounting, MSA Supply Chain, and MBA degrees. He got his BA in Economics and Management at the Faculty of Economics and Administrative Sciences at Bogazici University, Istanbul. He worked at Koc Holding, a private venture capital firm, and the University of California, Berkeley during and after his education at Bogazici University. His research interests are in the areas of financial accounting, capital markets, auditing, corporate governance, strategic alliances, taxation, CSR, and data analytics. Dr. Sebahattin Demirkan has published articles in Contemporary Accounting Research, JAPP, JAAF, TEM, Journal of Management, and other top academic journals. He teaches several different classes in both undergraduate and graduate levels in Accounting and Analytics programs. He is a treasurer and vice president of the TASSA, board member of the BURCIN and member of the American Accounting Association.",institutionString:"Manhattan College",position:null,outsideEditionCount:0,totalCites:0,totalAuthoredChapters:"0",totalChapterViews:"0",totalEditedBooks:"0",institution:{name:"Manhattan College",institutionURL:null,country:{name:"United States of America"}}}],coeditorOne:{id:"342242",title:"Dr.",name:"Irem",middleName:null,surname:"Demirkan",slug:"irem-demirkan",fullName:"Irem Demirkan",profilePictureURL:"https://s3.us-east-1.amazonaws.com/intech-files/0033Y000033HrA8QAK/Profile_Picture_1606729803873",biography:"Dr. Irem Demirkan earned her Ph.D. in International Management Studies and M.S. in Administrative Studies at Jindal School of Management at the University of Texas at Dallas, USA. She got her BA in Economics at the Faculty of Economics and Administrative Sciences at Bogazici University, Istanbul, Turkey. She worked in the finance and textile industries before joining to academia. Dr. Demirkan has published research in the areas of strategic management and corporate entrepreneurship in journals such as the Journal of Management, Journal of Business Research, Management Science, European Journal of Innovation and Management, IEEE Transactions on Engineering Management, among others. 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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:"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"}},{type:"book",id:"3621",title:"Silver Nanoparticles",subtitle:null,isOpenForSubmission:!1,hash:null,slug:"silver-nanoparticles",bookSignature:"David Pozo Perez",coverURL:"https://cdn.intechopen.com/books/images_new/3621.jpg",editedByType:"Edited by",editors:[{id:"6667",title:"Dr.",name:"David",surname:"Pozo",slug:"david-pozo",fullName:"David Pozo"}],productType:{id:"1",chapterContentType:"chapter",authoredCaption:"Edited by"}}]},chapter:{item:{type:"chapter",id:"52879",title:"Perovskite as Light Harvester: Prospects, Efficiency, Pitfalls and Roadmap",doi:"10.5772/65052",slug:"perovskite-as-light-harvester-prospects-efficiency-pitfalls-and-roadmap",body:'\nThe fast‐paced industrial development and population growth has increased the consumption of global energy to such an extent that it has become the ultimate necessity to use the renewable energy resources for long‐term sustainable development. Now it has become a challenge for both scientists and technologists to generate the cost‐effective and environmentally friendly renewable energy resources [1, 2].
\nAlthough solar cells based on the photovoltaic effect have attracted great attention due to the advantage of decentralization and sustainability, yet they suffer low cost effectiveness. Another emerging class of thin‐film energy devices based on amorphous silicon also tried to capture the market, making headway by processing of costs per unit area [3–5]. The manufacturing of inorganic thin‐films solar cells needs high‐temperature and high vacuum‐based techniques [6]. In addition, these techniques are limited and due to the inclusion of toxic elements, they are limited to large‐scale production and wide applications [7].
\nIn 1991, a new breakthrough emerged in the form of dye‐sensitized solar cells (DSSCs) that have attracted considerable attention due to their potential application in low‐cost solar energy conversion [8–16]. A high efficiency exceeding 12% was obtained by using 10 μm mesoporous TiO2 film sensitized with a cobalt redox electrolyte and an organic dye [17]. Furthermore, solid‐state DSSCs were also investigated where the liquid electrolyte was replaced by a solid hole‐transporting material (HTM) [e.g., poly(3‐hexylth‐iophene)(P3HT),2,2′,7,7′‐tetrakis‐(N,N‐di‐p‐methoxyphenyl‐amine)‐9,9′spirobifluorene (spiro‐MeOTAD)], polyaniline, and polypyrrole [8] to increase the open circuit voltage and stability of solar cells [18–22]. However, these ss‐DSSCs also suffer from faster electron recombination dynamics between electrons (TiO2) and holes (hole transporter), which results in the low efficiency of ss‐DSSCs [23]. So attempts were made to design various types of cells to increase the efficiency of solar cells [24].
\nThis efficiency criterion was increased by the introduction of the perovskite sensitizer ABX3 (A = CH3NH3, B = Pb, Sn, and X = Cl, Br, I), introduced by Prof. Grätzel and team, which has opened a new era in the field of DSSCs due to the excellent light‐harvesting capabilities [24–37]. These materials are composed of earth abundant materials, inexpensive, processable at low temperatures (printing techniques), generate charges freely (after absorption) in bulk materials, which qualify them as low energy‐loss charge generators and collectors [38–40]. Methylammonium lead trihalide (CH3NH3PbX3, where X is a halogen ion such as I−, Br−, and Cl−) have an optical bandgap between 2.3 and 1.6 eV depending on halide content, while formamidinum lead trihalide (H2NCHNH2PbX3) also have a bandgap between 2.2 and 1.5 eV. The minimum bandgap is closer to optimum for a single‐junction cell than methylammonium lead trihalide, which enhance to higher efficiencies [41]. The power conversion efficiency (PCE) of perovskite cells was improved from 7.2 to 15.9%, which is associated with the comparable optical absorption length and charge‐carrier diffusion lengths, making this device the most outperforming relative to the other third‐generation thin‐film solar cell technologies. Although two different configurations using CH3NH3PbI3 perovskite in a classical solid‐state DSSC and in a thin‐film planar configuration with CH3NH3PbI3−xCl\n\nx, having efficiency exceeding 16%, have been reported [26, 42], provided few issues related to the stability and hysteresis are to be solved effectively [43].
\nHere, it is necessary to mention that the lack of hysteresis that was an obstacle for stable operation in perovskite was observed recently using thin films of organometallic perovskites with millimeter‐scale crystalline grains with efficiencies approximately equal to 18% [44].
\nThe three recent reports have given high hopes in the field of solar cells as EPFL scientists have developed a new hole‐transporting material FDT that can reduce the cost and achieve the power conversion efficiency of 20.2% [45]. Another study by Hong Kong University claims that they have achieved the highest efficiency of 25.5% by perovskite‐silicon tandem solar cells [46]. In the meantime, it has been claimed that the efficiency of more than 30% can be achieved by tandem solar cells based on silicon and perovskites [47].
The basic structure of perovskite consists of a 3D network corner‐sharing BX6 octahedra, where A (e.g., A = Cs, CH3NH3, NH2CHNH2) cations are located in the larger 12‐fold coordinated holes between the octahedra [44]. It is composed of a metal cation (M = Sn, Pb, Ge, Cu) and its ligantanions (X = O2−, Cl−, Br−, I−, or S2−). In the case of inorganic perovskite compounds, the structures can be distorted as a result of the cation displacements, which give rise to some useful properties of ferroelectricity and antiferroelectricity due to the stereochemically active pairs of A cations [48]. The simple cubic structure of CH3NH3PbI3 is given in Figure 1.
\nThe crystal structure of perovskites, ABX3, a large cation (A) at center together with metal cation (B) bonded to the surrounded halides (X). Color code: A (CH3NH3),blue; B (Pb), green; and X (I), pink.
These inorganic‐organic hybrid compounds have the advantages of inorganic components that include structural order and thermal stability with interesting characteristics of organic materials such as low cost, mechanical flexibility, and functional versatility [49–53]. Numerous compounds have been reported by the covalent bonding between the inorganic and organic bonds [54]. Although the degree of interactions in organic‐inorganic systems with the van der Waals interacting system is relatively small, the reason for the small van der Waals interaction is the choice of organic cations, which is limited as the restricted dimension of the cuboctahedral hole formed by the 12 nearest‐neighbor X atoms. The synthesis of compounds CH3NH3 MX3 with M = Sn, Pb and X= Cl, Br, and I has been successfully carried out by some groups [55–57]. These organic cations show orientational disorder at high temperature, while at lower temperature the cubic phase results in a structural phase transition as the tolerance factor is smaller than unity. Upon cooling, the structure distorts to lower its symmetry as there are many restrictions to the motion of methylammonium cations [57].
\nMA, FA, Pb, and Sn perovskite combinations to identify three distinct phase transitions that occur are classified as a high temperature α phase, an intermediate β temperature phase, and a low temperature γ phase [54]. These different phases are represented in Figure 2.
\nGraphical representation of phase transitions of MA(Pb, Sn)X3 perovskite materials (a) α‐phase, (b) β‐phase, (c) γ‐phase. Precision images are taken at the [006] view. (d) The structural transformation of Br included in MAPbI3. Adapted with permission from reference [37].
The perovskites were first investigated by Goldschmidt in the 1920s [58] in work related to tolerance factors. The tolerance factor, t, with respect to the ionic radius of the actual ions is given in Eq. (1), where r\nA, r\nB, and r\nC are the ionic radius of the A, B, and C ions, respectively.\n
The tolerance factor of (0.9–1) is for an ideal cubic structure, for a cubic structure with the tolerance factor (0.7–0.9), the A ion is too small or the B ion is too large. This can be resulted in orthorhombic, rhombohedral, or tetragonal structure. For a large A cation, t becomes larger than one, which results in layered perovskite structures [59, 60]. The compiled results are given in Table 1 and the different forms of perovskite material CH3NH3PbI3 are given in Figure 3. The expected structure is also related to Pauling\'s rules (PRs) [61], given the expected coordination around a two‐component radii (cation/anion) system which is summarized in Table 2.
\nThe crystal structure of perovskites (CH3NH3PbI3) in different forms: (a) cubic, (b) tetragonal, (c) rhombohedral, and (d) orthorhombic. Color code: CH3NH3, pink; Pb, green and I, blue.
Structure | \nTolerance factor | \nComment for cation/anion |
---|---|---|
Tetragonal/rhombohedral/orthorhombic | \n0.7–0.9 | \nCation too large or anion too small |
Cubic | \n0.9–1.0 | \nIdeal perovskite |
Layered structures | \n>1.0 | \nCation too large |
Tolerance factors for the perovskite structures
Coordination | \nrc/ra | \nCoordination number |
---|---|---|
0.15–0.22 | \nTriangular | \n3 |
0.22–0.41 | \nTetrahedral | \n4 |
0.41–0.73 | \nOctahedral | \n6 |
0.73–1.0 | \nCubic | \n8 |
Coordination and ideal r\n\nc\nr\n\na (Pauling\'s rules). r\n\nc and r\n\na represent the cationic and anionic radii
The smaller tolerance factor is related to lower symmetry tetragonal or orthorhombic structures, whereas larger t (t > 1) could destabilize the three‐dimensional (3D) B‐X network.
\nThe other important parameter is an octahedral factor that plays an important role in these materials, and is given by,\n
where R\nB is the ionic radii of the B cation and R\nA is the ionic radii of A anion. If μ > 0.442, the formation of halide perovskite achieves, whereas below this value BX6 octahedron will become unstable and a perovskite structure will not form, although these factors provide a guidelines for the formation of halide perovskite, yet they are not sufficient to predict the structural formations within the perovskite family [62].
\nAlthough these materials already possessed useful physical properties, organic‐like mobility, nonlinear optical properties, enhanced exciton binding energies, electroluminescence, magnetic properties, and conductivity, they have emerged as DSSCs only in 2009 [63–68]. The performance of DSSCs is assessed by three major parameters: short‐circuit photocurrent (J\nSC), open‐circuit voltage (V\nOC), and fill factor (FF), which are further used to calculate the efficiency (PCE). V\nOC is proportional to the HOMO‐LUMO energy gap and J\nSC reflects the mobility, efficient light‐harvesting, and carrier generation. These values of different device structures are presented in Table 3.
\nPerovskite | \nPhoto anode | \nHTM | \nJ\nSC (mA/cm) | \nV\nOC (v) | \nFF | \nPCE (%) | \nReferences |
---|---|---|---|---|---|---|---|
CH3NH3PbI3 | \nmp (TiO2) | \nSpiro | \n17.6 | \n0.88 | \n0.62 | \n9.7 | \n[69] |
CH3NH3PbI3 | \nTiO2 NS | \nSpiro | \n16.1 | \n0.63 | \n0.57 | \n5.5 | \n[30] |
CH3NH3PbI3 | \nmp (TiO2) | \nSpiro | \n18.8 | \n0.71 | \n0.66 | \n8 | \n[70] |
CH3NH3PbI3 | \nmp (TiO2) | \nSpiro | \n18.3 | \n0.87 | \n0.66 | \n10.4 | \n[71] |
CH3NH3PbI2Cl | \nmp (Al2O3) | \nSpiro | \n17.8 | \n0.98 | \n0.63 | \n10.9 | \n[26] |
CH3NH3PbI3 | \nTiO2‐NWAs | \nSpiro | \n10.67 | \n0.74 | \n0.54 | \n4.29 | \n[72] |
CH3NH3PbI2Br | \nTiO2‐NWAs | \nSpiro | \n10.12 | \n0.82 | \n0.59 | \n4.87 | \n[72] |
CH3NH3PbI3 | \nmp (TiO2) | \nSpiro | \n20.0 | \n0.99 | \n0.73 | \n15.0 | \n[73] |
CH3NH3PbI3 | \nRutile (TiO2) | \nSpiro | \n15.6 | \n0.95 | \n0.63 | \n9.4 | \n[74] |
CH3NH3PbI3 | \nmp‐ZrO2 | \nSpiro | \n17.3 | \n1.07 | \n0.59 | \n10.8 | \n[75] |
CH3NH3PbI3 | \n(TiO2)crystal | \nSpiro | \n12.86 | \n0.79 | \n0.70 | \n7.29 | \n[76] |
CH3NH3PbI3 | \nmp (Al2O3) | \nSpiro | \n18.0 | \n1.02 | \n0.67 | \n12.3 | \n[37] |
CH3NH3PbI3 | \nCH3NH3PbI3 | \nSpiro | \n21.5 | \n1.07 | \n0.67 | \n15.4 | \n[77] |
CH3NH3PbI3 | \nmp (TiO2) | \nP3HT | \n12.6 | \n0.73 | \n0.73 | \n6.7 | \n[42] |
CH3NH3PbI3 | \nmp (TiO2) | \nPCPDTBT | \n10.3 | \n0.77 | \n0.67 | \n5.3 | \n[42] |
CH3NH3PbI3 | \nmp (TiO2) | \nPCPDTBT | \n10.5 | \n0.92 | \n0.43 | \n4.2 | \n[42] |
CH3NH3PbI3 | \nmp (TiO2) | \nPTAA | \n16.4 | \n0.90 | \n0.61 | \n9.0 | \n[42] |
CH3NH3PbI3 | \nmp (TiO2) | \nPTAA | \n19.3 | \n0.91 | \n0.70 | \n12.3 | \n[32] |
CH3NH3Pb(I1-xBr\nx)3 | \nMesoscopic and planar structures | \nPoly(triarylamine) | \n19.64 | \n1.11 | \n74.2 | \n16.2 | \n[79] |
CH3NH3PbI3 | \nMesoscopic TiO2 | \nSpiro | \n1.02 | \n21.2 | \n77.6 | \n16.7 | \n[80] |
FAPbI3 | \nMesoscopic TiO2 | \nSpiro | \n1.03 | \n20.97 | \n74 | \n16 | \n[78] |
CH3NH3PbI3-xCl\nx | \nPlanar heterojunction | \nSpiro | \n1.13 | \n22.75 | \n75.01 | \n19.3 | \n[81] |
CH3NH3PbI3 | \nFDT | \n1.148 | \n22.7 | \n0.76 | \n20.2 | \n[55] |
comprehensive summary of the performance of perovskite solar cells, including the perovskite materials, photoanodes, hole‐transport materials (HTMs), J\nSC (mA/cm), V\nOC (v), FF and PCE (%)
Abbreviations: mp, mesoporous; spiro, spiro OMeTAD.
The first perovskite‐sensitized TiO2 solar cell gave the efficiency of 3.8 and 3.1%, respectively [13]. Later on the titania\'s surface and CH3NH3PbI3‐based iodide liquid electrolyte solar cell have increased the efficiency to 6.5% [25]. In 2012, the liquid electrolyte was replaced with a solid electrolyte and a PCE of 9.7% was achieved [69]. A sequential deposition method for the formation of the perovskite pigment within the porous metal oxide film was developed with a PCE of 15% in 2013 (short‐circuit current density J\nSC = 21.5 mA/cm2, open‐circuit voltage V\nOC = 1.02 V, and fill factor FF = 0.71) [27]. An efficiency of 20% at low temperature was achieved in a processed solar cell, through the end of 2013 [70, 71]. Further, it is reported that the achieved efficiency has above 30% in 2016.
Mesoporous metal oxide films act as a working electrode for perovskite cells. The charge extraction rates are relatively faster for the perovskite solar cells than the conventional DSSCs [39]. Again the mesoporous TiO2 was replaced by Al2O3 with similar mesomorphology and it was seen that the PCE unexpectedly reached to 10.9% giving hopes for the future increase in efficiency. Furthermore, the DSSC efficiency has improved to 15.9% [27], yet there is the difficulty in pore filling because of the labyrinthine maze structure [72], which was alternatively substituted by a vertically aligned nanowire (NW) and nanotube (NT) structure. These nanotubes and nanowires can be used in pore filling due to their open porous structures. Moreover, they are reported to be better in electron transportation and recombination behavior and hole conductors presenting faster recombination than nanoparticulate films in liquid‐based DSSCs [73–75].
\nAs the absorption properties of perovskite are excellent, a possible decrease in the total surface area of the NWs/NTs compared to the nanoparticles does not stimulate the significant reduction of photocurrent. Later it was concluded that perovskite semiconductors in their simple architecture can exhibit sufficiently good ambipolar charge transport and the principal roles of photovoltaic operation, including charge generation, light absorption, and transport of both electrons and holes. Now the challenge is to determine whether mesostructure is essential or the thin‐film p‐i‐n can lead to a better performance [76].
While using the methylammonium lead halide (CH3NH3PbX3, X‐halogen) and its mixed‐halide crystals, corresponding to the 3D perovskite structures as light harvesters in solar cells, it is observed that substituting the I with Cl/Br ions, bandgap tuning of MAPbX3 is achieved, which occurred due to the strong dependence of electronic energies on the effective exciton mass [76]. The entire visible region was controlled by tuning the bandgap. Apart from that, the addition of Cl/Br into an iodide‐based structure shows a drastic improvement in the charge transport, relative stability, and separation kinetics within the perovskite layer [77]. It was also observed that the bandgap is reduced (1.48–2.23 eV), leading to high short‐circuit currents of >23 mA/cm2 and a PCE of up to 14.2%, when the cation size of perovskite materials is increased [42].
\nThere are a few solution‐based techniques that has been used for the fabrication of thin films, where a mixture of two precursors is used to form final absorber, but due to the lack of suitable solvents and high‐reaction rate of the perovskite component, the process results in thin film with pinhole formation and incomplete surface coverage, which deteriorates the film quality and thus effect the device performance.
\nThe two‐step deposition technique that was used previously to prepare the films of organic‐inorganic systems has incompatible solubility characteristics where the organic component is difficult to evaporate. Devices based on the planar CH3NH3PbI3 thin film via the modified two‐step deposition technique have also achieved the efficiency of 12.1% [78].
\nAnother technique that was developed was dual‐source vapor‐deposited organometallic trihalide perovskite solar cells based on a p‐i‐n thin‐film architecture with high efficiency. However, the deposition with the vacuum evaporation method will make it cost effective [26].
The conductivity of perovskite is high, which requires a thick layer of HTM to avoid pinholes. Spiro‐OMeTAD, due to being less conductive, offers high resistance because of thick capping layers. A wide variety of polymer hole conductors are also used, which is shown in Figure 4. Protic ionic liquids (PILs) are used as effective p dopants in hybrid solar cells [78] based on triarylamine hole‐transporting materials. Further, the efficiency is improved by replacing the lithium salts, p‐dopants for spiro‐OMeTAD with PILs [79]. While using other HTMs as P3HT and DEH HTM, the efficiency of spiro‐OMeTAD is much slower than P3HT and DEH HTM, respectively. However, a recent synthesis based on the pyrene‐based derivative Py‐C also exhibited an overall PCE of 12.7% [76]. As the hole conductors, spiro‐OMeTAD and P3HT are costly, so an inexpensive, stable, solution‐processable inorganic CuI as the hole conductor has been demonstrated [80]. A solution‐processed p‐type direct bandgap semiconductor CsSnI3 with a perovskite structure can also be used for hole conduction replacing a liquid electrolyte [34]. Overall we can say that perovskite materials play both the role of light harvesters and hole conductors. Recently, a hole‐conductor‐free mesoscopic CH3NH3PbI3 perovskite/TiO2 heterojunction solar cell has reported with a PCE of 5.5% [30], yet the photovoltaic performance was inferior to that of HTM. The tuning of bandgap of perovskite materials plays an important role in photophysical properties. The energy bandgaps of different hybrid materials and the hole‐transporting materials are given in Figures 5 and 6.
\nStructural representation of hole‐transporting materials (HTMs).
Energy bandgap diagram of hybrid perovskite materials.
Energy level diagram of hole transporting materials (HTMs).
Regarding the exciton or the electron and hole diffusion length, it was observed that 100‐nm long range diffusion length was obtained in solution‐processed CH3NH3PbI3 by applying femtosecond transient optical spectroscopy to bilayers that interface this perovskite with either selective‐electron or selective‐hole extraction materials [38]. The higher efficiency of these materials is only due to the comparable optical absorption length and charge‐carrier diffusion lengths. Photoluminescence quenching measurements were performed to extract the electron‐hole diffusion lengths in triiodide (CH3NH3PbI3) and mixed‐halide (CH3NH3PbI3−xCl\n\nx) perovskite thin films [39]. In mixed‐halide perovskite cells, the larger diffusion length is due to the much longer recombination time, requires both low recombination rates and high charge‐carrier mobility; however, the mechanism causing the extended diffusion length is still unclear. Few other things that remain unclear is the relative fraction of free and bound charge pairs at room temperature, the nature of the excited state, and the role of the two species [81, 82].
There are reports that prove that Density functional theory (DFT) calculations have already carried out before the first perovskite solar cell was reported experimentally [4, 13]. Various theoretical methods were adopted using exchange‐correlation functionals such as Local density approximation \x3c!-- Please define the acronyms "DFT, LDA, GGA, VBM, and PSC."
However, the defects does not affect much as they do not create a detrimental deep level within the bandgap [84, 85] that could be carrier traps and recombination centers for electron‐hole in solar cells. Ringwood [86] has included that the contribution of charges depends on the differences in electronegativity. Since lead is considered as a provider of the charge and size, it holds the perovskite crystals all together.
\nThe ambipolar activities of these materials can be defined by taking effective mass into consideration which is defined by formula:\n
where ε(k) is the energy dispersion relation functions, described by the band structures. If the band is more dispersive (flat), near the band edges, the effective mass is lighter (heavier). In perovskite materials, the lone‐pair Pb s electrons play a vital role. The electronic structure of CH3NH3PbI3 is inverted. The conduction band matrix is derived from Pb p orbitals, and the valence band matrix is a mixture of Pb s and I p (s‐p semiconductor) orbitals. A cation Pb p orbital has a much higher energy level than anion p orbitals, although the CBM is derived from Pb p orbitals, Therefore, the lower conduction band of CH3NH3PbI3 is more dispersive than the upper valence band, similarly the upper valence band of CH3NH3PbI3 is dispersive due to the strong s‐p coupling around the Valence band maximum (VBM). Due to the balance between the hole effective mass and the electron effective mass, CH3NH3PbI3 leads to higher ambipolar activities. It might be possible that many‐body effect plays a role for small carrier effective mass, as the effective mass calculated by the GW + SOC method [87] is even lower. The effective hole and electron masses are given in Table 4.
\nMaterials | \nm\ne\n*/m\n0 | \nm\nh\n*/m\n0 | \nBandgap (eV) |
---|---|---|---|
Silicon | \n0.26 | \n0.29 | \n1.11 |
GaAs | \n0.07 | \n0.34 | \n1.43 |
CsSnI3 | \n0.19 | \n0.09 (0.15) | \n1.14 |
CsSnI3 (SOC) | \n0.16 | \n0.07 | \n|
CH3NH3PbI3 | \n0.35 (0.32) | \n0.31 (0.36) | \n1.5–2.0 |
CH3NH3PbI3 (SOC) | \n0.18 (0.23) | \n0.21 (0.29) | \n
Calculated effective masses (electron and holes) and bandgap (eV) for different materials. Experimental values are in parenthesis
The optical absorption spectra of perovskite materials are determined by the energy bandgaps and partial density of states (pdos). The pdos graph for different materials is depicted in Figure 7. The energy bandgap measures the probability of each photoelectric transition and the density of states measures the total number of possible photoelectric transitions. Thus, we can easily conclude that the optical absorption coefficient of a material is closely related to its electronic structure. However, the effect of optical absorption spectra is not considered in the Shockley‐Queisser limit [42]. The theoretical maximum efficiency depends on the thickness of the absorber layer. Recently, a method has been developed by Yu et al. [88], in which they calculated the maximum efficiency based on the absorber thickness by taking absorption coefficient and absorber layer thickness both into consideration. So theoretical calculations were carried out on this basis and it was found that halide perovskites (CH3NH3PbI3 and CsPbI3) exhibit much higher conversion efficiencies for any given thickness. These materials are also capable of achieving high efficiencies with very thin absorber layers. On the basis of experimental calculations, it is proved that CH3NH3PbI3 perovskite has the capability of achieving a high fill factor. Improved interfaces and contact layers also improve the performance of a solar cell, while Pb chalcogenides exhibit abnormal bandgap changes with lattice constant and strain [89].
\n(a) The periodic structural model of Σ5 (310) GB for CH3NH3PbI3. (b) Comparison of DOS of bulk CH3NH3PbI3calculated from unit cell. (c–f) pdos of selected atoms highlighted in the above structure. Adapted with permission from reference [137].
One more theoretical aspect is the dipole moment of the noncentrosymmetric organic cation in perovskite materials. It was shown from electric dipole calculations of the organic cation that hybrid perovskites exhibit spontaneous electric polarization, which might be due to the two reasons: the alignment of the dipole moments of organic cations and the intrinsic lattice distortion breaking the crystal centrosymmetry. On the basis of this concept, it was proposed in the studies that the presence of ferroelectric domains will result in internal junctions might support electron‐hole separation and transportation. However, the calculated value of CH3NH3PbI3 bulk polarization is 38 mC/cm2, which is comparable to the value of ferroelectric oxide perovskites such as KNbO3 (30 mC/cm2) [90]. Frost and coworkers [91] suggested that it may be possible that the boundaries of ferroelectric domains may form “ferroelectric highways” that facilitate the transportation of electrons and holes. Furthermore, it was proposed that the favorable highways are energetically chosen in such a way that the holes and electrons avoid any collision with the opposite charges. It is directly seen in the recent experiment by direct observation of ferroelectric domains in the β phase of CH3NH3PbI3. Another important factor is that V\nOC can be larger than the bandgap, and charge separation and carrier lifetime can be enhanced due to the internal electric field [92].
The surface and interface between the absorber, carrier transport layers, and electrode contact layers are also important for efficient carrier transportation. However, the two‐step method, vacuum deposition and vapor‐assisted solution processing methods [85], have improved the quality much better by the one‐step method. The vacuum deposition method is used in small molecule‐based devices, which makes the use of insoluble materials more stable than their soluble analogues. There are at least three aspects worth consideration.
\nThe bandgaps and band alignments of perovskites can also be tuned by the chemical management of compositional elements, including organic cations [93, 94], Pb [95–97], and halogen elements [98, 99]. This is another way to optimize band alignment at interfaces.
The unusual hysteresis of the I–V curve of perovskite solar cells, which would reduce the working cell efficiency, was suspected to be related to the interface properties [99, 100].
Abate et al. [79] reported the existence of trap states at the perovskite surface, which generated charge accumulation and consequent recombination losses in working solar cells. They identified under coordinated iodine ions as responsible and used supramolecular halogen bond complexation for passivation.
The p‐ or n‐type absorbers were made from materials with intrinsic defects, or using intentional doping intrinsic defects that create deep energy levels in the absorber usually act as Shockley‐Read‐Hall nonradiative recombination centers and carrier traps, reducing the carrier lifetime and thus V\noc. A good solar cell absorber must exhibit proper doping and defect properties. There are many types of defects as a donor and acceptor which lies in the semiconductors. The formation energy of a defect depends on the chemical potential and environmental factors such as precursors, partial pressure, and temperature. So we can conclude that these experimental conditions play a vital role to determine the formation energies of all the possible defects and further impact the polar conductivity in these materials. Defect formation energies determine the polar conductivity of a semiconductor, whereas defect transition levels determine the electrical effect of any particular defect [101].
\nBesides point defects, Kim et al. [102] used DFT‐GGA to calculate the DOS and partial charge densities of two types of neutral defects in β phase CH3NH3PbI3: (a) Schottky defects (equal numbers of positive and negative vacancies) and (b) Frenkel defects (equal numbers of vacancies and interstitials of the same ion). The tunable polar conductivity and shallow defect properties may help to explain why high‐performance perovskite solar cells, with extremely long carrier lifetimes [40, 103] can be produced by a diverse range of growth approaches and a wide variety of solar cell architectures. These point defects would suggest new methods for perovskite solar cell architecture. It was observed that deep point defect levels could exist through large atomic relaxations, which is attributed to the strong covalency of the system [104].
In a recent investigation, Choi et al. [105] found that most of CH3NH3PbI3 (70%) is highly disordered with a local perovskite structure extending over a range of only 1.4 nm, which is about 2 lattice constants of the α phase [106].
\nThe mesoporous scaffold confined need the perovskite within the pores and reshaped the structures of perovskites. On the other hand, the low‐temperature growth process inevitably leads to polycrystalline perovskites with grain boundaries (GBs). Experimentally, it is very difficult to investigate the structural and electronic properties directly, as it requires a high resolution transmission spectroscopy (HRTEM). So, we have to rely on the theoretical calculations that can give direct insights into the electrical properties of structural disorders and topological defects in hybrid perovskites. Recent combined theoretical and experimental studies [106] have demonstrated that Cl segregated into the GB part of polycrystalline CdTe solar cells effectively taming the detrimental effects at GBs.
\nDue to the structural complicity of CH3NH3PbI3, the GB structures were constructed based on CsPbI3. It was observed that the DOS of the supercells with GBs are very similar to those of single‐crystal phases. None of these GBs introduce defect states within the bandgap region. The GW band structure diagram is given in Figure 8.
\nDOS graph of MASnI3 and MAPbI3materials. Adapted with permission from reference [116].
Hybrid perovskites exhibit unprecedented carrier transport properties that enable their stellar performance in photovoltaics. So more attention is needed to develop understanding the material properties and ways to improve these properties in all key directions for research. The electrical properties of perovskite materials are seen in the ambipolar carrier transport behavior and long carrier lifetime. These electrical properties are further investigated on the basis of corresponding device structure.
\nThe electrical characteristics of the materials are determined by the carrier type, concentration, and mobility, which is dependent on the method of preparation. It is necessary to use smooth and uniform films to perform measurements. The carrier type is determined by Hall measurements of the conductivity\'s response to an applied magnetic field, thin‐film transistor\'s response to a gating electric field, and thermoelectric measurements of the Seebeck coefficient. For example, CH3NH3PbI3 indicated n‐type conductivity, a carrier concentration of ~109 cm−3, and an electron mobility of 66 cm2/V/s [24]. Carrier concentration can also be adjusted by tuning the stoichiometry of the precursors during solution‐phase synthesis and even switch the carrier type to the p‐type when excess CH3NH3I is used in two‐step synthesis. The electron concentration was measured to be ~1017–1018 cm−3, and it was proposed that the iodide vacancies are responsible for the n‐type conductivity [107]. The electron mobility for n‐type films deposited from stoichiometric precursors was determined to be 3.9 cm2/V/s from the Hall measurements, although CH3NH3SnI3 prepared by a solid‐state reaction in a vacuum‐sealed tube showed an electron mobility of 2320 cm2/V/s [24], while solution processed material measured mobility of 200 cm2/V/s. It was observed that the electron mobility of polycrystalline CH3NH3PbI3 films is larger than the thin‐film mobility of polymers [107, 108] and colloidal quantum dots (10−3–1 cm2/V/s) [109] comparable to CdTe (10 cm2/V/s) [110] CIGS, Cu2ZnSnS4 (CZTS) (10–102 cm2/V/s) [111, 112], and polycrystalline Si (40 cm2/V/s) [101]. Film morphology plays an important role as the dark and light conductivities of CH3NH3PbI3−xCl\n\nx deposited on a planar scaffold on mesostructured aluminum oxide are quite different [113]. To further increase the photovoltaic performance and radiative lifetime, solvent annealing has been applied to increase the grain size of the films to ~1 μm [114].
The techniques used to measure the electrical parameters are given in subsections.
\nThis technique is used to identify the frequency dependence of capacitance, to measure charge diffusion lengths and lifetimes and to investigate carrier trapping and recombination. The carrier diffusion length was derived and has been estimated to be about ~1 μm for CH3NH3PbI3−xCl\n\nx [83].
Another method to obtain the electrical parameters is EBIC from which the calculated carrier diffusion length forCH3NH3PbI3−xCl\n\nx is 1.5–1.9 μm [40]. The carrier diffusion length is comparable or longer than that of other polycrystalline semiconductors with direct bandgaps used in solar cells [76, 77, 118–120]
It is very important to understand the optical response of the materials, as optical properties are the most important feature of perovskite materials and they provide insights into the electronic and chemical structures. The ability to tune the optoelectronic properties with ease presents a major attraction among researchers. Few important parameters that are used to define these properties are discussed herein:
\nA lot of research has been conducted on tuning the bandgap of perovskite, but a more detail understanding of these materials awaits further research. The major problem that occurs in perovskite materials is the difficulty of producing continuous films of sufficient smoothness [121] to avoid measurement artifacts from spectroscopic measurements of transmittance, reflectance, and ellipsometry. The absorption coefficients determined from the absorption of CH3NH3PbI3 films on quartz [122] and glass [123] yield values of ~104 cm−1 near the band edge without providing any corrections for the surface\'s inhomogeneity, so for accurate measurements is important to calculate the absorption coefficients based on the optical constants of CH3NH3PbI3 [124]. It is observed that the absorption spectrum for CH3NH3PbI3 differs, when deposited within a mesoscopic template and planar substrates, which might be due to the changes in the crystallite morphology that affects the optical transitions [125, 126].
Exitons play an important role in perovskites. The studies indicate, however, that there is not significant population of excitons in photovoltaics made from CH3NH3PbI3, whose exciton‐binding energy has been reported between 20 and 50 meV, comparable to the thermal energy at room temperature [127, 128]. These values have been obtained by fitting temperature‐dependent absorption spectra using the measured [88] reduced mass of the exciton. Excitonic radius from the binding energy and an appropriate dielectric constant study is still a subject of debate [129]. The excitonic transition significantly enhances the absorption of hybrid perovskites near the band edge [130, 131].
The photoluminescence (PL) efficiency depends on the pump fluence. The trapping of photogenerated charges competes effectively with direct radiative recombination of electrons while holes reduce luminescence at low excitation energies. The PL efficiency ofCH3NH3PbI3is ~17–30%. The PL efficiency falls at higher pumping and high charge carrier densities. The PL lifetime measurements reported shorter lifetime (between 3 and 18 ns) at low pump fluencies [127, 132–134]. These longer lifetimes have been found in a semiconductor in doped and undoped GaAs films. This might be due to the photon recycling and the PL lifetime dependency on surface recombination than radiative recombination. So we can conclude that photon cycling plays a major role in their excited state dynamics, when nonradiative decay pathways are suppressed. The absorption spectra and photoluminescence for perovskite materials are shown in Figure 9.
\n(a) Absorption spectra, (b) photoluminescence spectra of FAPbI\n\nxBr3−x (varying I:Br ratio), (c) XRD spectra of the phase transition Br‐rich cubic phase to the I‐rich tetragonal phase. Adapted with permission from reference [37].
IR spectroscopy also plays an important role in determining the chemical composition. If we look into the chemical structure of CH3NH3PbI3, CH3NH3PbBr3, and CH3NH3PbCl3, the first one is tetragonal, while the other two are cubic. Raman‐active modes are precluded in the symmetry of the lattice for cubic structures [135], though a weak broadband at 66 cm−1 is observed in CH3NH3PbCl3. For CH3NH3PbI3, the resonant Raman spectrum (DFT calculations) has been observed with nodes below 100 cm−1 (approximately) related to the inorganic octahedron. The higher energy modes indicate the disorder of CH3NH3\n+ cations. A lot of work in this field is still required to investigate how the modes shift occurs with the structural changes. Raman nodes can provide better tool in understanding the in homogeneity of perovskite films with submicron spatial resolution.
Perovskite solar cells exhibit an anomalous hysteresis in the current‐voltage and resistivity‐temperature dependence curves [136]. Though it was predicted that the hysteresis on resistivity verses temperature curves is associated with the structural phase transition while the reason for current‐voltage curves are still unknown. In an extensive [E‐CE6] studies carried out by Prof. Erik Christian Garnett et al. [136], several explanations have been proposed as ion migration, filling of interface, or surface trap states, accumulation of charges at grain boundaries and ferroelectricity, yet no convinced conclusion has been drawn. In structural perception, the cubic phases of the chloride and bromide perovskites do not allow a polar ferroelectric distortion. Various hypotheses have been suggested and it was further predicted that hysteresis should depend on the magnitude of the dipole moment of the organic cationic species and the connecting halide cage. Though the origin of this phenomenon is not yet understood properly, a number of possible causes have been proposed in which the noted causes are ferroelectricity or the presence of mobile ionic species [136]. The illustration for the hysteresis in the electrical transport in hybrid perovskites is given in Figure 10.
\nHysteresis representation in hybrid perovskites. (a) I‐V graph of CH3NH3PbI3 (single crystal) at room temperature, (b) schematic I‐V curve, (c) proposed phenomena for its origin. Adapted with permission from reference [104].
Here, it is necessary to mention that reporting results from single J–V sweeps, even in the absence of hysteresis, or choosing scan rates to report the highest efficiencies, will lead to misleading results. As it might be possible that the certified efficiencies for perovskite solar cells are deemed “not stabilized” though they were measured with negligible hysteresis.
There are so many reports that claim that perovskite solar cells have been shown to be stable for many hundreds of hours without any encapsulation. However, the solar cells were stored in the dark and only measured occasionally. So we can conclude that the sealing from environmental ageing is necessary because of operation at elevated temperature and humidity. Stability has become a bigger problem for tin (II) perovskites due to the decrease in stability of the oxidation state of tin (II) compare to lead (II).
Due to the toxic nature of lead, concerns have been raised on the possible environment and legalization problems from perovskite solar cells based on water soluble lead compounds. So efforts have been made to replace lead with other metal ions without degrading the photophysical properties with quantum mechanical calculations. As lead halogen perovskites are water soluble, the most pessimistic view is the consequences of damaged solar cells and panels with potential exposure to water followed by dissolution and distribution of lead ions into buildings, soil, air, and water.
\nLead is known to damage the nervous system and cause brain disorders. In this direction, a theoretical study carried out by De Angelis and group [137] has replaced Pb by Sn (Figure 11) with effective development of the GW method with spin‐orbit coupling to accurately model the properties of CH3NH3SnI3 and then compared it to the CH3NH3PbI3. They predicted that MASnI3 is a better electron transporter than MAPbI3 by the SR‐DFT method. Another study carried out by Jesper Jacobsson and group [138] has provided deep physical insights into the photophysical nature of a metal‐halogen perovskite by removing lead with strontium, which is relatively nontoxic and inexpensive. CCSD calculations and DFT study were performed on the two basic structures of CH3NH3SrI3 and CH3NH3PbI3 to extract and compare the electronic structures and the optical properties. This is based on the fact that the ionic radii of Sr2+ and Pb2+ are almost identical, so the exchange could be made as it will not affect the crystal structure. CH3NH3SrI3 gives a bandgap of 1.6 eV, which is fairly close to the experimental value reported to be around 1.55 eV [5, 42]. The second effect that was caused by shifting Sr for Pb is that the shape of the pdos graphs for both the halogen and the organic ion is shifted and slightly distorted. The lower electronegativity of Sr compared to Pb shifts the electronic cloud closer to the iodine atoms in the lattice, which perturb the local dipole moment as well as the bonding angles between the iodine octahedra and consequently their columbic interaction with the methylammonium dipoles. The charge distribution is similar to the two structures, with higher charge density around lead compared to strontium due to the higher atomic number of lead.
\nPictorial representation of replacement of lead by strontium in perovskite solar cells [138].
The Perovskite solar cell (PSC) field has now become an emerging field and reports on further improvement in performance are expected in the near future, achieving PCE of more than 30% efficiency has now become a realistic goal. Furthermore, PSC can be used as top cells in two‐level tandem configurations using crystalline silicon or copper indium gallium selenide‐based photovoltaic devices as bottom cells. It is expected that by using silicon‐based tandems, PCEs of 28–30% can be achieved. Yet there are issues related to the stability and toxicity, hysteresis in perovskite solar cells, which has to be solved. Experimental and theoretical investigations have demonstrated that that halide perovskites exhibit a series of superior electronic and optical properties for solar cell applications, such as proper bandgap and band alignment, high optical absorption, bipolar carrier conductivity, tunable doping ability, and benign defect properties. A lot of studies are required to optimize the material properties and to find new perovskite candidates for high‐efficiency, stable solar cells. Band structure engineering of CH3NH3PbI3 needs to be extensively investigated by replacing organic cations, Pb or I, with other choices. Furthermore, the mechanisms of performance degradations have to be resolved in a more prominent manner. Water‐corroded perovskites as rapid degradation occur in moist environments. So the reaction mechanism between H2O and the perovskite surface could be carefully studied, leading to the development of new methods for stabilizing perovskites. Although some groups have fabricated the long‐term stable perovskites in the laboratory through chemical composition engineering [32, 88], the fundamental reason for alloy stabilization of the structures requires more study. However, it is predicted that the study should converge to the p‐i‐n planar heterojunction perovskite solar cell to understand the device structure and properties from single crystal.
The intense appeal of hybrid organic‐inorganic perovskite materials such as solar cells is exceptionally promising. Their enhance optoelectronic properties, deposition techniques, and device structure have led to the higher power conversion efficiencies. Due to the high absorption coefficients and panchromatic absorptions of perovskite, they have become ideal materials for thin film solar cells. However, some complexities as the poor stability in humid air and the toxicity of lead used are a matter of concern. In some perovskite materials, the hysteresis is also pronounced due to the strong dependence of photocurrent to the voltage scan conditions. Still the exceptional performance of hybrid perovskite materials has created revolution in the field of renewable energy with cheap solar cells. Highly efficient solar cells with record performance are still an important milestone to be achieved. The highly innovative and new elegant designs, deep insights into the photophysics and mechanisms of cell operation should now be the main focus of future research.
\nFinally, we can conclude that the recent advances with perovskite materials will motivate the researchers to expand their horizons to other inorganic or organic pigments, for which the power of mesoscopic solar‐cell architectures will emerge to offers more promising opportunities.
The author acknowledges the financial assistance by the DST WOS‐A (CS‐1005/2014). The author is also thankful to her mentors Dr. G. Narahari Sastry, Head, Center for Molecular Modeling and Dr. K. Bhanuprakash, Chief Scientist, I& PC division, CSIR‐Indian Institute of Chemical Technology for the useful discussions and suggestions.
Heavy metals are those elements which have density greater than 5 g cm−3 [1]. Some heavy metals namely, cobalt (Co), copper (Cu), molybdenum (Mo), manganese (Mn), nickel (Ni) iron (Fe), and zinc (Zn) are considered to be essential for plants. These heavy metal elements directly impact on plant growth, development, senescence and energy producing processes and other physiological process due to their high reactivity. The concentration of heavy metals in soil after the admissible limits is toxic to plants either provoke oxidative stress through free radicals or crumbling up the functions of enzymes by replacing metals and nutrients which are essential [2, 3]. Cell metabolism changes by the affect of heavy metals at first reduce the plant growth. However, toxicity of metals depends on various stage of their growth stage [4]. Maksymiec and Baszynski [5] reported that dicotyledonous plants like various beans and Medicago sativa were more resistant to heavy metals at the early growth stage [6]. So, the heavy metals toxicity on the plant physiology and metabolism are much more noticeable. Among the heavy metals, chromium and cadmium are of special concern due to their potential toxicity on plants even at low concentrations [7, 8, 9]. The various types of chromium toxicity in plant had described by [10], and the inhibition of enzymatic activity by vaeious types mutagenesis had also be described. The visible symptoms are reduction in growth, leaf chlorosis, stunting, and yield reduction [7, 11]. [12] has explain that Cadmium (Cd) is particularly is one of the most dangerous pollutant due to its high level of toxicity and much solubility in water. [13, 14], have reported that in some plant species Cd interacts with the absorption of metal nutrients such as Fe, Zn, Cu and Mn, in addition to inducing a process named as peroxidation and breakdown of chlorophyll in plants, resulting in an enhanced production of reactive oxygen species (ROS) [15]. According to [16], Cadmium also inhibits the uptake of elements such as K, Ca, Mg, Fe because it uses the same transmembrane carriers. Cadmium acquisition in plants may also cause serious health hazard to human beings through food chain; however, it causes an extra risk to the children by direct ingestion of Cd-contaminated soil [17].
Heavy metals remain in environment in various forms like colloidal, ionic, particulate and dissolved phases. The soluble forms of heavy metal elements are remain in environment as ionised or unionized organometallic chelates. According to [18], the metal concentrations of soil ranges from low to 100,000 mg kg−1 which depends on the location, area and the types of metals. [19], studied that among chemical elements, Cr is considered to be the seventh most abundant elements on earth and constitutes 0.1 to 0.3 mg kg − 1 of the crystal rocks. According to McGrath [20], In alloys and 15 percent in chemical industrial processes, mainly leather tanning, pigments, electroplating and wood preservation, about 60–70 percent of the total world production of Cr is used. Chromium has many oxidation states ranging from Cr2− to Cr6 +; however, in a number of compounds, valences of I, II, IV and V have been shown to exist [21]. Cr (VI) is, however, considered the most toxic form of chromium and is also generally associated with oxygen as chromate (CrO42−) or dichromate (CrO42−) and dichromate (Cr2O72−) oxyanions. [22], observed that Cr (III) is less mobile and less toxic and is mainly bound to organic matter in soil and aquatic environments. According to [23], Cr present mostly in the form of Cr (III) in soil, and mineral environment. [24], has described that Cr and Fe (OH)3 is a solid phase of Cr(III) having even lower solubility than Cr(OH)3. Consequently, within the soil add up to solvent Cr(III) remains inside the allowable limits for drinking water for a wide extend of pH (4–12) due to precipitation of Cr(OH)3, Fe(OH)3[25, 26], moreover, major source of Cd is the parental fabric. Anthropogenic exercises have too been improved the sum of Cd in soil [27]. Overwhelming metals are regularly show at exceptionally moo concentrations in freshwaters [28], but the release of fluid squander from a wide assortment of businesses such as electroplating, metal wrapping up, calfskin tanning, chrome planning, generation of batteries, phosphate fertilizers, shades, stabilizers, and amalgams has solid impact in sea-going situations [29, 30, 31]. Cadmium pollution is also happened from rubber when car tires run over streets, and after a rain, the Cd is washed into sewage disposal systems and collected in the slush.
Heavy metals are enter in environment are transported by water and air, also deposited in soil and sediments where they could be immobilized [32]. However, the bonding process of metals may take considerably long time. At the starting of the official handle the bio accessible division of metal components in soil is tall, but diminishes continuously in due course of time [33]. Metal dissolvability and bioavailability to plant is basically affected by the chemical properties of soil such as, soil pH, stacking rate, cation trade capacity, soil surface, redox potential, clay substance and natural matter [34, 35, 36]. For the most part, higher the slime or natural matter and soil pH, the metals will be relentlessly bound to soil with longer time and will be less organically accessible to the plants. Soil temperature is additionally an vital calculate for varieties in metal amassing by crops [37]. The bioavailability of metals is make greater in soil through several means, the secretion of phytosiderophores into the rhizosphere to chelate and solubilise metals that are soil bound [38]. Acidification of the rhizosphere and exudation of carboxylates are deliberated potential means to enhancing metal consumption.
Heavy metals are taken through root cells of the vegetation after their mobilization inside the soil, and their improvement inside the soil relies upon in the main upon: (i) dissemination of steel additives alongside the attention attitude which has formed because of take-up of factors and ultimately inanition of the aspect inside the root region; (ii) interferences through roots, in which soil extent is uprooted through root extent after developing (iii) move of steel additives from enormous soil association down the water capacity slope [39]. Cell divider acts as a particle exchanger of relatively moo partiality and moo selectivity in which metals are first of all bound. From the mobileular divider, the shipping frameworks and intracellular high-affinity authoritative locations intercede and power the take-up of those metals over the plasma layer. A stable using power for the take-up of steel additives thru auxiliary transporters is made because of the layer capacity, that is bad at the indoors of the plasma movie and can exceed −200 mV in root epiderm. This is examined both in soil culture and in solution culture for Cd which might probably be due to low concentration of heavy metals per unit of absorption area [40, 41]. Both non-essential and essential metals are also preoccupied through leaves. Within the shape of gases, they input via thestomata withinside the leaves, while in ionic shape metals specifically input via theleaf cuticle [39, 42]. Hg in gaseous shape istaken up through stomata [43] and its uptake is recommended to bebetter in C3 than C4 flora [44]. The uptake of metals takes place viaectodesmata, non-plasmatic “channels” at a excessive level whichare much less dense elements of the cuticular layer which are located fundamental withinside theepidermal mobileular wall or cuticular membrane machine among shield cells andsubsidiary cells. Furthermore, the cuticle overlaying shield cells are oftenspecific to it overlaying everyday epidermal mobileular [39]. Most of the metallic factors are insoluble that won’t capin an edge toflow freely withinside the vascular machine of flora and, as a result typically shapesulphate, phosphate or carbonate precipitates immobilizing them inextracellular booths i.e. apoplastic and intracellular compartment i.e. symplastic [45]. In the apoplastic pathway solute and also the water debris diffuse via mobileular membrane, consequently the pathway stays unregulated. The mobileularwall of the endodermal mobileular layer acts as an impediment for apoplastic diffusioninto the vascular machine. Generally, prior to the access of metallic ions withinside thexylem, solutes must be haunted through root symplasm [46]. Ifmetals are obsessed through the premise symplasm, their similarly motion from root tothe xylem is specifically ruled through 3 processes, including: (i) metallicsequestration arise into the premise symplasm, (ii) symplastic shipping ariseinto the stele, and (iii) launch of metals arise into the xylem. The ionshipping into the xylem is often occured through membrane shipping proteins. Metal factors which are not wished through the flora successfully compete thecritical heavy metals for his or her shipping the usage of the equal transmembranecarriers. Cr(III) uptake through the plant is specifically a passive process, whilst Cr(VI) shipping is mediated through sulphate carrier [47]. Inhibitors like, sodium azide and di nitrophenol inhibits the uptake of Cr(VI) through barley seedlings however this is not happened just in case of Cr(III) [47]. In keeping with [48], Group VI anions like SO4−2 additionally inhibit the uptake of chromateswhile Ca2+ stimulates its shipping. This inhibition of chromate shipping is passed thanks to the aggressive inhibitiondue to the chemical similarity, whilst inspired shipping of Cr(VI) because of Ca is attributed to its critical position in flora for the receive and shipping of metallic factors [26, 49].
According to Kumar et al. [50], many plants species show an unusual capability to absorbe heavy metals through root system and accumulate of these heavy metals in their parts. Zayed and Terry [26] said that it seems a common tendency of all plant species to maintain Cr in their roots, but with quantitative differences. It is found that for the translocation of Cr to the plant tip, leafy vegetables such as spinach, turnip leaves that tend to acquire Fe appear to be the most effective [51]. While those leafy vegetables such as lettuce were considerably less effective for translocating Cr to their leaves, cabbage which accumulated relatively low Fe levels in their leaves. Zayed and Terry [26] have reported that some plant species attain substantially higher root or shoot concentration ratio than other species. However, a ‘Soil–Plant Barrier’ well protects the food chain from heavy metal toxicity, implying that, due to one or more of the following processes, heavy metal levels in edible plant tissues are reduced to safe levels for animals and humans: (i) prevention of metal element uptake due to soil insolubility, (ii) prevention of metal element translocation by making them immobile in roots, or (iii) prevention of metal element translocation for animals and humans to the permissible level [52]. Within plant tissues, some elements such as B, Mo, Cd, Mn, Se, and Zn are readily absorbed and translocated, while others such as Al, Ag, Cr, Fe, Hg, and Pb are less mobile because of their strong binding to soil components or root cell walls. However, at certain concentrations, all of these elements are mobilised, even against a concentration gradient, within the transport system of the plant. Kinetic data show, for instance, that essential Cu2 +, Ni2 + and Zn2 + and non-essential Cd2 + compete for their transport with the same transmembrane carrier [53]. As is the case of phytosiderophore such as Fe-transport in graminaceous species, metal chelate complexes can be transported by plasma membrane [54]. Among the most important parameter the most influencing factor of heavy metal accumulation in plants is soil pH [55, 56, 57, 58]. At higher soil pH, metal elements in soil solution decrease their bioavailability, and at lower soil pH metalelements in soil solution increase their bioavailability to plants [59].
Heavy metals mitigate the growth and development of the plant [60, 61]. The plant parts which are associated with the heavy metals polluted soils normally the roots express rapid and sensorial changes in their growth and development [62]. It is well observed that the very significant effects of a number of metals (Cd, Al, Cu, Fe, Ni, Pb, Hg, Cr, Zn,) on the growth of above ground plant parts vary [63]. Through the formation of free radicals and reactive oxygen species (ROS), heavy metals mainly affect plant growth, which causes constant oxidative damage by decreasing important cellular components. [64, 65]. For example, rice seedlings irradiated to Cd or Ni [66] and runner bean plants treated with Cd and Cu have shown an increase in carbohydrate content and a decrease in photosynthesis process, resulting in growth inhibition [67]. Similarly, in cucumber plants, Cu limits K uptake by leaf and inhibits the photosynthesis via sugar acquisition resulting into the inhibition of cell expansion [68]. Limped leaves, growth inhibition, progressive chlorosis in certain leaves and leaf sheaths and browned root systems, especially the root tips, are the symptoms of Cd toxicity in rice plants [7, 69]. Moreover, plant growth has also been retarded in maize (Zea mays) Cd [70, 71]. Some phenotypic abnormalities such as stunted growth, less branching and less fruiting are also shown by tomato plants irrigated with polluted water. However, acquisition of heavy metals is much more appears in stems, roots, and leaves as compared to fruits [72].
Seed germination is the breaking of seed dormancy which is inhibited by heavy metals. Germination of seeds and growth of seedling may sensitive towards environmental conditions [59]. So as per [73], the performance of germination, breaking of seed dormancy and seedlings growth rates are therefore often used to assess the abilities of plant tolerance to metal elementsIn comparison to control, higher concentrations such as 1 μM, 5 μM and 10 μM of heavy metals such as Cu, Zn, Mg and Na significantly inhibit seed germination and early growth of rice, barley, wheat and maize seedlings [74]. The ability of a seed to germinate in a moderate containing any metal element like Cr would be a direct indication of its level of tolerance to this metal, but seed germination is the first physiological process affected by toxic elements [73]. At 200 μM of Cr treatment, the seed germination of Echinochloa colona is decreased to 25 percent [75], and high levels (500 ppm) of Cr (VI) in soil decreased Phaseolus vulgaris germination by up to 48 percent [76]. Jain et al. [77] observed reductions in sugarcane bud germination of up to 35 per cent and 60 per cent at 20 and 80 ppm Cr application, respectively. In another study by Peralta et al. [73], at 40 ppm Cr (VI) treatment, Medicago sativacv germination was reduced to 23 percent.
Among the plant parts, roots are firstly come into contact with toxic elements and they usually absorbed more metals by root hair through absorbption process but shoots are not that [78, 79, 80]. The inhibition or retard of root elongation appears to be the first visible effect of metal toxicity. Elongations of root are reduced by the inhibition of cell division, the decrease of cell expansion, decrease of cell size in the elongation zone [81]. So the first visible effect of metal toxicity is the inhibition of root elongation, the root length can be used as most important tolerance index [82, 83, 84, 85]. Medicago sativa plants grown in solid media watered with 20 mg L−1 of Cr (VI) in another [73] study, the ratio of Cr in shoots to Cr in roots was approximately 43 percent. This is an indication that in the roots, 50 percent of the absorbed Cr is held. The response of roots to heavy metals in both herbaceous plant species and trees has been extensively studied. [86, 87, 88, 89]. After the work of numerous researchers [86, 87, 89, 90]. The main morphological and structural effects of metal root toxicity can be summarised as: (i) decrease in root elongation, (ii) decrease in biomass, (iii) decrease in vessel diameter, (iv) damage to tip, (v) collapse of root hair or decrease in number of roots, (vi) increase or decrease in lateral root formation, (vii) enhancement of suberification, (viii) enhancement of lignifications, (ix) translocation process become hampered. The research work of [91], revealed that Cr affects the root length than the other parts of plant as compared to other heavy metals. Mokgalaka-Matlala et al. [92], have observed that when increasing concentrations of As (V) and As (III) in Prosopis juliflora, the root elongation decreased significantly. It is reported that when Cr has applied on Salix viminalisis then the root length is affected more than by Cd and Pb [91]. In fact, the inhibition effect of Cr on the growth of the Salix alba root is similar to that of Hg and stronger than that of Cd and Pb, whereas the root length of Ni decreased less than Cr [93, 94]. In Salix viminalisis, the order of metal toxicity to the new root rimordial was reported to be Cd > Cr > Pb [91].
The heavy metal elements highly affect the plant height as well as shoot growth [95]. Cr transport to the various part of the plant have a direct impact on cellular metabolism as a result shoots contributing affected so plant height ultimately reduces [61]. It is observed that reduction of 11, 22 and 41% respectively compared to control in oat plants at 2, 10 and 25 ppm of Cr content in nutrient solutions in sand cultures [96]. Joseph et al. [97] observed a similar reduction in the height of Curcumas sativus, Lactuca sativa and Panicum miliaceum due to Cr (VI). Shoot growth in Medicago sativa is inhibited by Cr (III) [98]. In a glasshouse experiment after 32 and 96 days, Sharma and Sharma [99] noted a significant decrease in the height of Triticum aestivum when sown in sand with 0.5 μM sodium dichromate. A significant reduction in height of Sinapsis albaat a level of 200 or 400 mg kg−1 of Cr in soil along with N, P, K and S fertilizers was reported by Hanus and Tomas [100]. Very recently, it is found that a reduction in stem height at various concentrations (10, 20, 40 and 80 ppm) of Cd and Cr have been reported in Dalbergia sisso seedlings compared to the control [101].
The heavy metal elements severely affect the leaf height as well as leaf growth. Metal elements like Cd induce morphological changes such as drying of older leaves, wilt, and chlorosis and necrosis of younger leaves. Datura innoxia, D. metel, plants grown in a contaminated environment with Cr(VI) exhibited toxic symptoms at 0.1 mM to 0.2 mM of Cr(VI) in the form of leaf fall and wilting of leaves at 0.4 to 0.5 mM Cr(VI) in soil [97, 102]. A similar reduction in the height of Curcumas sativus, Lactuca sativa and Panicum miliaceum due to Cr(VI) was observed (1995). In Medicago sativa, shoot growth is inhibited by Cr(III) [98]. Sharma and Sharma [99] noted a significant drop in the height of Triticum aestivum when sown in sand with 0.5 μM sodium dichromate in a glasshouse experiment after 32 and 96 days [103]. In Zea mays, Acacia holosericeaOryza sativa, and Leucaena leucocephala plants treated with tannery effluent of varying concentrations, leaf dry weight and leaf area slowly decreases [104]. The effect of Cr(III) and Cr(VI) on the Spinacia oleracea plant was found in a study. Singh [105] reported that Cr applied to soil at a rate of 60 mg kg−1 and higher levels decreased the size of the leaves, causing leaf foliage, leaf tips or margins to burn, and slowed the rate of leaf growth.
The physiological process of the plant is severely affected by heavy metal elements. In reaction to heavy metal stress, plants show morphological, physiological, biochemical and metabolic changes which are thought to be adaptive responses [106]. Cd not only inhibits growth, for example, but also changes different physiological and biochemical features such as water balance, nutrient uptake, photosynthesis, breathing, mineral, nutrition and ion uptake, translocation, plant hormone [107, 108, 109] and Photosynthetic electron transport around PS I and PS II photosystems [110, 111, 112]. Likewise, Cr inhibits electron transport, decreases CO2 fixation, malformation of chloroplast [113, 114, 115], decreases water potential, increases transpiration rate, decreases diffusive resistance, and causes a reduction intercalary meristem [116].
The photosynthetic mechanism is significantly impacted by the heavy metal elements. The photosynthetic apparatus tends to be very susceptible to the toxicity of heavy metals, which directly or indirectly affect the photosynthetic process by inhibiting the enzyme activities of the Calvin cycle and CO2 deficiency in the plant body due to stomatal closure [59, 117, 118]. Cr has a well-cited detrimental effect on the photosynthic process in terrestrial plants. The influence of Cr on the PS I was more conspicuous than on the PS II operation in isolated chloroplasts of Pisumsativum plant [119] according to different reports. Photo inhibition in the leaves of Lolium perenne due to the influence of 250 μM Cr on the primary photochemistry of PS II, according to the Vernay et al. [120] report and A decrease in the overall photochemical efficiency of plant PS II at 500 μM of Cr was noted. Shanker et al. [61] argued that Cr triggered oxidative stress in plants because, due to the loss of molecular oxygen, Cr improves alternate sinks for the electrons. The ultimate influence of Cr ions on photosynthesis and conversion of excitation energy will be attributed to Cr-induced anomalies such as thylakoid expansion and reduction in the amount of grana in the ultrastructure of the chloroplast [121]. The impact of Cr on photosynthesis in higher plants is widely known [122, 123], it is not well known to what degree Cr induces photosynthesis inhibition either because of ultra-structure chloroplast malformation and the influence of Cr on the Calvin cycle enzymes or because of electron transport inhibition [116]. Krupa and Baszynski explained in 1995 that some theories applied to all photosynthesis pathways of heavy metal toxicity and introduced a list of primary photosynthetic carbon reduction enzymes that inhibited mainly cereal and legume crops in heavy metal treated plants. The 40 percent inhibition of whole plant photosynthesis in 52-day-old Pisum sativum seedlings at 0.1 mM Cr(VI) was further increased to 65 and 95 percent after 76 and 89 days of growth respectively [119]. A potential explanation of Cr mediated reduction rate of photosynthetic is a malformation of the chloroplast ultra structure and inhibition or returdation of electron transport processes due to Cr and a diversion of electrons from the electron donation side of PS-I to Cr (VI). It is likely that, as demonstrated by the low photosynthetic rate of the Cr stressed plants, electrons generated by the photo chemical process are not generally used for carbon fixation. According to [124, 125, 126], bioaccumulation of Cr and its toxicity to photosynthetic pigments in various crops and trees has been investigated. [127]; has extensively studied the effect of Cr present in tannery effluent sludge which directly get into chloroplast pigment content in Vigna radiata and reported that irrespective of Cr concentration, chlorophyll a, chlorophyll b, chlorophyll d and total chlorophyll decreased in 6 days old seedlings as compared to control. Chatterjee and Chatterjee [128] have reported that a dramatic decrease in chlorophylls a, b and d in leaves was recorded in Brassica oleracea grown in distilled sand with full nutrition with control and Co, Cr and Cu at 0.5 mM each. The stress order was Co > Cu > Cr. Conversely, a broad analysis on the tolerance of Cr and Ni in Echinochloa colona found that in terms of survival under elevated Cr concentration, the chlorophyll content was high in resistant calluses [129]. Chromium (VI) at 1 and 2 mg L−1 significantly decreased chlorophylls a, b and d and carotenoid concentrations in Salvinia minima [130]. The decrease in the chlorophyll a/b ratio brought about by Cr indicates that Cr toxicity possibly reduces the size of the peripheral part of the antenna complex [114]. It has been hypothesized that the decrease in chlorophyll b due to Cr could be due to the destabilization and degradation of the proteins of the peripheral part [61]. The interaction of heavy metals with the functional SH groups of proteins according to Van Assche and Clijsters [131, 132] is a possible mechanism of action for heavy metals.
Every physiological process is directly linked to water’s chemical potential. Water’s chemical potential is a quantitative expression of water-related energy. In plant growth regulation, water can be considered as the most important factor because it affects all growth processes directly or indirectly [133]. Plants grown in contaminated heavy metal soils often suffer from drought stress due primarily to poor physicochemical properties of the soil and shallow root system; researchers are interested in investigations on plant water relation under heavy metal stress. According to Barcelo et al. [134], Selection of drought resistance species can be considered to be an important trait in phytoremediation of soils polluted with heavy metals. The heavy metal stress can induce stress in plants through a series of events leading to decreased water loss like enhanced water conservation, decrease in number and size of leaves, decrease in root hair, malformation of parenchymatous cells stomatal size, number and diameter of xylem vessels, increased stomatal resistance, enhancement of leaf rolling and leaf abscission, higher degree of root suberization [90]. It has been suggested that through various mechanisms operating on the apoplastic and/or the symplastic pathway, heavy metals may influence root hydraulic conductivity. Reduced cell expansion can occur in the growth medium at relatively low concentrations without damaging the integrity of the cells. In bean plants, for instance, leaf expansion growth was inhibited after 48 h in bean plants exposed to 3 uM Cd. The most significant higher toxic effect of Cr (VI) is to degenerate the stomatal conductance that could damage the cells and membranes of stomatal guard cells. In this way, the relationship between water and many plant species has been affected.
Complex processes has used by plants to adjust their metabolism to rapidly changing environment. These processes include transduction, transcription, perception, and transmission of stress stimuli [135, 136, 137]. During stressing conditions plants adopt various process likes mechanisms of resistance and tolerance, later involves the immobilization of a metal in roots and in cell walls [138]. The plants adopt a series of mechanisms to avoid heavy metal toxicity which include: (i) Through auto oxidation and Fenton reaction plant produce reactive oxygen, (ii) blocking of main functional group, and (iii) from biomolecules displacement of metal ions, [139]. Plants are capable of growing in polluted soils because; (i) plants avoid metal absorption by aerial components or sustain low metal concentrations over a wide range of metal concentrations in soil by trapping metals in their roots [140]; (ii) plants deliberately absorb metals in their epidermal tissues due to the development of metal binding chelators (iii) they storing metals in non-sensitive parts by alter metal compartmentalisation pattern that is called metal indicators, and (iv) by the process of hyperaccumulators i.e. they can accumulate metals at much higher levels than soil in their aerial components [141, 142]. The processes used for hyperaccumulation are still unclear. Plants that can accumulate either As, Cu, Cr, Ni, Pb, or Co > 1000 mg kg−1 or zinc >10,000 mg kg−1 in their shot dry matter ([141, 143, 144, 145]; Baker and Reeves 2000) or Mo > 1500 mg kg−1 [146] are the standard for classifying plants as hyperaccumulators. (ii) Plants that absorb metals 10–500 times higher than average amounts in shoots [147], (iii) plants that accumulate metal components more in shoots than in roots [141]. Very few higher plant species have adaptations that enable them to live and replicate with Zn, Cu, Pb, Cd, Ni, and As highly polluted soils. [148, 149]. The tree roots of these plants can deliberately forage towards less polluted soil areas [150] and can “rest and wait” for optimal growth conditions even with highly reduced growth [151].
For the biological, biochemical and physiological functions of plants, various types of heavy metal elements are very important, including protein biosynthesis, lipids, nucleic acids, growth substances, hormones, chlorophyll and secondary metabolism synthesis, stress tolerance, morphological, structural and functional integrity of different membranes and other cellular compounds. These metal components, however, become poisonous in nature, above allowable limits, depending on the types of plants and the nature of the metal. Metal toxicity can inhibit the transport chain of electrons, reduce CO2 fixation, decrease the production of biomass, and cause chloroplast malformation. It can also affect plant growth by generating free radicals and ROS and other substances, which, by decreasing important cellular components, pose a threat to continuous oxidative damage. In addition, heavy metal stress can induce many events in plants leading to decrease in number and size of leaves, enhancement of leaf rolling and leaf abscission, leave erosion, changes in stomatal size, guard cell size, and stomatal resistance, and higher degree of root ligninization, suberization. Symptoms that are visible in plant by the affect of heavy metal toxicity include drying of older leaves, chlorosis, and necrosis of young leaves, stunting, wilting, canker, colour changes, blotch wrinkling and yield reduction. However, plants use complex processes (perception, transduction, and transmission of stress stimuli) and several non enzymatic and enzymatic mechanisms such as CAT, SOD, POD, and APX that activate the cell for their metabolism to heavy metal stress.
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\n\nOur platform – IntechOpen is the world’s leading publisher of OA books, built by scientists, for scientists.
\n\nOur reputation – Everything we publish goes through a two-stage peer review process. We’re proud to count Nobel laureates among our esteemed authors. We meet European Commission standards for funding, and the research we’ve published has been funded by the Bill and Melinda Gates Foundation and the Wellcome Trust, among others. IntechOpen is a member of all relevant trade associations (including the STM Association and the Association of Learned and Professional Society Publishers) and has a selection of books indexed in Web of Science's Book Citation Index.
\n\nOur expertise – We’ve published more than 4,500 books by more than 118,000 authors and editors.
\n\nOur reach – Our books have more than 130 million downloads and more than 146,150 Web of Science citations. We increase citations via indexing in all the major databases, including the Book Citation Index at Web of Science and Google Scholar.
\n\nOur services – The support we offer our authors and editors is second to none. Each book in our program receives the following:
\n\nOur end-to-end publishing service frees our authors and editors to focus on what matters: research. We empower them to shape their fields and connect with the global scientific community.
\n\n"In developing countries until now, advancement in science has been very limited, because insufficient economic resources are dedicated to science and education. These limitations are more marked when the scientists are women. In order to develop science in the poorest countries and decrease the gender gap that exists in scientific fields, Open Access networks like IntechOpen are essential. Free access to scientific research could contribute to ameliorating difficult life conditions and breaking down barriers." Marquidia Pacheco, National Institute for Nuclear Research (ININ), Mexico
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