nanomaterials Review
One-Dimensional Electron Transport Layers for Perovskite Solar Cells Ujwal K. Thakur 1, *,† , Ryan Kisslinger 1,† and Karthik Shankar 1,2 1 2
* †
Department of Electrical and Computer Engineering, University of Alberta, Edmonton, AB T6G 1H9, Canada; [email protected] (R.K.); [email protected] (K.S.) National Research Council, National Institute for Nanotechnology, 11421 Saskatchewan Drive NW, Edmonton, AB T6G 2M9, Canada Correspondence: [email protected]; Tel.: +1-780-492-1354 These authors contributed equally.
Academic Editor: Shuangqiang Chen Received: 12 February 2017; Accepted: 24 April 2017; Published: 29 April 2017
Abstract: The electron diffusion length (Ln ) is smaller than the hole diffusion length (Lp ) in many halide perovskite semiconductors meaning that the use of ordered one-dimensional (1D) structures such as nanowires (NWs) and nanotubes (NTs) as electron transport layers (ETLs) is a promising method of achieving high performance halide perovskite solar cells (HPSCs). ETLs consisting of oriented and aligned NWs and NTs offer the potential not merely for improved directional charge transport but also for the enhanced absorption of incoming light and thermodynamically efficient management of photogenerated carrier populations. The ordered architecture of NW/NT arrays affords superior infiltration of a deposited material making them ideal for use in HPSCs. Photoconversion efficiencies (PCEs) as high as 18% have been demonstrated for HPSCs using 1D ETLs. Despite the advantages of 1D ETLs, there are still challenges that need to be overcome to achieve even higher PCEs, such as better methods to eliminate or passivate surface traps, improved understanding of the hetero-interface and optimization of the morphology (i.e., length, diameter, and spacing of NWs/NTs). This review introduces the general considerations of ETLs for HPSCs, deposition techniques used, and the current research and challenges in the field of 1D ETLs for perovskite solar cells. Keywords: photovoltaics; ordered bulk heterojunctions; solution processing; light scattering; surface traps; electrochemical anodization; solvothermal synthesis; metal oxide; TiO2 ; ZnO
1. Introduction The increasing global demand for energy has spurred research efforts to find new and improved sources of cheap, environmentally neutral, renewable energy. Inorganic solar cells based on materials such as crystalline silicon, cadmium telluride, or copper indium germanium selenide (CIGS) constitute mature technologies that exhibit a relatively high power conversion efficiency (PCE) of around 12%–20% in deployed modules [1] and thus dominate commercially available photovoltaic technologies. However, the relatively long energy payback times of inorganic solar cells [2,3] have partially impeded their pace to widespread deployment, and thus alternative approaches are being explored. Organic photovoltaics [4], dye-sensitized solar cells [5], halide perovskite solar cells [6], and quantum-dot solar cells [7] are examples of next generation solution-processable solar cell technologies that have emerged as lower cost, lower energy payback time alternatives to replace conventional solar cells [8,9]. Among these technologies, halide perovskite solar cells (HPSCs) are currently the topic of intense scientific and engineering interest due to their facile synthesis, use of earth-abundant constituent elements and high device performance [10]. A major breakthrough occurred in 2012 when Nanomaterials 2017, 7, 95; doi:10.3390/nano7050095
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performance [10]. A major breakthrough occurred in 2012 when Snaith et al. [11] reported an HPSC Snaith et al. [11] reported HPSCa device a PCE of 11% using a mixed perovskite layer device with a PCE of 11%anusing mixed with halide perovskite layer (CH PbI3−xCl 3NH3halide x) as the active (CH3 NH PbI Cl ) as the active layer on nanoporous aluminum oxide. The first report of a HPSC layer on nanoporous aluminum oxide. The first report of a HPSC was by Miyasaka and co-workers, 3 3−x x was Miyasaka and obtained a PCElayer of 3.8% in 2009of[12] an3active layer who by obtained a PCE of co-workers, 3.8% in 2009who [12] using an active consisting CHusing (henceforth 3NH3PbI consisting NH PbI (henceforth referred to as MAPbI ). referred to of asCH MAPbI ). 33 3 3 3 Perovskites, named named after after the the Russian Perovskites, Russian mineralogist mineralogist Lev Lev A. A. Perovski, Perovski, are are compounds compounds having having the the molecular formula cations together with X molecular formula ABX ABX33 and and aa specific specificcrystal crystalstructure structureconsisting consistingofofAAand andB B cations together with anions arranged in in a cubic array of BX6 octahedra sharing corners, with the the A cations placed in the X anions arranged a cubic array of BX6 octahedra sharing corners, with A cations placed in cuboctahedral interstices which belong to the Pm3m crystal structure as shown in Figure 1 [13]. the cuboctahedral interstices which belong to cubic the cubic Pm3m crystal structure as shown in Figure 1 + + , CH ++ In halide perovskites, X is X a halide ion ion while A isAaismonovalent ionion such as as CsCs [13]. In halide perovskites, is a halide while a monovalent such , CH (MA), 3NH 3 NH 3 3 (MA), or NH=CHNH and BB is is aa divalent Unlike oxide or NH=CHNH33++, ,and divalent ion ion such such as as Pb Pb2+2+ or or Sn Sn2+2+.. Unlike oxide perovskites, perovskites, halide halide perovskites are thethe bond between the the Group IV metal atomatom and the atom perovskites arenot notstrictly strictlyionic ionicsince since bond between Group IV metal andhalide the halide has some covalent character, whichwhich is maximum for iodide perovskites. atom has some covalent character, is maximum for iodide perovskites.
Figure Schematicof of cubic metal halide perovskites with the composition ABX , Univalent with A = Figure 1.1.Schematic cubic metal halide perovskites with the composition ABX3 , with A3= Univalent alkali metal cation (shown in green), B = Group IV metal cation (shown in grey) and ion X= alkali metal cation (shown in green), B = Group IV metal cation (shown in grey) and X = halide halide ion (shown in purple). Reprinted with permission from Macmillan Publishers Ltd.: Nature (shown in purple). Reprinted with permission from Macmillan Publishers Ltd.: Nature Materials Materials Ref. [14], Copyright 2014. Ref. [14], Copyright 2014.
Halide perovskites have unique properties [15] such as a direct optical bandgap, broadband Halide perovskites have unique properties [15] such as a direct optical bandgap, broadband light light absorption, low carrier effective masses, dominant shallow point defects, benign grain absorption, low carrier effective masses, dominant shallow point defects, benign grain boundaries, boundaries, ambipolar transport, and long carrier diffusion lengths, due to which they have been ambipolar transport, and long carrier diffusion lengths, due to which they have been investigated as investigated as light-absorbing and charge transporting materials in photovoltaic devices. In an light-absorbing and charge transporting materials in photovoltaic devices. In an astonishingly short astonishingly short period, this has led to an as-of-yet highest power conversion efficiency of 21.1% period, this has led to an as-of-yet highest power conversion efficiency of 21.1% [16]. The highest [16]. The highest efficiencies reported thus far, have been obtained using iodide perovskites, and efficiencies reported thus far, have been obtained using iodide perovskites, and mixed iodide-bromide mixed iodide-bromide perovskites. One challenge associated with perovskite solar cells is the perovskites. One challenge associated with perovskite solar cells is the choice of electron transport layer choice of electron transport layer (ETL) in the solar cell architecture. It is important for the ETL to (ETL) in the solar cell architecture. It is important for the ETL to possess certain properties including possess certain properties including an appropriate work function, high conductivity, fast charge an appropriate work function, high conductivity, fast charge transport, and a low recombination transport, and a low recombination rate at the interface. Both inorganic and organic semiconductors rate at the interface. Both inorganic and organic semiconductors have been used, with TiO2 being have been used, with TiO2 being the most commonly used and having seen the most success. The the most commonly used and having seen the most success. The morphology of the ETL layer morphology of the ETL layer is also of importance with planar film layers, mesoscopic particulate is also of importance with planar film layers, mesoscopic particulate layers, and nanostructured layers, and nanostructured layers being used. Planar film layers, while being the easiest to fabricate, layers being used. Planar film layers, while being the easiest to fabricate, are required to have a are required to have a sufficient thickness in order to absorb all of the incident solar light. This sufficient thickness in order to absorb all of the incident solar light. This thickness, however, is usually thickness, however, is usually required to be longer than the diffusion length of electrons, which required to be longer than the diffusion length of electrons, which has been measured to be 100 nm has been measured to be 100 nm or higher in iodide perovskites [17]. Mesoscopic electron transport or higher in iodide perovskites [17]. Mesoscopic electron transport layers have the advantage of layers have the advantage of allowing for infiltration of the perovskite, meaning that any dimension allowing for infiltration of the perovskite, meaning that any dimension of the perovskite is kept of the perovskite is kept to a minimum while still being able to absorb all the sun’s incident light to a minimum while still being able to absorb all the sun’s incident light [18]. However, it can be [18]. However, it can be very difficult to completely fill the pore network of a mesoscopic structure very difficult to completely fill the pore network of a mesoscopic structure with perovskite, and any with perovskite, and any unfilled areas inevitably lead to recombination at the exposed surfaces. In unfilled areas inevitably lead to recombination at the exposed surfaces. In addition, a mesoscopic addition, a mesoscopic structure consisting of an interconnected network of nanoparticles, results in
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non-directional electron transport involving a random walk [19]. One dimensional nanostructures (1D-NS),consisting however,of are to lever the network same advantages of mesoscopic structures, while being able structure anable interconnected of nanoparticles, results in non-directional electron to allowinvolving for a more complete of perovskite into the electron transport a random walk infiltration [19]. One dimensional nanostructures (1D-NS),transporting however, are layer. able Furthermore, their directional charge transport properties enable increased solar cell efficiencies to lever the same advantages of mesoscopic structures, while being able to allow for a more complete [20–23]. Inof addition, with optimized geometries the improved management infiltration perovskite1D-NS into the electron transporting layer. enable Furthermore, their directional chargeof incident properties photons inenable the solar cell. This aims to [20–23]. summarize the fundamentals preparing transport increased solar review cell efficiencies In addition, 1D-NS withofoptimized perovskite solar cells and how they relate to using one-dimensional electron transport layers geometries enable the improved management of incident photons in the solar cell. This review aims (1D-ETLs), with emphasis on TiO and ZnO nanostructures as the leading candidates. The 2 to summarize the fundamentals of preparing perovskite solar cells and how they relate to using fundamentals of selecting and layers fabricating ETLswith will be discussed, as ZnO well nanostructures as the special one-dimensional electron transport (1D-ETLs), emphasis on TiO2 and considerations that one has to take into account when dealing with one-dimensional as the leading candidates. The fundamentals of selecting and fabricating ETLs will be nanostructures. discussed, as Finally, still need tothat be one solved order foraccount 1D-NS when to achieve commercial viability are well as theissues specialthat considerations has in to take into dealing with one-dimensional addressed. nanostructures. Finally, issues that still need to be solved in order for 1D-NS to achieve commercial
viability are addressed. 2. Architecture and Working Mechanism of Devices 2. Architecture Working Mechanism of Devices As shownand in Figure 2, perovskite solar cells are fabricated in two major architectures, p-i-n and n-i-pAstype. In the p-i-n type architecture, p-type hole transporting layerarchitectures, (HTL) such as CuO, shown in Figure 2, perovskite solaracells are fabricated in two major p-i-n andNiO n-i-por PEDOT: is type deposited on a transparent oxide namely type. In thePSS p-i-n architecture, a p-type holeconductive transporting layer(TCO) (HTL)coated such asglass CuO,substrate NiO or PEDOT: fluorine doped tin oxide (FTO) or indium tin oxide (ITO) coated glasses. This is followed by the PSS is deposited on a transparent conductive oxide (TCO) coated glass substrate namely fluorine deposition of (FTO) the perovskite layer which then coated over by by a the n-type film of doped tin oxide or indium active tin oxide (ITO) coatedisglasses. This is followed deposition acidwhich methyl ester (PCBM), ZnO, or C60 acts as an61 -butyric ETL and 61-butyric of[6,6]-phenyl-C the perovskite active layer is then coated over by a n-type filmwhich of [6,6]-phenyl-C subsequently a low work-function metal such is subsequently evaporated toa complete the device acid methyl ester (PCBM), ZnO, or C60 which actsasasaluminum an ETL and low work-function [24–29]. n-i-p type architecture,toan n-type the ETLdevice such [24–29]. as TiO2, In ZnO, SnO2type or WO 3 is deposited metal suchInasthe aluminum is evaporated complete the n-i-p architecture, an on a ETL TCO-coated glass substrate which is then followed by perovskite deposition. Over the n-type such as TiO , ZnO, SnO or WO is deposited on a TCO-coated glass substrate which is 2 2 3 perovskite, a p-type hole transporting layer (typically spiro-MeOTAD) is deposited and finally then followed by perovskite deposition. Over the perovskite, a p-type hole transporting layer (typically a high work function metal such as golda is deposited to complete [30–38]. This n-i-p spiro-MeOTAD) is deposited and finally high work function metal the suchdevice as gold is deposited to configuration is necessarily used for the formation of solar cells involving 1D-ETLs to allow for complete the device [30–38]. This n-i-p configuration is necessarily used for the formation of solar cells proper infiltration the for perovskite into the ETL. of noteinto is the thatETL. ETL-free involving 1D-ETLs toofallow proper infiltration of theAlso perovskite Also ofand noteHTL-free is that perovskite cells do exist butsolar theircells photovoltaic performance is low [33,39]. ETL-free andsolar HTL-free perovskite do exist but their photovoltaic performance is low [33,39].
Figure configuration forfor (a) (a) p-i-n typetype andand (b) n-i-p type type perovskite cell architectures. ETL and Figure2.2.Layer Layer configuration p-i-n (b) n-i-p perovskite cell architectures. ETL HTL refer to electron transporting layer and hole transporting layer respectively. FTO and ITO refer to and HTL refer to electron transporting layer and hole transporting layer respectively. FTO and ITO fluorine tin oxide coated glass and indium tin oxide coated glass respectively refer to fluorine tin oxide coated glass and indium tin oxide coated glass respectively
3.3.Halide HalidePerovskite PerovskiteDeposition DepositionTechniques Techniques The Theperformance performanceofofperovskite perovskitesolar solarcells cellsisishighly highlydependent dependenton onthe thecrystal crystalstructure structureand and morphology of the perovskite absorber, as well as the degree of contact the perovskite makes with the morphology of the perovskite absorber, as well as the degree of contact the perovskite makes with charge transport layers. layers. These factors significantly in accordance with the deposition the charge transport These vary factors vary significantly in accordance with theprocedure, deposition which shouldwhich ensureshould good infiltration and infiltration contact when with 1D-ETLs. to procedure, ensure good anddealing contact when dealingFurthermore, with 1D-ETLs. prevent direct contact between the electron transporting layer and hole transporting layer, an optimum Furthermore, to prevent direct contact between the electron transporting layer and hole thickness of perovskite overlayer thickness is needed.ofThis overlayer helps toisensure a sufficiently highhelps valueto transporting layer, an optimum perovskite overlayer needed. This overlayer ensure a sufficiently high value for the shunt resistance. Typically, single step spin coating, two step
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for the shunt resistance. Typically, single step spin coating, two step spin coating, and sequential spin coating, and sequential deposition techniques arelayer used in to perovskite deposit thesolar activecells. layerFigure in perovskite deposition techniques are used to deposit the active 3a is a solar cells. Figure 3a is a block diagram of method the one which step spin casting block diagram of the one step spin casting involves themethod mixingwhich of AXinvolves and BX2 the in mixingsolvents of AX and polar solvents (GBL), such asdimethylformamide γ-butyrolactone (GBL), dimethylformamide (DMF) polar suchBX as2 in γ-butyrolactone (DMF) and dimethyl sulfoxide and dimethyl sulfoxide (DMSO) to make the perovskite precursor solution. solution Spin casting of the (DMSO) to make the perovskite precursor solution. Spin casting of the precursor at sufficient precursor solution at sufficient per the minute (RPM) used to This achieve the desired film revolutions per minute (RPM) is revolutions used to achieve desired film is thickness. technique generally thickness.two This technique generally involves twoanother spinning steps—one RPM and another at involves spinning steps—one at low RPM and at high RPM. Inatalow typical synthesis, toluene high RPM. In a typical synthesis, toluene or chlorobenzene is added to the spinning substrate prior or chlorobenzene is added to the spinning substrate prior to the completion of the second spinning to theAfter completion the second spinning step. the spin coating step, substrates are step. the spin of coating step, the substrates areAfter annealed in order to force thethe crystallization of annealed in order to forcelayer. the crystallization of for the perovskite deposited perovskite This procedure for the deposited perovskite This procedure active layerlayer. deposition was initially perovskite active layer deposition was initially introduced by Miyasaka and with coworkers in 2009 and introduced by Miyasaka and coworkers in 2009 and perovskite solar cells the highest PCEs perovskite with thetechnique highest PCEs reported tosolar date cells employ this [12]. reported to date employ this technique [12].
Figure 3. Schematic Schematicillustration illustrationofof(a)(a)one one step spin casting (b) sequential deposition (c) step two spin step Figure 3. step spin casting (b) sequential deposition (c) two spin casting and (d) dual source vapor deposition techniques for perovskite deposition. Adapted casting and (d) dual source vapor deposition techniques for perovskite deposition. Adapted from from Refs. [40–43] with permission from Macmillan Ltd. andSociety The Royal Society of Refs. [40–43] with permission from Macmillan PublishersPublishers Ltd. and The Royal of Chemistry. Chemistry.
Figure 3b illustrates the methodology of the sequential deposition technique in which BX is Figure 3b illustrates the methodology of the sequential deposition technique in which BX22 is dissolved in polar solvents such as DMF and DMSO while another solution of AX is made in 2-propanol. dissolved in polar solvents such as DMF and DMSO while another solution of AX is made in First, BX2 is spin coated over the substrate followed by calcination. After cooling down the substrate 2-propanol. First, BX2 is spin coated over the substrate followed by calcination. After cooling down to room temperature, it is dipped into AX solution followed by annealing to crystallize the perovskite. the substrate to room temperature, it is dipped into AX solution followed by annealing to crystallize the perovskite. The sequential deposition procedure was initially developed by Mitzi and colleagues in 1998 [44] while Gratzel et al. re-introduced this technique to fabricate perovskite
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The sequential deposition procedure was initially developed by Mitzi and colleagues in 1998 [44] while Gratzel et al. re-introduced this technique to fabricate perovskite solar cells in 2013 [45]. A major problem with this methodology is the length of time needed to convert BX2 into ABX3 , during which some of the formed ABX3 can be leached away from the substrate. Two-step spin coating, illustrated in Figure 3c, is a modified version of sequential deposition in which BX2 is first spin coated over the substrate followed by calcination. After cooling down the substrate to room temperature AX dissolved in 2-propanol is spin coated over the dry BX2 layer. Another important deposition technique that has the ability to produce high performance perovskite solar cells is the dual source vapor deposition technique which was reported in 2013 by Snaith et al. [40]. As shown in Figure 3d, AX and BX2 are evaporated simultaneously from two different sources in a particular evaporation ratio to form ABX3 film on substrate which is then annealed. Other deposition techniques include sequential vacuum deposition [46], chemical vapor deposition [47], inkjet printing [48,49], spray coating [50,51], and slot die coating [52], but these methods have not been successful thus far in producing high efficiency photovoltaic devices. 4. One Dimensional Nanostructures 1D-NS used in photovoltaics, taking the form of familiar structures such as rods, tubes, and wires, possess two dimensions of a size between 1 and 100 nm while the third dimension is typically in the range 200 nm–1 µm. A wide variety of top-down and bottom-up fabrication approaches exist for their synthesis, with varying degrees of complexity that allow for greater or lesser control over the final structure. Chemical synthesis strategies for 1D-NS are often the cheapest and least demanding in terms of deposition equipment, and include electrodeposition, sol–gel synthesis, solvothermal methods, and electrochemical anodization. While ease of fabrication and relatively high-throughput make these methods attractive options, they often suffer from the drawback of having a greater variability in final properties due to the indirect measures of control inherent to these methods. Strategies based on physical or physicochemical synthesis of 1D-NS such as vapor phase deposition, chemical vapor deposition, vapor-liquid-solid growth, and atomic layer deposition often result in superior electronic properties due to lower impurities and superior crystallinity while requiring dedicated deposition equipment and extreme conditions such as high vacuum and/or elevated temperatures. Even more precise control over the final structure can be obtained by techniques such as electron beam lithography or focused-ion beam writing or x-ray lithography, although these processes are much more expensive and of low-throughput. Several studies have found that the diffusion length of photogenerated electrons in halide perovskites is lower than that of photogenerated holes as shown in Figure 4, which calls for the application of nanostructured ETLs in perovskite solar cells [53,54]. 1D-NS offer a large surface area and the possibility of confinement of phonons and charge carriers, which leads to distinct electrical, optical and structural properties when contrasted with those of bulk materials. They may be used to limit the “random walk” of charges through a material; as there is only one direction in which charges may travel, the overall length of the path a charge takes on its way to being collected is reduced and thus charge recombination is limited. It is also important to use an optimized thickness of ETLs in perovskite solar cells (corresponding to the length of 1D ETL nanostructures). Because most perovskite semiconductors used in solar cells have a high extinction coefficient, an increase in the thickness of 1D ETLs does not generally improve the overall absorption of the device. However, increasing the thickness of 1D ETLs can reduce the photovoltaic performance of perovskite solar cells. The open circuit voltage decreases as the nanostructure length increases because of increased recombination at the ETL/perovskite interface [55–57]. The short circuit current too typically decreases because of ultraviolet photons absorbed by thicker ETLs which cannot be transmitted to the perovskite absorber layer [55,58]. The fill factor also reduces because of an increased series resistance of the solar cell. On the other hand, too thin an ETL does not provide a sufficient mesoscopic effect. If left unoptimized, forward- and back-scattering due to thick nanostructured ETLs can outcouple incident photons out of
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the device and reduce the amount of light harvested [59]. The nanorod packing density in 1D ETLs is 6 of 26 Nanomaterials 2017, 7, 95 another important parameter which plays a crucial role in the photovoltaic performance of solar cells. If the nanorods are densely packed, then there is less room between adjacent nanorods/nanotubes filling and lower photovoltaic performance of the solar cells. Moderate and low density packing of for the perovskite to be filled, resulting in poor filling and lower photovoltaic performance of the the nanorods constituting the 1D ETL provide better filling and thus improved light harvesting solar cells. Moderate and low density packing of the nanorods constituting the 1D ETL provide better efficiency [60–62]. Thus, it is important to optimize the thickness and morphology of 1D ETLs to filling and thus improved light harvesting efficiency [60–62]. Thus, it is important to optimize the take proper advantage of their directional charge transport and light management properties thickness and morphology of 1D ETLs to take proper advantage of their directional charge transport without harming other performance parameters of the solar cell. For high aspect ratio nanorods in and light management properties without harming other performance parameters of the solar cell. the ETL, field emission of electrons into the perovskite is promoted, which in turn, may increase the For high aspect ratio nanorods in the ETL, field emission of electrons into the perovskite is promoted, dark current in the solar cells and thereby reduce the Voc value [59]. A superficial coating of which in turn, may increase the dark current in the solar cells and thereby reduce the Voc value [59]. perovskite is favored for high aspect ratio NRs with polar surfaces due to wetting considerations, as A superficial coating of perovskite is favored for high aspect ratio NRs with polar surfaces due to opposed to volumetric filling of the inter-rod spaces, which can exacerbate problems with wetting considerations, as opposed to volumetric filling of the inter-rod spaces, which can exacerbate extracting holes. problems with extracting holes.
Figure 4. Time-resolved photoluminescence (along with stretched exponential of MAPbI Figure 4. Time-resolved photoluminescence (along with stretched exponential fits)fits) of MAPbI 3 using 3 using electron quencher [6,6]-phenyl-C acid methyl ester (PCBM) shown as blue trianges thethe electron quencher [6,6]-phenyl-C acid methyl ester (PCBM) shown as blue trianges or or 61-butyric 61 -butyric using the the holehole quencher layerlayer Spiro-MeOTAD, shown as redas circles. The data withoutwithout the use the using quencher Spiro-MeOTAD, shown red circles. Theobtained data obtained of ause quencher, instead instead using insulating polymerpolymer poly(methylmethacrylate) (PMMA)(PMMA) is shown is asshown black as of a quencher, using insulating poly(methylmethacrylate) squares. Ref. [53] with permission The American for the Advancement black Adapted squares. from Adapted from Ref. [53] withfrom permission from Association The American Association for the in Science. Advancement in Science.
5. Materials One Dimensional Electron Transport Layers 5. Materials forfor One Dimensional Electron Transport Layers Both inorganic and organic semiconductors have been used electron transport materials, Both inorganic and organic semiconductors have been used as as electron transport materials, although it is inorganic that have received attention for their applicability as although it is inorganic materialsmaterials that have received attention for their applicability as one-dimensional one-dimensional since the morphological integrity of organic semiconductor nanostructures since nanostructures the morphological integrity of organic semiconductor nanostructures typically nanostructures typically doessolution not survive the subsequent deposition the halide does not survive the subsequent deposition of the halidesolution perovskite due to theofpartial or perovskite due toofthe complete solubility of the such organic semiconductors in solvents such complete solubility thepartial organicorsemiconductors in solvents as GBL, DMF, and DMSO [63,64]. GBL,noting, DMF, however, and DMSO It efforts is worth noting, thatofresearch efforts towards It isasworth that[63,64]. research towards thehowever, development one-dimensional organicthe development of organic semiconductors being made synthesis, through techniques such semiconductors areone-dimensional being made through techniques such as are solution-phase templating, as solution-phase synthesis, templating, [65]. TiO2, ZnO, electrospinning, and nanolithography [65]. electrospinning, TiO2 , ZnO, SnO2and , andnanolithography WOx are the most commonly SnO mostdiagram commonly usedinmaterials (energy level diagram shown in inorganic Figure 5) for used materials (energy level shown Figure 5) for 1D-ETLs, although other 2, and WO x are the 1D-ETLs, although other inorganic semiconductors that could potentially be such used as in a semiconductors exist that could potentially be used in a exist one-dimensional nanostructure, nanostructure, such as Zn SnO [66], BaSnO [67], and SrTiO [68]. While not a Znone-dimensional SnO [66], BaSnO [67], and SrTiO [68]. While not a focus of this review, common organic electron 2 4 3 3 2 4 3 3 focus materials of this include review,fullerenes, commonmethanofullerenes, organic electronandtransport materials include transport perylene derivatives. There are fullerenes, several methanofullerenes, and perylene several major considerations when selecting major considerations when selecting derivatives. the material There to useare as ETL, including the energy level alignment the material to use as ETL, including the energy level alignment with respect to the particular perovskite absorber used, the doping density, the density and energetic depth of trap states in the material, the electron mobility, and hole blocking action. The material most commonly used as the ETL is TiO2, which exhibits good electron transporting properties and is known to be non-toxic and
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with respect to the particular perovskite absorber used, the doping density, the density and energetic Nanomaterials 2017, 7, 95 in the material, the electron mobility, and hole blocking action. The material 7most of 26 depth of trap states commonly used as the ETL is TiO2 , which exhibits good electron transporting properties and is known chemically stable. three TiO crystalline phases—anatase, brookite, and rutile [69], among 2 exists in to be non-toxic andTiO chemically stable. 2 exists in three crystalline phases—anatase, brookite, and which the anatase has beenphase used TiO the most widely and achieved the highest performance rutile [69], among phase whichTiO the2 anatase 2 has been used the most widely and achieved the in photovoltaic applications due to possessing a higher effectivea surface area, faster electron highest performance in photovoltaic applications due to possessing higher effective surface area, transport, and longer electron lifetime than the other two phases [70,71]. The anatase phase of TiO2 faster electron transport, and longer electron lifetime than the other two phases [70,71]. The anatase also exhibits blocking, which is highly desirable. major issue withissue TiO2 phase of TiO2exceptional also exhibitshole exceptional hole blocking, which is highlyHowever, desirable. aHowever, a major and its potential to be used in commercial applications, is the high temperature processing typically with TiO2 and its potential to be used in commercial applications, is the high temperature processing required to anneal the TiOthe crystalline forms, since thethe as-fabricated often 2 into typically required to anneal TiO2these into these crystalline forms, since as-fabricatedTiO TiO2,2 , is is often amorphous. this problem, problem, efforts efforts have have been been made made to to develop develop crystalline crystalline TiO TiO2 without without the the amorphous. In In light light of of this 2 need for high-temperature processes [72]. Compared to other candidate ETL materials, TiO need for high-temperature processes [72]. Compared to other candidate ETL materials, TiO2 possesses2 possesses a high densityand of deep-trapping shallow- and states deep-trapping [73] thatShockley-Read-Hall in turn promote a high density of shallow[73] that instates turn promote Shockley-Read-Hall type recombination and Fermi-level pinning at interfaces with other materials. type recombination and Fermi-level pinning at interfaces with other materials. The most widely The most widely investigated replacement for TiO is ZnO, which has a 5–10 fold higher electron 2 investigated replacement for TiO2 is ZnO, which has a 5–10 fold higher electron mobility [74] and mobility [74] and suitable energy levels. However, processing issues and the poorer chemical suitable energy levels. However, processing issues and the poorer chemical stability of ZnO have stability havedevelopment hindered theofuse development of ZnO as an ETL. SnOnearly 2 has an hinderedof theZnO use and ZnOand as an ETL. SnO2 has an electron mobility twoelectron orders mobility nearly two orders of magnitude higher than that of TiO [75], yet shows much lower PCEs 2 PCEs due to non-optimal energy of magnitude higher than that of TiO2 [75], yet shows much lower due toand non-optimal energy levels andSimilarly, high recombination rates. Similarly, WOx has exhibited poor levels high recombination rates. WOx has exhibited poor performance when used by performance when used by itself. However, both SnO and WO have shown increased 2 x itself. However, both SnO2 and WOx have shown increased performance when used in combination performance with ZnO and as in a core shell can structure [38]. 2, such with ZnO andwhen TiO2 ,used suchin ascombination in a core shell structure [38].TiO Such a core-shell structure effectively Such a core-shell structure can effectively suppress recombination and improve the electron transfer suppress recombination and improve the electron transfer at the ETL/perovskite interface, resulting in at the ETL/perovskite interface, resulting improved solar cell performance [61,76]. in improved solar cell performance [61,76].
Figure 5. Figure 5. Energy Energy level level diagrams diagrams illustrating illustrating the the position position of of the the conduction conduction band band minimum minimum vs. vs. the the vacuum level in various electron transport layer materials. Adapted from Ref. [77] with permission vacuum level in various electron transport layer materials. Adapted from Ref. [77] with permission from The Royal Society of Chemistry. from The Royal Society of Chemistry.
6. Classes Classes of of One One Dimensional Dimensional Nanostructures Nanostructures Used Used as 6. as ETLs ETLs in in Perovskite Perovskite Solar Solar Cells Cells The vast of 1D-ETLs take take the form nanotubes or nanorods (also known as nanowires). The vastmajority majority of 1D-ETLs the of form of nanotubes or nanorods (also known as However, other morphologies do exist, including nanofibers and core-shelland structures utilizing two nanowires). However, other morphologies do exist, including nanofibers core-shell structures or more materials as the electron transporting layer. Herein, we focus on the structure and function utilizing two or more materials as the electron transporting layer. Herein, we focus on the structure of TiO and ZnO nanorods, with the reported solar cell performance of 2 nanotubes, 2 nanorods, and function of TiOTiO TiO 2 nanotubes, 2 nanorods, and ZnO nanorods, with the reported solar cell performance of TiO2 1D-ETLs and ZnO 1D-ETLs summarized in Table 1 and Table 2 respectively. Table 3 and Section 6.4 summarize unorthodox 1D-ETL morphologies and materials. 6.1. TiO2 Nanotube Arrays
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TiO2 1D-ETLs and ZnO 1D-ETLs summarized in Tables 1 and 2 respectively. Table 3 and Section 6.4 summarize unorthodox 1D-ETL morphologies and materials. 6.1. TiO2 Nanotube Arrays Vertically oriented, self-organized, highly ordered TiO2 nanotubes (NTs) have attracted interest for use in dye-sensitized solar cells, quantum dot-sensitized solar cells, and bulk heterojunction photovoltaic devices since the mid-2000s [78–82]. While various methods to fabricate TiO2 nanotubes exist—including sol–gel [83], atomic layer deposition into nanoporous templates [84], and hydrothermal methods [85]—by far the simplest route to obtain highly uniform TiO2 nanotube arrays is the anodization method. The anodization method involves applying a sufficiently anodic voltage to Ti metal foils or Ti thin films vacuum deposited on to a TCO-coated glass or plastic substrates in an electrochemical cell with an appropriately selected electrolyte [86–88]. The key to the process is the simultaneous oxidation of Ti to form a TiO2 oxide layer along with the electrochemical/chemical dissolution of TiO2 in the form of pitting, a feat accomplished by the presence of anions such as F− , Cl− or ClO4 − in the electrolyte [89–92]. While the exact formation process is not fully understood and remains contentious [93–96], the end result is that an entire TiO2 nanotube array is typically formed all across the Ti film over the course of minutes or hours. Depending on the conditions used and the thickness of the precursor Ti film, these nanotubes have lengths ranging from a few hundred nanometers to several hundred micrometers, with pore diameters ranging from tens to hundreds of nanometers [97–99]. For perovskite solar cells, a nanotube length (ETL film thickness) of
One-Dimensional Electron Transport Layers for Perovskite Solar Cells Ujwal K. Thakur 1, *,† , Ryan Kisslinger 1,† and Karthik Shankar 1,2 1 2
* †
Department of Electrical and Computer Engineering, University of Alberta, Edmonton, AB T6G 1H9, Canada; [email protected] (R.K.); [email protected] (K.S.) National Research Council, National Institute for Nanotechnology, 11421 Saskatchewan Drive NW, Edmonton, AB T6G 2M9, Canada Correspondence: [email protected]; Tel.: +1-780-492-1354 These authors contributed equally.
Academic Editor: Shuangqiang Chen Received: 12 February 2017; Accepted: 24 April 2017; Published: 29 April 2017
Abstract: The electron diffusion length (Ln ) is smaller than the hole diffusion length (Lp ) in many halide perovskite semiconductors meaning that the use of ordered one-dimensional (1D) structures such as nanowires (NWs) and nanotubes (NTs) as electron transport layers (ETLs) is a promising method of achieving high performance halide perovskite solar cells (HPSCs). ETLs consisting of oriented and aligned NWs and NTs offer the potential not merely for improved directional charge transport but also for the enhanced absorption of incoming light and thermodynamically efficient management of photogenerated carrier populations. The ordered architecture of NW/NT arrays affords superior infiltration of a deposited material making them ideal for use in HPSCs. Photoconversion efficiencies (PCEs) as high as 18% have been demonstrated for HPSCs using 1D ETLs. Despite the advantages of 1D ETLs, there are still challenges that need to be overcome to achieve even higher PCEs, such as better methods to eliminate or passivate surface traps, improved understanding of the hetero-interface and optimization of the morphology (i.e., length, diameter, and spacing of NWs/NTs). This review introduces the general considerations of ETLs for HPSCs, deposition techniques used, and the current research and challenges in the field of 1D ETLs for perovskite solar cells. Keywords: photovoltaics; ordered bulk heterojunctions; solution processing; light scattering; surface traps; electrochemical anodization; solvothermal synthesis; metal oxide; TiO2 ; ZnO
1. Introduction The increasing global demand for energy has spurred research efforts to find new and improved sources of cheap, environmentally neutral, renewable energy. Inorganic solar cells based on materials such as crystalline silicon, cadmium telluride, or copper indium germanium selenide (CIGS) constitute mature technologies that exhibit a relatively high power conversion efficiency (PCE) of around 12%–20% in deployed modules [1] and thus dominate commercially available photovoltaic technologies. However, the relatively long energy payback times of inorganic solar cells [2,3] have partially impeded their pace to widespread deployment, and thus alternative approaches are being explored. Organic photovoltaics [4], dye-sensitized solar cells [5], halide perovskite solar cells [6], and quantum-dot solar cells [7] are examples of next generation solution-processable solar cell technologies that have emerged as lower cost, lower energy payback time alternatives to replace conventional solar cells [8,9]. Among these technologies, halide perovskite solar cells (HPSCs) are currently the topic of intense scientific and engineering interest due to their facile synthesis, use of earth-abundant constituent elements and high device performance [10]. A major breakthrough occurred in 2012 when Nanomaterials 2017, 7, 95; doi:10.3390/nano7050095
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performance [10]. A major breakthrough occurred in 2012 when Snaith et al. [11] reported an HPSC Snaith et al. [11] reported HPSCa device a PCE of 11% using a mixed perovskite layer device with a PCE of 11%anusing mixed with halide perovskite layer (CH PbI3−xCl 3NH3halide x) as the active (CH3 NH PbI Cl ) as the active layer on nanoporous aluminum oxide. The first report of a HPSC layer on nanoporous aluminum oxide. The first report of a HPSC was by Miyasaka and co-workers, 3 3−x x was Miyasaka and obtained a PCElayer of 3.8% in 2009of[12] an3active layer who by obtained a PCE of co-workers, 3.8% in 2009who [12] using an active consisting CHusing (henceforth 3NH3PbI consisting NH PbI (henceforth referred to as MAPbI ). referred to of asCH MAPbI ). 33 3 3 3 Perovskites, named named after after the the Russian Perovskites, Russian mineralogist mineralogist Lev Lev A. A. Perovski, Perovski, are are compounds compounds having having the the molecular formula cations together with X molecular formula ABX ABX33 and and aa specific specificcrystal crystalstructure structureconsisting consistingofofAAand andB B cations together with anions arranged in in a cubic array of BX6 octahedra sharing corners, with the the A cations placed in the X anions arranged a cubic array of BX6 octahedra sharing corners, with A cations placed in cuboctahedral interstices which belong to the Pm3m crystal structure as shown in Figure 1 [13]. the cuboctahedral interstices which belong to cubic the cubic Pm3m crystal structure as shown in Figure 1 + + , CH ++ In halide perovskites, X is X a halide ion ion while A isAaismonovalent ionion such as as CsCs [13]. In halide perovskites, is a halide while a monovalent such , CH (MA), 3NH 3 NH 3 3 (MA), or NH=CHNH and BB is is aa divalent Unlike oxide or NH=CHNH33++, ,and divalent ion ion such such as as Pb Pb2+2+ or or Sn Sn2+2+.. Unlike oxide perovskites, perovskites, halide halide perovskites are thethe bond between the the Group IV metal atomatom and the atom perovskites arenot notstrictly strictlyionic ionicsince since bond between Group IV metal andhalide the halide has some covalent character, whichwhich is maximum for iodide perovskites. atom has some covalent character, is maximum for iodide perovskites.
Figure Schematicof of cubic metal halide perovskites with the composition ABX , Univalent with A = Figure 1.1.Schematic cubic metal halide perovskites with the composition ABX3 , with A3= Univalent alkali metal cation (shown in green), B = Group IV metal cation (shown in grey) and ion X= alkali metal cation (shown in green), B = Group IV metal cation (shown in grey) and X = halide halide ion (shown in purple). Reprinted with permission from Macmillan Publishers Ltd.: Nature (shown in purple). Reprinted with permission from Macmillan Publishers Ltd.: Nature Materials Materials Ref. [14], Copyright 2014. Ref. [14], Copyright 2014.
Halide perovskites have unique properties [15] such as a direct optical bandgap, broadband Halide perovskites have unique properties [15] such as a direct optical bandgap, broadband light light absorption, low carrier effective masses, dominant shallow point defects, benign grain absorption, low carrier effective masses, dominant shallow point defects, benign grain boundaries, boundaries, ambipolar transport, and long carrier diffusion lengths, due to which they have been ambipolar transport, and long carrier diffusion lengths, due to which they have been investigated as investigated as light-absorbing and charge transporting materials in photovoltaic devices. In an light-absorbing and charge transporting materials in photovoltaic devices. In an astonishingly short astonishingly short period, this has led to an as-of-yet highest power conversion efficiency of 21.1% period, this has led to an as-of-yet highest power conversion efficiency of 21.1% [16]. The highest [16]. The highest efficiencies reported thus far, have been obtained using iodide perovskites, and efficiencies reported thus far, have been obtained using iodide perovskites, and mixed iodide-bromide mixed iodide-bromide perovskites. One challenge associated with perovskite solar cells is the perovskites. One challenge associated with perovskite solar cells is the choice of electron transport layer choice of electron transport layer (ETL) in the solar cell architecture. It is important for the ETL to (ETL) in the solar cell architecture. It is important for the ETL to possess certain properties including possess certain properties including an appropriate work function, high conductivity, fast charge an appropriate work function, high conductivity, fast charge transport, and a low recombination transport, and a low recombination rate at the interface. Both inorganic and organic semiconductors rate at the interface. Both inorganic and organic semiconductors have been used, with TiO2 being have been used, with TiO2 being the most commonly used and having seen the most success. The the most commonly used and having seen the most success. The morphology of the ETL layer morphology of the ETL layer is also of importance with planar film layers, mesoscopic particulate is also of importance with planar film layers, mesoscopic particulate layers, and nanostructured layers, and nanostructured layers being used. Planar film layers, while being the easiest to fabricate, layers being used. Planar film layers, while being the easiest to fabricate, are required to have a are required to have a sufficient thickness in order to absorb all of the incident solar light. This sufficient thickness in order to absorb all of the incident solar light. This thickness, however, is usually thickness, however, is usually required to be longer than the diffusion length of electrons, which required to be longer than the diffusion length of electrons, which has been measured to be 100 nm has been measured to be 100 nm or higher in iodide perovskites [17]. Mesoscopic electron transport or higher in iodide perovskites [17]. Mesoscopic electron transport layers have the advantage of layers have the advantage of allowing for infiltration of the perovskite, meaning that any dimension allowing for infiltration of the perovskite, meaning that any dimension of the perovskite is kept of the perovskite is kept to a minimum while still being able to absorb all the sun’s incident light to a minimum while still being able to absorb all the sun’s incident light [18]. However, it can be [18]. However, it can be very difficult to completely fill the pore network of a mesoscopic structure very difficult to completely fill the pore network of a mesoscopic structure with perovskite, and any with perovskite, and any unfilled areas inevitably lead to recombination at the exposed surfaces. In unfilled areas inevitably lead to recombination at the exposed surfaces. In addition, a mesoscopic addition, a mesoscopic structure consisting of an interconnected network of nanoparticles, results in
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non-directional electron transport involving a random walk [19]. One dimensional nanostructures (1D-NS),consisting however,of are to lever the network same advantages of mesoscopic structures, while being able structure anable interconnected of nanoparticles, results in non-directional electron to allowinvolving for a more complete of perovskite into the electron transport a random walk infiltration [19]. One dimensional nanostructures (1D-NS),transporting however, are layer. able Furthermore, their directional charge transport properties enable increased solar cell efficiencies to lever the same advantages of mesoscopic structures, while being able to allow for a more complete [20–23]. Inof addition, with optimized geometries the improved management infiltration perovskite1D-NS into the electron transporting layer. enable Furthermore, their directional chargeof incident properties photons inenable the solar cell. This aims to [20–23]. summarize the fundamentals preparing transport increased solar review cell efficiencies In addition, 1D-NS withofoptimized perovskite solar cells and how they relate to using one-dimensional electron transport layers geometries enable the improved management of incident photons in the solar cell. This review aims (1D-ETLs), with emphasis on TiO and ZnO nanostructures as the leading candidates. The 2 to summarize the fundamentals of preparing perovskite solar cells and how they relate to using fundamentals of selecting and layers fabricating ETLswith will be discussed, as ZnO well nanostructures as the special one-dimensional electron transport (1D-ETLs), emphasis on TiO2 and considerations that one has to take into account when dealing with one-dimensional as the leading candidates. The fundamentals of selecting and fabricating ETLs will be nanostructures. discussed, as Finally, still need tothat be one solved order foraccount 1D-NS when to achieve commercial viability are well as theissues specialthat considerations has in to take into dealing with one-dimensional addressed. nanostructures. Finally, issues that still need to be solved in order for 1D-NS to achieve commercial
viability are addressed. 2. Architecture and Working Mechanism of Devices 2. Architecture Working Mechanism of Devices As shownand in Figure 2, perovskite solar cells are fabricated in two major architectures, p-i-n and n-i-pAstype. In the p-i-n type architecture, p-type hole transporting layerarchitectures, (HTL) such as CuO, shown in Figure 2, perovskite solaracells are fabricated in two major p-i-n andNiO n-i-por PEDOT: is type deposited on a transparent oxide namely type. In thePSS p-i-n architecture, a p-type holeconductive transporting layer(TCO) (HTL)coated such asglass CuO,substrate NiO or PEDOT: fluorine doped tin oxide (FTO) or indium tin oxide (ITO) coated glasses. This is followed by the PSS is deposited on a transparent conductive oxide (TCO) coated glass substrate namely fluorine deposition of (FTO) the perovskite layer which then coated over by by a the n-type film of doped tin oxide or indium active tin oxide (ITO) coatedisglasses. This is followed deposition acidwhich methyl ester (PCBM), ZnO, or C60 acts as an61 -butyric ETL and 61-butyric of[6,6]-phenyl-C the perovskite active layer is then coated over by a n-type filmwhich of [6,6]-phenyl-C subsequently a low work-function metal such is subsequently evaporated toa complete the device acid methyl ester (PCBM), ZnO, or C60 which actsasasaluminum an ETL and low work-function [24–29]. n-i-p type architecture,toan n-type the ETLdevice such [24–29]. as TiO2, In ZnO, SnO2type or WO 3 is deposited metal suchInasthe aluminum is evaporated complete the n-i-p architecture, an on a ETL TCO-coated glass substrate which is then followed by perovskite deposition. Over the n-type such as TiO , ZnO, SnO or WO is deposited on a TCO-coated glass substrate which is 2 2 3 perovskite, a p-type hole transporting layer (typically spiro-MeOTAD) is deposited and finally then followed by perovskite deposition. Over the perovskite, a p-type hole transporting layer (typically a high work function metal such as golda is deposited to complete [30–38]. This n-i-p spiro-MeOTAD) is deposited and finally high work function metal the suchdevice as gold is deposited to configuration is necessarily used for the formation of solar cells involving 1D-ETLs to allow for complete the device [30–38]. This n-i-p configuration is necessarily used for the formation of solar cells proper infiltration the for perovskite into the ETL. of noteinto is the thatETL. ETL-free involving 1D-ETLs toofallow proper infiltration of theAlso perovskite Also ofand noteHTL-free is that perovskite cells do exist butsolar theircells photovoltaic performance is low [33,39]. ETL-free andsolar HTL-free perovskite do exist but their photovoltaic performance is low [33,39].
Figure configuration forfor (a) (a) p-i-n typetype andand (b) n-i-p type type perovskite cell architectures. ETL and Figure2.2.Layer Layer configuration p-i-n (b) n-i-p perovskite cell architectures. ETL HTL refer to electron transporting layer and hole transporting layer respectively. FTO and ITO refer to and HTL refer to electron transporting layer and hole transporting layer respectively. FTO and ITO fluorine tin oxide coated glass and indium tin oxide coated glass respectively refer to fluorine tin oxide coated glass and indium tin oxide coated glass respectively
3.3.Halide HalidePerovskite PerovskiteDeposition DepositionTechniques Techniques The Theperformance performanceofofperovskite perovskitesolar solarcells cellsisishighly highlydependent dependenton onthe thecrystal crystalstructure structureand and morphology of the perovskite absorber, as well as the degree of contact the perovskite makes with the morphology of the perovskite absorber, as well as the degree of contact the perovskite makes with charge transport layers. layers. These factors significantly in accordance with the deposition the charge transport These vary factors vary significantly in accordance with theprocedure, deposition which shouldwhich ensureshould good infiltration and infiltration contact when with 1D-ETLs. to procedure, ensure good anddealing contact when dealingFurthermore, with 1D-ETLs. prevent direct contact between the electron transporting layer and hole transporting layer, an optimum Furthermore, to prevent direct contact between the electron transporting layer and hole thickness of perovskite overlayer thickness is needed.ofThis overlayer helps toisensure a sufficiently highhelps valueto transporting layer, an optimum perovskite overlayer needed. This overlayer ensure a sufficiently high value for the shunt resistance. Typically, single step spin coating, two step
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for the shunt resistance. Typically, single step spin coating, two step spin coating, and sequential spin coating, and sequential deposition techniques arelayer used in to perovskite deposit thesolar activecells. layerFigure in perovskite deposition techniques are used to deposit the active 3a is a solar cells. Figure 3a is a block diagram of method the one which step spin casting block diagram of the one step spin casting involves themethod mixingwhich of AXinvolves and BX2 the in mixingsolvents of AX and polar solvents (GBL), such asdimethylformamide γ-butyrolactone (GBL), dimethylformamide (DMF) polar suchBX as2 in γ-butyrolactone (DMF) and dimethyl sulfoxide and dimethyl sulfoxide (DMSO) to make the perovskite precursor solution. solution Spin casting of the (DMSO) to make the perovskite precursor solution. Spin casting of the precursor at sufficient precursor solution at sufficient per the minute (RPM) used to This achieve the desired film revolutions per minute (RPM) is revolutions used to achieve desired film is thickness. technique generally thickness.two This technique generally involves twoanother spinning steps—one RPM and another at involves spinning steps—one at low RPM and at high RPM. Inatalow typical synthesis, toluene high RPM. In a typical synthesis, toluene or chlorobenzene is added to the spinning substrate prior or chlorobenzene is added to the spinning substrate prior to the completion of the second spinning to theAfter completion the second spinning step. the spin coating step, substrates are step. the spin of coating step, the substrates areAfter annealed in order to force thethe crystallization of annealed in order to forcelayer. the crystallization of for the perovskite deposited perovskite This procedure for the deposited perovskite This procedure active layerlayer. deposition was initially perovskite active layer deposition was initially introduced by Miyasaka and with coworkers in 2009 and introduced by Miyasaka and coworkers in 2009 and perovskite solar cells the highest PCEs perovskite with thetechnique highest PCEs reported tosolar date cells employ this [12]. reported to date employ this technique [12].
Figure 3. Schematic Schematicillustration illustrationofof(a)(a)one one step spin casting (b) sequential deposition (c) step two spin step Figure 3. step spin casting (b) sequential deposition (c) two spin casting and (d) dual source vapor deposition techniques for perovskite deposition. Adapted casting and (d) dual source vapor deposition techniques for perovskite deposition. Adapted from from Refs. [40–43] with permission from Macmillan Ltd. andSociety The Royal Society of Refs. [40–43] with permission from Macmillan PublishersPublishers Ltd. and The Royal of Chemistry. Chemistry.
Figure 3b illustrates the methodology of the sequential deposition technique in which BX is Figure 3b illustrates the methodology of the sequential deposition technique in which BX22 is dissolved in polar solvents such as DMF and DMSO while another solution of AX is made in 2-propanol. dissolved in polar solvents such as DMF and DMSO while another solution of AX is made in First, BX2 is spin coated over the substrate followed by calcination. After cooling down the substrate 2-propanol. First, BX2 is spin coated over the substrate followed by calcination. After cooling down to room temperature, it is dipped into AX solution followed by annealing to crystallize the perovskite. the substrate to room temperature, it is dipped into AX solution followed by annealing to crystallize the perovskite. The sequential deposition procedure was initially developed by Mitzi and colleagues in 1998 [44] while Gratzel et al. re-introduced this technique to fabricate perovskite
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The sequential deposition procedure was initially developed by Mitzi and colleagues in 1998 [44] while Gratzel et al. re-introduced this technique to fabricate perovskite solar cells in 2013 [45]. A major problem with this methodology is the length of time needed to convert BX2 into ABX3 , during which some of the formed ABX3 can be leached away from the substrate. Two-step spin coating, illustrated in Figure 3c, is a modified version of sequential deposition in which BX2 is first spin coated over the substrate followed by calcination. After cooling down the substrate to room temperature AX dissolved in 2-propanol is spin coated over the dry BX2 layer. Another important deposition technique that has the ability to produce high performance perovskite solar cells is the dual source vapor deposition technique which was reported in 2013 by Snaith et al. [40]. As shown in Figure 3d, AX and BX2 are evaporated simultaneously from two different sources in a particular evaporation ratio to form ABX3 film on substrate which is then annealed. Other deposition techniques include sequential vacuum deposition [46], chemical vapor deposition [47], inkjet printing [48,49], spray coating [50,51], and slot die coating [52], but these methods have not been successful thus far in producing high efficiency photovoltaic devices. 4. One Dimensional Nanostructures 1D-NS used in photovoltaics, taking the form of familiar structures such as rods, tubes, and wires, possess two dimensions of a size between 1 and 100 nm while the third dimension is typically in the range 200 nm–1 µm. A wide variety of top-down and bottom-up fabrication approaches exist for their synthesis, with varying degrees of complexity that allow for greater or lesser control over the final structure. Chemical synthesis strategies for 1D-NS are often the cheapest and least demanding in terms of deposition equipment, and include electrodeposition, sol–gel synthesis, solvothermal methods, and electrochemical anodization. While ease of fabrication and relatively high-throughput make these methods attractive options, they often suffer from the drawback of having a greater variability in final properties due to the indirect measures of control inherent to these methods. Strategies based on physical or physicochemical synthesis of 1D-NS such as vapor phase deposition, chemical vapor deposition, vapor-liquid-solid growth, and atomic layer deposition often result in superior electronic properties due to lower impurities and superior crystallinity while requiring dedicated deposition equipment and extreme conditions such as high vacuum and/or elevated temperatures. Even more precise control over the final structure can be obtained by techniques such as electron beam lithography or focused-ion beam writing or x-ray lithography, although these processes are much more expensive and of low-throughput. Several studies have found that the diffusion length of photogenerated electrons in halide perovskites is lower than that of photogenerated holes as shown in Figure 4, which calls for the application of nanostructured ETLs in perovskite solar cells [53,54]. 1D-NS offer a large surface area and the possibility of confinement of phonons and charge carriers, which leads to distinct electrical, optical and structural properties when contrasted with those of bulk materials. They may be used to limit the “random walk” of charges through a material; as there is only one direction in which charges may travel, the overall length of the path a charge takes on its way to being collected is reduced and thus charge recombination is limited. It is also important to use an optimized thickness of ETLs in perovskite solar cells (corresponding to the length of 1D ETL nanostructures). Because most perovskite semiconductors used in solar cells have a high extinction coefficient, an increase in the thickness of 1D ETLs does not generally improve the overall absorption of the device. However, increasing the thickness of 1D ETLs can reduce the photovoltaic performance of perovskite solar cells. The open circuit voltage decreases as the nanostructure length increases because of increased recombination at the ETL/perovskite interface [55–57]. The short circuit current too typically decreases because of ultraviolet photons absorbed by thicker ETLs which cannot be transmitted to the perovskite absorber layer [55,58]. The fill factor also reduces because of an increased series resistance of the solar cell. On the other hand, too thin an ETL does not provide a sufficient mesoscopic effect. If left unoptimized, forward- and back-scattering due to thick nanostructured ETLs can outcouple incident photons out of
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the device and reduce the amount of light harvested [59]. The nanorod packing density in 1D ETLs is 6 of 26 Nanomaterials 2017, 7, 95 another important parameter which plays a crucial role in the photovoltaic performance of solar cells. If the nanorods are densely packed, then there is less room between adjacent nanorods/nanotubes filling and lower photovoltaic performance of the solar cells. Moderate and low density packing of for the perovskite to be filled, resulting in poor filling and lower photovoltaic performance of the the nanorods constituting the 1D ETL provide better filling and thus improved light harvesting solar cells. Moderate and low density packing of the nanorods constituting the 1D ETL provide better efficiency [60–62]. Thus, it is important to optimize the thickness and morphology of 1D ETLs to filling and thus improved light harvesting efficiency [60–62]. Thus, it is important to optimize the take proper advantage of their directional charge transport and light management properties thickness and morphology of 1D ETLs to take proper advantage of their directional charge transport without harming other performance parameters of the solar cell. For high aspect ratio nanorods in and light management properties without harming other performance parameters of the solar cell. the ETL, field emission of electrons into the perovskite is promoted, which in turn, may increase the For high aspect ratio nanorods in the ETL, field emission of electrons into the perovskite is promoted, dark current in the solar cells and thereby reduce the Voc value [59]. A superficial coating of which in turn, may increase the dark current in the solar cells and thereby reduce the Voc value [59]. perovskite is favored for high aspect ratio NRs with polar surfaces due to wetting considerations, as A superficial coating of perovskite is favored for high aspect ratio NRs with polar surfaces due to opposed to volumetric filling of the inter-rod spaces, which can exacerbate problems with wetting considerations, as opposed to volumetric filling of the inter-rod spaces, which can exacerbate extracting holes. problems with extracting holes.
Figure 4. Time-resolved photoluminescence (along with stretched exponential of MAPbI Figure 4. Time-resolved photoluminescence (along with stretched exponential fits)fits) of MAPbI 3 using 3 using electron quencher [6,6]-phenyl-C acid methyl ester (PCBM) shown as blue trianges thethe electron quencher [6,6]-phenyl-C acid methyl ester (PCBM) shown as blue trianges or or 61-butyric 61 -butyric using the the holehole quencher layerlayer Spiro-MeOTAD, shown as redas circles. The data withoutwithout the use the using quencher Spiro-MeOTAD, shown red circles. Theobtained data obtained of ause quencher, instead instead using insulating polymerpolymer poly(methylmethacrylate) (PMMA)(PMMA) is shown is asshown black as of a quencher, using insulating poly(methylmethacrylate) squares. Ref. [53] with permission The American for the Advancement black Adapted squares. from Adapted from Ref. [53] withfrom permission from Association The American Association for the in Science. Advancement in Science.
5. Materials One Dimensional Electron Transport Layers 5. Materials forfor One Dimensional Electron Transport Layers Both inorganic and organic semiconductors have been used electron transport materials, Both inorganic and organic semiconductors have been used as as electron transport materials, although it is inorganic that have received attention for their applicability as although it is inorganic materialsmaterials that have received attention for their applicability as one-dimensional one-dimensional since the morphological integrity of organic semiconductor nanostructures since nanostructures the morphological integrity of organic semiconductor nanostructures typically nanostructures typically doessolution not survive the subsequent deposition the halide does not survive the subsequent deposition of the halidesolution perovskite due to theofpartial or perovskite due toofthe complete solubility of the such organic semiconductors in solvents such complete solubility thepartial organicorsemiconductors in solvents as GBL, DMF, and DMSO [63,64]. GBL,noting, DMF, however, and DMSO It efforts is worth noting, thatofresearch efforts towards It isasworth that[63,64]. research towards thehowever, development one-dimensional organicthe development of organic semiconductors being made synthesis, through techniques such semiconductors areone-dimensional being made through techniques such as are solution-phase templating, as solution-phase synthesis, templating, [65]. TiO2, ZnO, electrospinning, and nanolithography [65]. electrospinning, TiO2 , ZnO, SnO2and , andnanolithography WOx are the most commonly SnO mostdiagram commonly usedinmaterials (energy level diagram shown in inorganic Figure 5) for used materials (energy level shown Figure 5) for 1D-ETLs, although other 2, and WO x are the 1D-ETLs, although other inorganic semiconductors that could potentially be such used as in a semiconductors exist that could potentially be used in a exist one-dimensional nanostructure, nanostructure, such as Zn SnO [66], BaSnO [67], and SrTiO [68]. While not a Znone-dimensional SnO [66], BaSnO [67], and SrTiO [68]. While not a focus of this review, common organic electron 2 4 3 3 2 4 3 3 focus materials of this include review,fullerenes, commonmethanofullerenes, organic electronandtransport materials include transport perylene derivatives. There are fullerenes, several methanofullerenes, and perylene several major considerations when selecting major considerations when selecting derivatives. the material There to useare as ETL, including the energy level alignment the material to use as ETL, including the energy level alignment with respect to the particular perovskite absorber used, the doping density, the density and energetic depth of trap states in the material, the electron mobility, and hole blocking action. The material most commonly used as the ETL is TiO2, which exhibits good electron transporting properties and is known to be non-toxic and
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with respect to the particular perovskite absorber used, the doping density, the density and energetic Nanomaterials 2017, 7, 95 in the material, the electron mobility, and hole blocking action. The material 7most of 26 depth of trap states commonly used as the ETL is TiO2 , which exhibits good electron transporting properties and is known chemically stable. three TiO crystalline phases—anatase, brookite, and rutile [69], among 2 exists in to be non-toxic andTiO chemically stable. 2 exists in three crystalline phases—anatase, brookite, and which the anatase has beenphase used TiO the most widely and achieved the highest performance rutile [69], among phase whichTiO the2 anatase 2 has been used the most widely and achieved the in photovoltaic applications due to possessing a higher effectivea surface area, faster electron highest performance in photovoltaic applications due to possessing higher effective surface area, transport, and longer electron lifetime than the other two phases [70,71]. The anatase phase of TiO2 faster electron transport, and longer electron lifetime than the other two phases [70,71]. The anatase also exhibits blocking, which is highly desirable. major issue withissue TiO2 phase of TiO2exceptional also exhibitshole exceptional hole blocking, which is highlyHowever, desirable. aHowever, a major and its potential to be used in commercial applications, is the high temperature processing typically with TiO2 and its potential to be used in commercial applications, is the high temperature processing required to anneal the TiOthe crystalline forms, since thethe as-fabricated often 2 into typically required to anneal TiO2these into these crystalline forms, since as-fabricatedTiO TiO2,2 , is is often amorphous. this problem, problem, efforts efforts have have been been made made to to develop develop crystalline crystalline TiO TiO2 without without the the amorphous. In In light light of of this 2 need for high-temperature processes [72]. Compared to other candidate ETL materials, TiO need for high-temperature processes [72]. Compared to other candidate ETL materials, TiO2 possesses2 possesses a high densityand of deep-trapping shallow- and states deep-trapping [73] thatShockley-Read-Hall in turn promote a high density of shallow[73] that instates turn promote Shockley-Read-Hall type recombination and Fermi-level pinning at interfaces with other materials. type recombination and Fermi-level pinning at interfaces with other materials. The most widely The most widely investigated replacement for TiO is ZnO, which has a 5–10 fold higher electron 2 investigated replacement for TiO2 is ZnO, which has a 5–10 fold higher electron mobility [74] and mobility [74] and suitable energy levels. However, processing issues and the poorer chemical suitable energy levels. However, processing issues and the poorer chemical stability of ZnO have stability havedevelopment hindered theofuse development of ZnO as an ETL. SnOnearly 2 has an hinderedof theZnO use and ZnOand as an ETL. SnO2 has an electron mobility twoelectron orders mobility nearly two orders of magnitude higher than that of TiO [75], yet shows much lower PCEs 2 PCEs due to non-optimal energy of magnitude higher than that of TiO2 [75], yet shows much lower due toand non-optimal energy levels andSimilarly, high recombination rates. Similarly, WOx has exhibited poor levels high recombination rates. WOx has exhibited poor performance when used by performance when used by itself. However, both SnO and WO have shown increased 2 x itself. However, both SnO2 and WOx have shown increased performance when used in combination performance with ZnO and as in a core shell can structure [38]. 2, such with ZnO andwhen TiO2 ,used suchin ascombination in a core shell structure [38].TiO Such a core-shell structure effectively Such a core-shell structure can effectively suppress recombination and improve the electron transfer suppress recombination and improve the electron transfer at the ETL/perovskite interface, resulting in at the ETL/perovskite interface, resulting improved solar cell performance [61,76]. in improved solar cell performance [61,76].
Figure 5. Figure 5. Energy Energy level level diagrams diagrams illustrating illustrating the the position position of of the the conduction conduction band band minimum minimum vs. vs. the the vacuum level in various electron transport layer materials. Adapted from Ref. [77] with permission vacuum level in various electron transport layer materials. Adapted from Ref. [77] with permission from The Royal Society of Chemistry. from The Royal Society of Chemistry.
6. Classes Classes of of One One Dimensional Dimensional Nanostructures Nanostructures Used Used as 6. as ETLs ETLs in in Perovskite Perovskite Solar Solar Cells Cells The vast of 1D-ETLs take take the form nanotubes or nanorods (also known as nanowires). The vastmajority majority of 1D-ETLs the of form of nanotubes or nanorods (also known as However, other morphologies do exist, including nanofibers and core-shelland structures utilizing two nanowires). However, other morphologies do exist, including nanofibers core-shell structures or more materials as the electron transporting layer. Herein, we focus on the structure and function utilizing two or more materials as the electron transporting layer. Herein, we focus on the structure of TiO and ZnO nanorods, with the reported solar cell performance of 2 nanotubes, 2 nanorods, and function of TiOTiO TiO 2 nanotubes, 2 nanorods, and ZnO nanorods, with the reported solar cell performance of TiO2 1D-ETLs and ZnO 1D-ETLs summarized in Table 1 and Table 2 respectively. Table 3 and Section 6.4 summarize unorthodox 1D-ETL morphologies and materials. 6.1. TiO2 Nanotube Arrays
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TiO2 1D-ETLs and ZnO 1D-ETLs summarized in Tables 1 and 2 respectively. Table 3 and Section 6.4 summarize unorthodox 1D-ETL morphologies and materials. 6.1. TiO2 Nanotube Arrays Vertically oriented, self-organized, highly ordered TiO2 nanotubes (NTs) have attracted interest for use in dye-sensitized solar cells, quantum dot-sensitized solar cells, and bulk heterojunction photovoltaic devices since the mid-2000s [78–82]. While various methods to fabricate TiO2 nanotubes exist—including sol–gel [83], atomic layer deposition into nanoporous templates [84], and hydrothermal methods [85]—by far the simplest route to obtain highly uniform TiO2 nanotube arrays is the anodization method. The anodization method involves applying a sufficiently anodic voltage to Ti metal foils or Ti thin films vacuum deposited on to a TCO-coated glass or plastic substrates in an electrochemical cell with an appropriately selected electrolyte [86–88]. The key to the process is the simultaneous oxidation of Ti to form a TiO2 oxide layer along with the electrochemical/chemical dissolution of TiO2 in the form of pitting, a feat accomplished by the presence of anions such as F− , Cl− or ClO4 − in the electrolyte [89–92]. While the exact formation process is not fully understood and remains contentious [93–96], the end result is that an entire TiO2 nanotube array is typically formed all across the Ti film over the course of minutes or hours. Depending on the conditions used and the thickness of the precursor Ti film, these nanotubes have lengths ranging from a few hundred nanometers to several hundred micrometers, with pore diameters ranging from tens to hundreds of nanometers [97–99]. For perovskite solar cells, a nanotube length (ETL film thickness) of
