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Author(s): Yogesh Kumar Dongre* and Sanjay Tiwari

Email(s): yogielectro@gmail.com

Address: School of Studies in Electronics & Photonics, Pt. Ravishankar Shukla University, Raipur-492010, Chhattisgarh (India)

Published In:   Volume - 33,      Issue - 1,     Year - 2020


Cite this article:
Dongre et al. (2020). Perovskite Solar Cells an Efficient, Low Cost, Emerging Photovoltaic Technology. Journal of Ravishankar University (Part-B: Science), 33(1), pp. 73-81.




Perovskite Solar Cells an Efficient, Low Cost, Emerging Photovoltaic Technology

Yogesh Kumar Dongre* and Sanjay Tiwari

School of Studies in Electronics & Photonics, Pt. Ravishankar Shukla University, Raipur-492010, Chhattisgarh (India)

*Corresponding author: yogielectro@gmail.com

[Received: 20 November 2019; Accepted: 22 September 2020]

Abstract: Organometal halides compound shortly named as perovskite represent an emerging active layer materials for photovoltaic technology. In recent years perovskite shows capability of developing high performance photovoltaic devices with higher efficiency at a low cost. This review article  discuss the current status of methylammonium metal halide (perovskite) based photovoltaic devices and provide a comprehensive review of ABX3 device structures, fabrication methods,synthetization, film properties, and photovoltaic performance. The flexibility, simplicity and low cast processing of perovskite solar cell fabrication methods allow using various types of device architectures. The article also focuses on the journey of perovskite solar cell. In 2009 first perovskite solar cell was reported and it shows power conversion efficiency (PCE) of around 3–4%.In 2017 the PCE was reported around 22.1%, now a day (in 2019) 28% power conversion efficiency is reported by Oxford PV’s which is tandem solar cell based on perovskite-silicon. In this article the issue related to efficiency enhancement, stability and degradation mechanism are presented.

Keywords: solar cells, methyl ammonium metal halide, perovskites, stability, crystal structure.

Introduction

Perovskite name comes from a Russian mineralogist L. A. Perovski and discovered by Gus-tav Rose in 1839. In 1978, the material that is responsible for the main part of perovskite solar cells was introduced as organo metal halide CH3NH3BX3 by Weber. Here, B stands for metal elements and X substitutes for halide elements (Mitzi, et al. 1994).CH3NH3BX3 has a specific crystal structure with the ABX3 formula (X = oxygen, halogen). The larger A cation occupies a cubo-octahedral site shared with twelve X anions while the smaller B cation is stabilized in an octahedral site shared with six X anions.The perovskite materials raises very earlier from 2006 at this stage it was very new technology and shows efficiency around 2.2%, but the first incorporation into a solar cell was reported by Miyasaka et al., 2009 (Kojima et al., 2009). This was based on dye-sensitized solar cell architecture, and generated only 3.8% power conversion efficiency (PCE) with a thin layer of perovskite on mesoporous TiO2 as electron-collector. Moreover, because a liquid corrosive electrolyte was used, the cell was only stable for a matter of minutes. Park et al., 2011 improved, using the same dye-sensitized concept, achieving 6.5% PCE (Im et al., 2011).There are some another low cost solar PV technology like Polymer, Dye synthesized, Quantum Dot are also available, The low efficiency is major issue in 3rd generation Solar cell (Verma et al., 2017). Because of high efficiency researcher gives keen interest on the development of perovskite based solar cell.

Mike Lee et al., 2012 reported that the perovskite was stable if contacted with a solid-state hole transporter such as spiro-OMeTAD and replaced the requirement of mesoporous TiO2 layer in order to transport electrons (Lee et al., 2012, Hadlington, 2012).They showed that efficiencies of almost 10% were achievable using the 'sensitized' TiO2 architecture with the solid-state hole transporter, for higher efficiencies, above 10%, were attained by replacing it with an inert scaffold (Kim et al., 2012). Furthere xperiments in replacing the mesoporous TiO2 with Al2O3 resulted in increased open-circuit voltage and a relative improvement in efficiency of 3–5% more than those with TiO2 scaffolds (Liu, et al. 2013).Scaffold architecture shows hypothesis which is not needed for electron extraction, which was later, proved correct. The result from scaffold architectures is then closely demonstrated the result that the perovskite itself could also transport both holes and electrons (Ball et al., 2013). A thin-film perovskite solar cell, with no mesoporous scaffold, of more than 10% efficiency was reported (Eperon et al., 2014, Saliba et al., 2014, Tan et al., 2014). Summarised data of introduction with their efficiency and specified parameters is listed below in table 1.

Table 1. Reported efficiency of perovskite solar cell

 

S. No.

 

Year

 

Researcher

 

Efficiency

 

Attention

1.

2006

Kojima, A., Teshima, K., Miyasaka, T. & Shirai, Y.

2.2%,

Organic-inorganic halide perovskite photovoltaics.

2.

2009

Miyasaka et al

3.8%

Based on dye-sensitized solar cell architecture

3.

2011

Park et al.

6.5%

Same dye-sensitized concept

4.

2012

Henry Snaith and Mike Lee

10%

Solid-state hole transporter such as spiro-OMeTAD and replaced the requirement of mesoporous TiO2 layer

5.

2013

Burschka et al.

15%

Two-step solution processing

6.

2014

Yang Yang

19.3%

Planar thin-film architecture

7.

2016

Researchers from KRICT and UNIST

22.1%

Single-junction perovskite solar cell

8.

2017

Researchers from KRICT

22.2%

Single-junction with different architecture perovskite solar cell

9.

2019

Oxford PV’s

28%

Single-junction, Tandem solar cell based on perovskite-silicon

Burschka et al., (2013) for increasing the efficiency of cell, a deposition technique was demonstrated with the sensitized architecture,efficiency exceeding from 15% by a two-step solution processing, (Burschka et al., 2013). Olga Malinkiewicz et al. and  Liu et al., 2013 also worked on these and gives a proposed  possible  way to fabricate planar solar cells by thermal co-evaporation techniques and achieved more than 12% and 15% efficiency in a p-i-n and an n-i-p architecture respectively (Malinkiewicz et al., 2014, Liu et al., 2013).Docampo et al., 2013 showed 10% efficiency of fabricated perovskite solar cells in the typical 'organic solar cell' architecture, an 'inverted' configuration with the hole transporter below and the electron collector above the perovskite planar film (Docampo et al., 2013).

New deposition techniques and higher efficiencies were reported. A reverse-scan efficiency of 19.3% was claimed by Yang Yang [2014] using the planar thin-film architecture (Zhou et al., 2014). PCE values over 20% are realistically accepted with the use of cheap organometal halide perovskite materials, because of efficiencies have quickly raised to 18-22 % in just 2 years. In addition, comments on the issues to current and future challenges are mentioned.

Perovskite material structure

The perovskite (the mineral) is composition of calcium, titanium and oxygen in the form CaTiO3. Meanwhile, a perovskite structure is anything that has the generic form ABX3 and thesame crystallographic structure as perovskite(Giorgi et al., 2013). The perovskite lattice and morphology arrangement is discussed below.A large atomic or molecular cation (positively-charged) of type A are situated in the centre of a cube. And the corners of the cube are then occupied by atoms B (positively-charged cations) and the cube faces are occupied by a smaller atom X with negative charge (anion).

 

Figure 1. ABX3 perovskite structure showing BX6 octahedral and larger A cation occupied in cubo-octahedral site and Unit cell of cubic CH3NH3PbI3 perovskite, (Giorgi, et al. 2013).

The structure of the perovskites currently used in solar cells consists of a network of corner-sharing BX6 octahedral with the B cation (typically Sn2+ or Pb2+) and X is a halogen grouptypically F-, Cl-, Br- or I-. The cation A is selected to balance the total charge and it can be an organic (eg. Methylammonium CH3NH3+, Formamidinium NH2CH=NH2+) or inorganic material like Cs+ ion (Borriello, et al. 2008, Kagan, et al. 1999). Perovskites are well known for their phase complexity, with accessible cubic, tetragonal, orthorhombic, trigonal and monoclinic polymorphs depending on the tilting and rotation of the BX6 polyhedra in the lattice (Tributsch, H. 2004). Phase transitions are frequently observed in lead perovskites under the influence of temperature, pressure and/or applied electric field (Mitzi, et al. 1995).

CH3NH3PBX3Perovskite light absorber: Structure

A and B are usually divalent and tetravalent, respectively whenever O2- anion is used.Charge neutrality is done by perovskite halogen anions allow monovalent and divalent cations in A and B sites, respectively. In CH3NH3PbI3, the A-site cation is CH3NH3+ and the B-site cation is Pb2+, as shown in Fig. 1. The formability of perovskite is estimated based on its geometric tolerance factor (t) t = (rA + rX)/[H2(rB + rX)], where rA, rB and rX are the effective ionic radii for A, B and X ions, respectively(Goldschmidt, V. M.1927). For transition metal cations containing oxide perovskite, an ideal cubic perovskite is expected when t = 1 while octahedral distortion is expected when t < 1. Symmetry also decreases for t < 1, which may affect electronic properties (Rini, et al. 2007). For alkali metal halide perovskite, formability is expected for 0.813 < t < 1.107 (Li, et al.2008).

Optical band gap and absorption coefficient of CH3NH3PbX3

The absorption coefficient of ABX3, here CH3NH3PbX3 was estimated from a nanocrystalline TiO2 thin film surface coated with CH3NH3PbX3. Table 2 shows the absorption coefficient as a function of wavelength for the CH3NH3PbX3 nanodot-coated TiO2 film.

Absorption coefficient (α) as a function of wavelength for perovskite CH3NH3PbX3 nanodot coated with 1.4 µm TiO2 film (amount of adsorbed perovskite = 3.2 ×10^4 /µm2), α was obtained from T = I/I0 = exp (_α l), where T, I, I0 and l represent transmittance, transmitted light intensity, incident light intensity and TiO2 film thickness, respectively.

 

Table 2.Absorption coefficients, as a function ofwavelength.

Text Box: Figure 2. Wavelength Vs Absorption Coefficient

The absorption coefficient was estimated to be 1.5 ×10^4 cm-1 at 550 nm, indicating that the penetration depth for 550 nm light is only 0.66 µm. At 700 nm, the absorption coefficient was 0.5 ×10^4 cm-1, corresponding to a penetration depth of 2 µm. Incoming light mostly absorbed by the perovskite within a thin layer of about 2 µm, which is suitable as a sensitizer for high efficiency solid-state sensitized solar cells(Kim, et al. 2012).

 

 

 

 

 

 

Physical device structure of perovskite solar cells

As the technology mature the structure of perovskite solar cell offered variety of structure with theirown significant. With respect to the time the physical structural designed and concept are changed. Perovskite material is basically chemical compound so the structure is also based on chemical reaction of materials. The various structures with their concept and maturity are listed below.

 

Table 3.Various Spectrum analysis of CH3NH3PbI3

Text Box: Figure 3. Diffuse reflectance spectral data plot from Kubelka–Munk.

 

Text Box: Figure 4. UPS spectrum (Binding Energy Vs Intensity) of CH3NH3PbI3-adsorbed TiO2 film.

Text Box: Figure 5.Schematic energy level diagram of TiO2, CH3NH3PbI3 and spiro- MeOTAD.

From ultraviolet photoelectron spectroscopy (UPS) and the Tauc plot obtained with UV–vis spectral data, valance band maximum (VBM), band gap, and conduction band minimum (CBM) for CH3NH3PbI3 were estimated to be 5.43 eV, 3.93 eV and 1.5 eV, respectively, as depicted in Fig. 5. From a thermodynamic view-point, the VBM position is suitable for hole separation while CBM is suitable for electron separation. On the basis of band gap energy, the absorption onset wavelength is expected to be around 826 nm(Kim, et al. 2012).

 

 

 

 

 

 

 

 

 

Table 4. Absorption coefficients as a function of wavelength

Text Box: Figure 6. Molecular Dye concept

 

Perovskite was first used as in which molecular dye concept was replaced by perovskite a sensitizer in dye-sensitized solid-state devices. In the sensitization concept shown in Fig. 6, to induce heterojunction concept HTM should be fully infiltrated inside the mesoporous oxide layer. In addition, oxide layers with electron accepting properties are required to separate the photo-excited electrons in perovskite(Kim, et al. 2012).

 

 

Text Box: Figure 7. Solid state dye concept

 

The Al2O3 served as a scaffold layer because electron injection from perovskite to Al2O3 was not allowed. So the result of this architecture the sensitization concept is not always necessary for perovskite solar cell design. So perovskite solar cells were confirmed to work in the absence of a mesoporous TiO2 layer. As shown in Fig. 7, the CH3NH3PbI3_xClx thin layer coated Al2O3 film had a PCE of 10.9% (Lee, et al. 2012).

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Text Box: Figure 8. Pillared structure concept

 

 

A pillared structure was designed in which the pores of a mesoporous TiO2 film (pillars) were filled with perovskite instead of a surface coating. As shown in Fig. 8, a thin capping layer (over active layer) was formed after infiltration with the perovskite.  PCE of 12% was reported using CH3NH3PbI3 and polytriarylamine (PTAA) (Heo, et al. 2013).For higher PCE in pillar structure, the pillared structure with a two-step coating procedure was used. CH3NH3PbI3 layer was prepared by dipping the PbI2 layer formed in mesoporous TiO2 film into a diluted CH3NH3I solution while the perovskite layer was in contact with spiro-MeOTAD, 15% PCE was achieved in this structure (Burschka, et al. 2013).

 

 

 

 

 

 

 

 

 

 

 

Text Box: Figure 9. Planar structure concept

 

Planar structure with deposited CH3NH3PbI3_xClx film was designed.  In addition to the sensitization and planar pin junction concepts, a pn junction structure is available. A pn junction structure with FTO/TiO2/CH3NH3PbI3/Au configuration was proposed Fig. 9 in which CH3NH3PbI3 was used as a p-type semiconductor (Laban,et al.2013).5.5% PCE with a 500 nm-thick nanosheet TiO2 film for the n-type layer with HTM-free perovskite solar cell was showed initially. Then after replacing the TiO2 nanosheet with a thinner nanoparticle TiO2 film, PCE was improved to 8%(Green, et al. 2017).

 

Perovskite solar cells efficiency from beginning to now

https://media.springernature.com/original/springer-static/image/art%3A10.1007%2Fs40820-018-0221-5/MediaObjects/40820_2018_221_Fig4_HTML.pngPlots show the progress in perovskite solar cell efficiency by year. Since 2009, organolead halide perovskites have been used for solar cells and 3.8% PCE were reported. For improvement in efficiency and stability in 2012 liquid dye was replaced by solid HTM. Since then, solid-state perovskite-containing solar cells have been called perovskite solar cells.

 

(a)                                                                                                        (b)

Figure 10. (a&b) Progress in perovskite solar cell efficiency by year (Vidyasagar, et al. 2018).

As of June 10th 2014, the certified record PCE of 17.9% was achieved by the Korean Research Institute of Chemical Technology (KRICT), which was certified by the National Renewable Energy Laboratory (NREL, 2018). Recently in 2017 the 22.1% PCE was reported by KRICT co-authorship (Seo, et al. 2016) and 2018 from the Energy Environmental Science report 23.9% PCE was achieved (Vidyasagar, et al. 2018).

Stability and degradation issue in perovskite solar cell

Previous years reported result, shown very well understanding about the efficiency enhancement with different architecture. Perovskite materials offers higher efficiency with compare to other standing solar technology, because of the absorption coefficient is higher, higher charge carrier mobility and higher open circuited voltage.  But the major issue related to the performance of perovskite solar cell are their degradation and instability in environment and another changing atmosphere. The life time of cell is very short and it degrades within very short time some of the cells shown degrade in less than 10 min during the measurement procedure itself. Due to degradation Perovskite solar cell shows instability. There are various issues for instability the chemical reaction between perovskite with other materials shows rapid crystallization between organic cations and PbI2” is stressed as is the role of manipulating “the chemical composition of the perovskites via solvent engineering and intra molecular exchange process” ((Vidyasagar et al., 2018). The luminescent properties of the perovskite materials need to be better understood to improve open-circuit voltage (Voc). To overcome degradation issues, replace metal electrodes with something like indium−tin oxide because the halogens in the perovskite react with most metals.

Encouraging stability results, however, have recently been reported for solid solutions of Cs and FA lead-halide perovskites (Berhe et al., 2016). Another way to increase the stability of perovskite at high relative humidity is to form the mixed halide perovskite. The simple solution mixture of CH3NH3PbI3 and CH3NH3PbBr3 was reported to result in a solid-solution of CH3NH3PbI3_xBrx (x = 0–3) (McGehee M, 2016). Since triio-dide and tribromide perovskite have a band gap difference, the solid solution resulted in band gap tuning and colour control. The inclusion of bromide in CH3NH3PbI3 will likely enhance the stability of the CH3NH3+ cation in the lattice.

 

Hysteresis effects in perovskite solar cell

The current-voltage response curves fluctuations are depending on the presence of Hysteresis, so the corresponding photovoltaic parameters vary depending on the rate of the scan and scanning direction. Reliable photovoltaic operation and stability of organic-inorganic perovskite solar cells affected by the influence of hysteresis effects. Ferroelectric polarization, ion migration, charge trapping, and capacitive effects, are the major responsible mechanisms behind the origin of hysteresis phenomenon in perovskite solar cells(Noh et al., 2013).

Text Box: Figure 11.  Hysteresis in perovskite solar cell

 

 

 

 

 

 

 

The phenomenon of hysteresis in ferromagnetic materials is the result of two effects, rotation of magnetization and changes in size or number of magnetic domains. In general, the magnetization varies (in direction but not magnitude) across a magnet. For high efficient solar cell we require very low hysteresis loss (Elumalai et al., 2016).

Because of metal materials Hysteresis Effects originated in perovskite solar cell. For observation of capacitive effects in perovskite-absorber devices of different architecture and study changes in devices during degradation, Staircase voltammetry is used. Hysteretic phenomena have been observed in solar cells other than perovskite-absorber solar cells (Jacobs et al., 2017).

Future challenges

Recent progress most of cell was designed with organolead halides, lead is toxic material and it react with environment and gives harmful effect to human being so researcher took around the other material (Sn, K) in place of lead. With these materials, a PCE of 20% is expected from single junction structures and a PCE of 29% is expected from tandem structures (Unger, et al. 2014, Park, N. G. 2013).Higher efficiency is still possible through structural modification (Park N. G., 2013), along with band gap tuning. Modification of the bond distance and/or angle of X–Pb–X in CH3NH3PbX3 is one of strategies to tune band gap energy. More recently, a PCE approaching 30% was achieved from a single junction perovskite solar cell (Snaith H. J., 2013). Pb-free compounds such as MA2AgBiI6, with a double-perovskite unit cell, also have excessively high band gap (Yin et al., 2014, Volonakis et al., 2016).The same approaches will be done using Sn based perovskite material. Preciously control of the luminescent property of perovskite could further improve Voc, hence contributing to an even higher PCE.

Conclusion

Clean and green electricity is most requiring thing for human being. The sun is the source of light energy, and we are converting this light into electricity by using device called solar cell. Today varieties of solar cell are present with various specific parameters. Now solar industries are based on Silicon (Si) technology, we know its mature technology but the cost and processing of Si solar cell is very high. Now a day a new kind of solar cell were reported and on progresses named perovskite solar cell. This review article, represent perovskite solar cells in the order of historical background, materials used, production of perovskite solar cells and their properties and mechanisms to explain them properly. Within a journey in term of efficiency, its dominant some other solar cell technology like Dye solar cell, Organic solar cell, etc. The instability and degradation and toxicity in case of Pb based perovskite are major issue in perovskite solar cell. More broadly, the progress work will create a transformative, high efficient, low cost, and easy to fabrication to serve as bridge between basic Photovoltaic sciences, applied sciences and engineering and photovoltaic technology. In future so its stand with Silicon based technology.

Acknowledgements

I would like to express my sincere gratitude to my supervisor Prof. Sanjay Tiwari for the continuous support of my research, for his motivation, and immense knowledge. I am also thankful to Photonics Research Laboratory, Pt. Ravishankar Shukla University, Raipur, Chhattisgarh (India) for research facilities, and Group members are also thankful and acknowledged.

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