Recent Advances in Halide-Based Perovskite Crystals and Their

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Recent Advances in Halide-based Perovskite Crystals and Its Optoelectronic Applications Ramavath Babu, Lingamallu Giribabu, and Surya Prakash Singh Cryst. Growth Des., Just Accepted Manuscript • DOI: 10.1021/acs.cgd.7b01767 • Publication Date (Web): 23 Feb 2018 Downloaded from http://pubs.acs.org on February 24, 2018

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Crystal Growth & Design

Article type: Review

Recent

Advances

in

Halide-based

Perovskite

Crystals

and

Its

Optoelectronic Applications Ramavath Babu,[a] Lingamallu Giribabu,[a] and Surya Prakash Singh[a]*

Inorganic and Physical Chemistry Division, CSIR-Indian Institute of Chemical Technology (IICT), Uppal road, Tarnaka, Hyderabad, 500007, India E-mail: [email protected] Keywords: halide-based perovskite, crystal growth, electron and hole-transport, carrier mobility, optoelectronic

Abstract Halide based perovskite materials have attracted as a promising candidate for the optoelectronic applications, predominantly in photovoltaic device, due to their superior potential properties such as high absorption coefficient, direct bandgap, long carrier lifetime, high balanced hole and electron mobility, low cost and facile deposition techniques, etc. Despite of this, their fundamental understanding of physico-chemical properties are still debatable to the scientific community. In this review article we provide the deep insight into the development of perovskite single crystals using different techniques, their potential properties and practical applications in the various optoelectronic applications. In addition, we have compared all the reported protocols available for crystal growth and highlighted the best technique to achieve high quality of crystals with better size, shape and possessing potential key quantities to be more useful in optoelectronics. At last, we emphasized difficulties in view of chemical uses and suggested new direction for the further research and development in the area of the halide based perovskite materials. 1 ACS Paragon Plus Environment

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1. Introduction Photovoltaic device or solar cell, in which harvested light is directly convert into an electricity. Depending on this concept, many photovoltaic technologies have been developed, such as silicon based,1-4 CdTe or CIGS5,6 and excitonic solar cells,7-9 which are categorised as first, second, and third generation photovoltaics (PVs), respectively. The first two generation solar cells are either cost effective or hazardous nature of materials used, while the third generation solar cells have many technical constrains before commercialization of technology. Among excitonic solar cells, dye-sensitised solar cells (DSSCs) are at verge of commercialization. In order to overcome the drawbacks recently, halide based perovskite solar cells have came into the existence to overcome the difficulties of excitonic solar cells. In 2009 Kojima. et al.10 has made first attempt to use halide based perovskites (MAPbBr3 and MAPbI3, where MA = CH3NH3+) as sensitizers in DSSCs using volatile liquid-electrolyte. Therefore, due to corrosion effect of perovskite by the liquid electrolyte, whereas obtained power conversion efficiency (PCE) is very less and cell stability also poor. Further, more advances made in 2012 by replacing the liquid electrolyte with hole transport materials (HTM), as a result efficiency enhanced to 9.7% and durability of the device also increased.11 Since then, many groups across the globe are attracted remarkably and effort devoted to the research of halide-based perovskite solar cell.12-29 Over the past seven years, a variety of device architectures have been developed and the PCEs reached to 22.7%.30 Halide based perovskite materials not only limited to solar cell, which

also show impressive

performance in light emitting diodes,31-35 lasers,36-38 ultraviolet-to-infrared photodetectors,39-41 X-ray42,43 and γ-ray detectors.44-46A key success due to their incredible properties, such as appropriate bandgap,47,48 high absorption coefficient over the visible region,49 long and balanced electron–hole diffusion lengths,42,50,51 large dielectric constant,52,53 low exciton binding energy,54 high carrier mobility and wide optical absorption range.55,56 2 ACS Paragon Plus Environment

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However, vast majority reported perovskite devices are depending on polycrystalline thin films.57-60 The polycrystalline materials that immensely suffers from high trap density, grain boundaries and excitonic band gap, which are obviously limit the potential performance in photovoltaic devices.61-63 Recently, it was reported remarkably reduced trap densities (6 times lower than their polycrystalline films) a clear cut band edge with no excitonic signature, high carrier diffusion lengths and carrier mobilities from single crystal of halide perovskites, these are the parameters that indicating minimum defects of materials. However, in this review, we presented recent progress of crystal growth, their basic properties and direct application of halogen based perovskite crystals.

2. Crystal structure of Perovskite

Figure 1. A typical crystal structure of halogen based perovskite present in unit cell.

Perovskite materials have a common chemical formula with ABX3 (where A & B are cations, and X is anion), cation A occupy corner and B occupy body center of the unit cell. In a packing diagram of perovskite crystal, cation B is octahedrally coordinated by the six X– anions and form a octahedral share corners of three dimensional network, while cation A sit in the 12-coordinate cubo-octahedral voids of this network, as depicted in Figure 1. Herein, the A-part it may be contain organic (CH3NH3+, HNCHNH2+etc.) or inorganic (Cs+, Rb+ and K+), while B-part is consist with Pb2+, Sn2+ and X is an halogen anions (I–, Br–, and Cl–). 3 ACS Paragon Plus Environment


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Goldschmidt proposed a tolerance factor (t) to explain the stability of ABX3 perovskite structure. Principle of the tolerance factor (t) fallow as equation (1),

(1) where rA, rB and rX represent their corresponding ionic radii. From Table 1, the cubic crystal structure of perovskite can be possible when the t value is from 0.9 to 1, but when it is lower than 0.9 the high symmetry of the structure will be reduce into a low symmetry. Accordingly, the (t) value when it present from 0.7 to 0.9, the possible structures are tetragonal and orthorhombic or rhombohedral with smaller A or larger B (unequal cations). When (t) value is larger than 1.0 the existing crystal structure either hexagonal or tetrahedral symmetry with larger A cation. Therefore, a stable structure of perovskite exist when the tolerance factor should be present from 0.7 to 1.0. The effect of tolerance factor (t) of perovskite crystal structure provides information for exploring some novel and abnormal properties of materials. However, tolerance factor (t) is not the only major factor to conclude formability and stability of a perovskite structure because other non-geometric factors like bond valence and chemical stability are also important. Table 1. Tolerance factor (t) and possible structure of perovskites. Reproduced with permission.64 Copyright 2015, The Royal Society of Chemistry. S. No Factor (t) Structure Description 1

>1

2

0.9-1

3

0.71-0.9

4

< 0.71

Hexagonal or Tetragonal

A large and B small

Cubic

A and B are have ideal size

Orthorhombic/Rhombohedral

A small or B large.

Different structures

A and B have similar ionic radii.

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3. Single crystal growth by different approaches Recently, various techniques were adopted to grow the single crystal of halide based perovskite materials such as; (1) Slow evaporation (SE); (2) Inversion temperature crystallization (ITC); (3) Modified inversion temperature crystallization (MITC); (4) Antisolvent vapour assisted (ASV); (5) Top seeded solution crystal growth (TSSC); (6) Bottom seeded solution crystal growth (BSSC); (7) Temperature lowering method (TLM); (8) Bridgman growth method (BG). However, we have summarized in a very simple and attractive way of perovskite single crystals grown by various techniques which may be very useful to the readers as display in Figure 2. Here we offered only one which is the best among repeatedly reported the same perovskite crystals.



Figure 2. Illustration of different halide based perovskites crystals grown by various techniques. SE; BA2PbCl465: ITC; MAPbCl339, MAPbBr366, MAPbI366, CsPbBr367, FAPbBr368 and FAPbI368: MITC; MAPbCl369, MAPbBr369, MAPbI369, CsPbBr370 and FAPbI371: AVS; MAPbI372, MAPbBr342, CsPbBr373 and (NH4)3Sb2I974: TSSC; MASnI375, FASnI375 and MAPbI346: BSSC; MAPbI340: TLM; MAPbI3Cl76 and MAPbI3 77: BG; CsPbBr345. Reproduced with permission.40,65,66 Copyright 2015, Nature Publishing Group. Reproduced with permission.39 Copyright 2015, American Chemical Society. Reproduced with permission.67,73,76 Copyright 2016, American Chemical Society. Reproduced with permission.68 Copyright 2016, The Royal Society of Chemistry. Reproduced with permission.77 Copyright 2015, The Royal Society of Chemistry. Reproduced with permission.45 Copyright 2013, American Chemical Society. Reproduced with permission.69 Copyright 2015, Wiley-VCH. Reproduced with permission.70 Copyright 2017, WileyVCH. Reproduced with permission.71 Copyright 2016, Wiley-VCH. Reproduced with permission.74 Copyright 2017, Wiley-VCH. Reproduced with permission.42 Copyright 2016, Nature Publishing Group. Reproduced with permission.46,72 Copyright 2015, AAAS. Reproduced with permission.75 Copyright 2016, Wiley-VCH.

3.1. Slow evaporation method (SE) It is well known and simplest technique for air stable samples to grow the single crystals. In this method, solution was prepared by mixing two or more reactant nearly saturate point of a suitable solvent and then sample can be left in a sample vial that has a perforated cap. Therefore, most of the organic and inorganic single crystals are grown by this method, a schematic diagram of this method depicted in Figure 3. Under this circumstance only two perovskite crystals were reported by Daub et al.78 and Xiong et al.65 Daub et al.78 grown the single crystals of perovskite analogous MA2Pb(SCN)2I2, where I– partially substituted by SCN– ion. The black colour crystals of MA2Pb(SCN)2I2 obtained via dissolving a stoichiometric molar ratio of Pb(SCN)2 and MAI in dimethyl formamide (DMF) solution and then followed by slow evaporation at room temperature. The obtained crystals were characterized by IR, UV-Visible, and Photoluminescence, while purity of the crystals provided by powder X-ray diffraction. While the other single crystal of BA2PbX4 (BA = benzylammonium and X = Cl, Br) perovskite materials reported by Xiong et al.65 The small crystals of BA2PbX4 were obtained via dissolving a stoichiometric mixture of BACl2 and PbCl2 in concentrated HCl aqueous solution, while the large size transparent crystal exhibited from DMF solution through slow evaporation at 90 °C, crystal images are depicted in Figure 2. The purity of bulk size crystal verified by powder X-ray diffraction and 6 ACS Paragon Plus Environment

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IR-spectra, and ferroelectric properties of the crystals demonstrated at high temperature. Although, this technique is highly effective and applicable to grow the good quality single crystals from various low boiling point (up to 100 ºC) solvents. However, attempts to perovskite crystals by this method very less, it may be due to less solubility of the reactant of the perovskite precursor.

Figure 3. Schematic representation of crystal growth by slow evaporation method.

3.2. Inversion temperature crystallization method (ITC) This technique was suitable for retrograde solubility of the materials in appropriate solvent at high temperature, a schematic diagram of the technique given in Figure 4. Using this method vast majority of the perovskite single crystals were reported, due to its inverse solubility of the material at high temperature and faster growth rate of the crystals. Moreover, whereas seen that the exhibited crystals are with shape controlled, high quality and time consuming process is very less, when compared to other techniques. However, ITC method first initiated by Saidaminov et al.66 with care full observation of retrograde solubility of MAPbX3(X = I– and Br–) perovskite materials at elevated temperature. In addition, were also suggested that the improvement of basic properties, such as carrier life time, carrier mobility, diffusion length and low-trap density than that of other method crystals. Moreover, the growth rate of MAPbI3 and MAPbBr3 crystals were also estimated, for MAPbI3 crystal increased from 3 mm3/h (first hour) to 20 mm3/h (third hour), while for MAPbBr3 was 7 ACS Paragon Plus Environment


observed faster growth rate up to 38 mm3/h. This growth rate values are order of magnitude higher than the previous reported highest growth rate77. Since, the discovery of this method, utilization for crystal growth of lead halide perovskite materials has been increased enormously.

Figure 4. Schematic representation of the ITC apparatus in which the crystallization vial is immersed within a heating bath.

Kadro et al.79 also have grown the single crystals of MAPbI3 using γ -butyrolactone (GBL) solution prior to Saidaminov et al. A free standing single crystals of MAPbI3 grown without relying on any additives such as capping agents or seeding particles using ITC method. However, the grown crystals were unstable while cooling or remove the vial from the hot plate. The black colour crystals of MAPbI3 obtained via dissolving a stoichiometric molar ratio salts of PbI2 and CH3NH3I in GBL solution under vigorous stirring at 100 °C and then followed by rapidly increase temperature from 100 °C to 190 °C until the formation of desired dimensions of the crystal (Figure 5).


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Figure 5. (a) Schematic illustration of crystals growth at high temperature while decrease temperature the crystals are disappear. (b) Photo of the grown crystals at 190 ºC. Reproduced with permission.79Copyright 2015, Nature Publishing Group.

Bark and co-workers have extended this technique by grown the single crystals of FAPbX3 (X = Br and I) materials68. Then it became a general method not only for MAPbX3 but also applied to grow crystals for many perovskite materials. However, the single crystals of FAPbX3 (X = Br and I) were grown by careful observation of retrograde solubility in appropriate pure or mixture of solvents. Thus, when the GBL concentration is 1M and constant heating at 100 ºC for about 3 hours, the resulting crystals are in the form of needle like yellow colour and unstable. While in further trial, the concentration of solution was reduced from 1M to 0.8 M and temperature of the solution was amplified to 115 ºC, successfully observed crack- and grain boundary-free a large size black crystal of FAPbI3 within 3 hours. Similarly, for FAPbBr3 single crystals the 1M DMF solution heated at 120 ºC for about 3 hours and resulting crystals are very small, while obtained a large size high quality and shape controlled crystal by reducing the polarity of DMF with mixing of GBL (1:1) solution onset heating at 55 oC for three hours, both MAPbI3 and MAPbBr3 crystals presented in Figure 2. Moreover, the basic key parameters such as carrier life time, mobility, diffusion length and trap-density of the crystals were explored and which the parameters and indicated that superior to their polycrystalline thin film and MAPbX3 single crystals.80 9 ACS Paragon Plus Environment


By adopting same method, unwilling dopant crystals of MAPbBr3 were also reported by Bakr and co-workers.81Therefore, the dopant crystals of MAPbBr3 synthesized via incorporation of trivalent bromide salts of Bi3+, Au3+, In3+ and MABr into a crystallization mixture of PbBr2 and MABr in DMF solution and then followed by inverse heating at 100 ºC for about 3 hours. Apart from the three dopant crystals, incorporation of Bi significantly showed red shift in absorption maxima from 570 nm to 680 nm with narrowing band gap, while the other dopant of Au and In crystals showed no noticeable spectral changes from the undoped crystal, as depicted in Figure 6. In addition, the colour changes of crystal observed upon increase the incorporation of Bi% from orange to black depending on content of Bi%, while no results in colour changes with increasing dopants of Au and In percentage. However, all the three dopant (Bi3+, Au3+ and In3+) and various ratio of Bi% crystals were obtained without any crack and larger size parallelepiped shape controlled crystals (Figure 6). (a)

(b)

Figure 6. (a) Single crystals of MAPbBr3 and other dopants of Au, In and Bi with different contents. (b) UV-Visible spectra of MAPbBr3 and dopants of Au, In and Bi crystals. Reported with permission. Reproduced with permission.81 Copyright 2016, American Chemical Society.

Previous, the chloride based perovskite crystals grown by classical techniques for structural characterization.82A large size high quality single crystal of MAPbCl3 were also reported by Bakr and co-workers under this method.39 In addition, the basic information of 10 ACS Paragon Plus Environment

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crystal such as charge mobilities and trap-density were calculated to use directly in optoelectronic application. Therefore, the aforesaid results are several fold better than that of polycrystalline thin-film and make them to use as a UV-Visible photodetectors. A high quality large size single crystal of MAPBCl3 successfully grown after several attempts in various solvents using a equi-molar ratio of MACl and PbCl2 in mixture of DMF and DMSO (1:1 ratio) solution at a fixed temperature of 50 ºC for about 6 hours. After 6 hours a colourless with parallelepiped shape transparent crystal were obtained, image of the crystal presented in Figure 2. Under this method all-inorganic single crystal of CsPbBr3 developed by Dirin et al.67 In addition, similar all-inorganic single crystal of CsPbBr3 were also grown from hydrohalic solution. It is noteworthy to mention that the ITC method is best suitable to grow a large and high quality crystals of CsPbBr3. Therefore, the crystals of CsPbBr3 perovskite grown via dissolving of CsBr and PbBr2 precursors (1:2 molar ratio) in DMSO solution by addition of cyclohexanol (CyOH)/DMF mixture and then followed by heating at 110 ºC for about 12 hours, image of the crystal depicted in Figure 2. Where the addition of CyOH/DMF mixture into the reaction for protecting the formation of multinuclei or polycrystal and to make smoothened surface to the crystals. Moreover, the measured properties such as trap density, carrier mobility, and diffusion length as well as gamma-photon absorptivity showed higher than that of previous reported from Bridgman and anti-solvent methods. 3.3. Modified inversion temperature crystallization method (MITC) To grow a bulk size single crystal of perovskite the ITC method were modified. Under this technique, two direction can be followed to grow as large as conveniently the single crystals, one is seed crystal growth while the other one is impurity avoiding of the undesired materials. A seed crystal growth technique is favourable for organic-inorganic perovskite materials, while the impurity avoiding of undesired materials is familiar to grow 11 ACS Paragon Plus Environment


all-inorganic crystal. However, Liu et al.69,71 reported various large size single crystals of organic-inorganic perovskite using MITC method, such as MAPbI3, MAPbBr3, MAPbCl3 and FAPbI3, and also explored the potential parameters of carrier life time, carrier mobility, diffusion length and trap-density.

Figure 7. Schematic illustration of large size crystal growth using seed crystal by MITC method.

A large size and high quality single crystals of MAPbX3 (where X = Cl¯, Br¯, and I¯) and FAPbI3 grown by following step-wise process, in first step prepared number of seed crystals via dissolving MAX or FAX and PbX2 in appropriate solution and then inversely heating for about overnight. Out of large number of seed crystals, only one good quality selected seed crystal were placed into a freshly prepared precursor solution and then applied heat for overnight. The original ~1-2 mm seed is grown into a larger (7 mm) size, using this larger seed crystal as new seed and repeated the process and obtained much larger single crystals, the schematic picture of the process, as depicted in Figure 7 and occurred large size single crystal presented in Figure 2. However, the potential properties of the crystals such as optical absorption and photoluminescence suggested red-shift than the corresponding thin-film, but individually compared the photoluminescence shifted toward blue-shift, which indicating low trap-density of the crystal. In addition, a photodetector device fabricated using wafer crystal of FAPbBr3, which showed superior performance almost 90 times higher photoresponse than 12 ACS Paragon Plus Environment

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that of thin-film. Han et al.83 also reported a similar crystal of FAPbI3 using this MITC method. Moreover, the growth process of the crystal also similar except the use of precursors (Pb(ac)2.3H2O and FAac) for seed crystal growth and temperature condition. The measured optical absorption and photoluminescence properties suggested that the lower bandgap with red-shift emission. Furthermore, the key parameters of single crystal exhibited very larger value of carrier lifetime and carrier mobility as well as low trap-density than that of thin-film results. Yang et al.84 reported a large size single crystal of MAPbI3 using this technics in order to investigate nonlinear optical properties and amplified spontaneous emission (ASE) properties. Therefore, the growth process of the crystal same as to Liu and co-workers procedure except the use of temperature condition. The nonlinear optical properties of the crystal measured using open aperture Z-scan technique and the absorption coefficient resulted lower value than that of reported of MAPbBr3 crystal 85 and polycrystalline of MAPbI3.86 The ASE measurement study carried out using three different input power excitation wavelength (nm): 1300, 1600, and 2100; corresponding absorption photon: 1.54, 2.29 and 3.1 respectively. Results of bulk crystal supported under two (1600 nm) and three (2100 nm) photon excitation over a range of operation temperature. Rao et al.87 prepared a 16 µm thickness of laminar MAPbBr3 single crystal by adapting MITC method. Previous, reported wafer (~100 µm) type FAPbI3 single crystal showed a high power conversion efficiency than that of high dense thickness crystal in photovoltaic application.71 Moreover, this laminar single crystal showed clear-cut optical and photoluminescence band edge, superior crystal quality, high mobility, low-trap density and high power efficiency to that of thin-film polycrystalline materials. However, a laminar and controllable thickness-size single crystal of MAPbBr3 were synthesized via constructing a box with appropriate space gap using TiO2 coated FTO glass, the schematic illustration as depicted in Figure 8. The precursors of MABr 13 ACS Paragon Plus Environment


and PbBr2 in DMF solution was inserted into the provided gap and then followed by local area of solution heating at 90 ºC.

Figure 8. (a) Schematic diagram of growth module and local heating with homothermal aluminium block (b) Laminar single crystal of MAPbBr3. Reproduced with permission.87 Copyright 2017, The Royal Society of Chemistry.

To grow a pure single crystal of all-inorganic CsPbBr3 is much more complicated due to unbalance solubility of the precursors CsBr2 and PbBr3 (i.e., poor solubility of CsBr and good solubility of PbBr3). Typically, due to this phenomena, mixture formation of three single crystals of CsPbBr3, Cs4PbBr6 and CsPb2Br5 were observed. To avoid the undesired single crystals of Cs4PbBr6 and CsPb2Br5 were adopted to MITC method by Rakita et al.73 and Bakr co-workers.70 However, growth procedure of both the group slightly different at the initial step, Rakita et al.73 initially prepared a saturated solution before heating, while Bakr group synthesised by varying molar ratio of the precursor and temperature condition. Rakita et al.73 grown the crystals of CsPbBr3 via saturating the precursors (CsBr and PbBr2) DMF solution using anti-solvents. Here, they tried with nine anti-solvents to make a saturate solution, but saturated precipitation existing only from acetonitrile (MeCN), methanol (MeOH) and water (H2O). The saturated solution of MeCN and MeOH is in yellow-orange colour, while treated with H2O exhibited in white colour precipitate due to its bleaching capability of materials. The precipitate of impurity whereas avoided from the saturated solution of MeCN and MeOH by filtration and then followed by heating to a desired temperature until the mixture of crystals (yellow-green and orange) appeared, the solution 14 ACS Paragon Plus Environment

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was cooled to room temperature with continues stirring up to disappear the orange colour crystals. The cooled solution was again filtered to avoid undesired crystal and then followed by slow heating up to formation of desired crystals, schematic illustration of the procedure given in Figure 9. The formation of single crystal initiated at 120 ºC and 40 ºC from saturated solution of MeCN and MeOH respectively.

Figure 9. Schematic procedure for preparation of pure CsPbBr3 crystals using modified ITC method. Reproduced with permission.73 Copyright 2016, American Chemical Society.

Bakr and co-workers70 developed a shape controlled desired single crystal of CsPbBr3 by varying the molar ratio of CsBr and PbBr2 precursors under this method. At high temperature (120 ºC) with equal molar ratio of precursor presented the formation of dominated yellow colour Cs4PbBr6 crystal, while occurred reduce part of yellow colour crystals when increases the ratio of PbBr2 (1.5) at same temperature. However, the pure crystal of CsPbBr3 were grown using the molar ratio of PbBr2 double than that of CsBr (1:2) by filtration of solution at 100 ºC and then followed by further heating from 100 ºC to 120 ºC for about 3 hours, image of the crystal presented in Figure 2. Moreover, were also explored the basic properties, such as optical absorption, photoluminescence, and transport properties of the obtained crystal.

3.4. Anti-solvent vapour assisted method (ASV) In this method solvent play significant role, because we have to select two or more solvents, one is good solvent which is less volatility and other one is more volatility which is 15 ACS Paragon Plus Environment


bad solvent. The precursors of halide perovskite will be dissolved in good solvent of small vial. This vial will be placed in a large size containing a second bad solvent vial and then sealed. The principle of this method, when the bad solvent slowly diffuses into the precursor solution the proficiency of the crystal formation increase at the bottom of the sample vial due to insolubility of material in the bad solvent. The schematic diagram of AVS method depicted in Figure 10.

Figure 10. Schematic illustration of anti-solvent method for single crystal growth.

First time AVS technique was utilized by Bakr's group72 to grow the perovskite crystals and obtained millimetre size single crystal of MAPbX3 (X = Br¯ and I¯). The single crystals of MAPbBr3 and MAPbI3 were grown using DMF and GBL are as good solvents respectively, while DCM (dichloromethane) used as a bad solvent for both cases. However, the single crystals of MAPbX3 grown via dissolving the equimolar ratio of MAX and PbX2 precursors in good solvents and followed by anti-solvent diffusion in closed vial, the size of the crystals exceeded 100 cm after several days. In addition, the potential properties of optical and electrical properties were measured to know its suitability for optoelectronic applications. The absorption and luminescence results exhibited no excitonic signature with clear band edge cut-off than that of thin-film polycrystalline material, which indicating minimal of in gap defects. Moreover, the higher value of carrier mobility and carrier lifetime as well as low trap density showed than that of thin-film polycrystalline materials. Wei et al. 42 synthesized a high quality and large size single crystal of MAPbBr3 using AVS method following Bakr's72 16 ACS Paragon Plus Environment

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procedure and used for X-ray detector application. However, due to unbalance solubility of MABr and PbBr2 were observed opaque and cracks of the crystal with respect to time grown via equimolar ratio. Therefore, to avoid the opaque nature of the crystal were reduced the molar ratio of PbBr2 from 1 to 0.8. The reduced molar ratio single crystal of MAPbBr3 presented high quality and more stable with respect to time as well as shape controllable. The image of the crystal presented in Figure 2. Using this cubic shape single crystal of MAPbBr3, a device was constructed for X-rays detection and the performance was significantly improved 70 times higher than that of thin-film polycrystalline. All-inorganic single crystal of CsPbBr3 were also grown via AVS method by Rakita et al.73 using saturated stock solutions. The procedure is as fallow; a saturated solution of either MeCN or MeOH were filtered and placed in a cleaned Petri dish by covering filter paper and on top with a Petri glass. This covered crystallization flask was then placed in a second Petri dish at elevated position level of anti-solvent, here the anti-solvent should be chosen similar to the saturated solution. Outer flask were also sealed by a filter paper and then followed by Petri dish glass similar to the inner crystallization flask, a schematic illustration of setup depicted in Figure 11. The slow growth rate of CsPbBr3 crystallization show at room temperature, while accelerate growth rate of crystallization observed by placing the whole setup on hot plate. After 48 hours well shaped and orange colour crystals developed in both (MeCN and MeOH) saturated solution.



Figure 11. Schematic illustration of single crystal growth using saturated solution by AVS method. Reproduced with permission.73 Copyright 2016, American Chemical Society.

Zuo et al.74 synthesized a series of lead free perovskite materials of (NH4)3Sb2IxBr9-x, where x changes from 9 to 0 (0 ≤ x ≥ 9). Among the series of perovskite materials, only one (NH4)3Sb2I9 single crystal were grown via AVS method. They have reported not only the replacement of Pb but also used eco-friendly solvents for reaction procedure. Basic information of absorption, photoluminescence, and charge carrier mobility were provided which may be useful for the optoelectronic application. However, large size high quality single crystal of (NH4)3Sb2I9 grown via dissolving the NH4I and SbI3 precursors in ethanol solution and followed by CHCl3 used as an anti-solvent.

3.5. Top seeded solution growth method (TSSG) Dang et al.75 reported the high quality large size Pb free single crystals of MASnI3 and FASnI3 under ambient condition by using this method. The crystals of MASnI3 exhibited unstability, while FASnI3 crystal showed stable for about period of one month at ambient condition, the unstability of MASnI3 indicating that the oxidation state of Sn transforming from Sn2+ to Sn4+. The potential properties of crystals were also measured such as band gap, thermal expansion and specific heat measurement for directly use this materials in 18 ACS Paragon Plus Environment

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optoelectronic applications. The single crystals of both material were synthesized by dissolving the raw material of SnO and MAI or FAI in the mixture of HI and H3PO2 stirring at 78 ºC under ambient condition for about keeping one month of period using top seeded solution method. The black and shiny single crystal images presented in Figure 2. Furthermore, a high quality lead halide single crystal of MAPbI3 were also reported by Dong et al.46 using TSSG method. The measured carrier life time, carrier mobility and diffusion length of the crystal show 10 times longer and several fold greater than that of thin-film polycrystalline materials. However, the single crystals of MAPbI3 grown via a saturated precursor solution transferred into the bottom of closed vial and then silicon substrate was inserted. The temperature of bottom of bottle was maintain at 75 ºC using oil-both and top of the container that is area of Si substrate was cooled by air flow. Several seeds of MAPbI3 crystal were observed on Si substrate, except one seed crystal all are removed from the substrate to grow a large size single crystal. After several hours a high quality and large size single crystal were grown. The schematic illustration presented in Figure 12 and obtained crystal picture depicted in Figure 2.

Figure 12. Schematic illustration of top seeded single crystal growth techniques. Reproduced with permission.46 Copyright 2015, AAAS.



3.6. Bottom seeded solution growth methods (BSSG) Two large size and high quality single crystals of MAPbI3 and MAPbI3(Cl) were obtained by Lian et al.

40,76

using BSSG technique. For MAPbI3 single crystal, the seed

crystals were prepared by following the Poglitsch and Weber’s88 method via dissolving lead(II) acetate trihydrate and methylamine in hydroiodic acid aqueous solution for about five days. A good quality seed crystal selected and attached at the end of Pt wire and then placed to immerse in bottom of the precursor vial while temperature was reduced slowly from 373 K to 320 K 5K per hour for about 15 days, the image of the grown crystal presented in Figure 2. Using this large size single crystal of MAPbI3 constructed a device for photodetector application. The photodetector device performance suggested much better than that of thin-film polycrystalline detector. Second high quality large size single crystal of chloride incorporated MAPbI3(Cl) grown by two different methods. A seed crystal of MAPbI3(Cl) prepared by temperature lowering method, while a large size crystal of MAPbI3(Cl) grown by bottom seeded solution growth method. Seed of the MAPbI3(Cl) crystal grown via dissolving lead acetate, methyl amine hydroiodide and methyl amine hydrochloride in hydroiodic acid separately by heating at 130 ºC and mixing together this hot solution of precursors and followed by rapidly lower the temperature from 130 ºC to 60 ºC. From large number of seed crystals selected a good quality seed and placed into the bottom of the precursor solution of second bottle and then followed by preheating at 105 ºC for about 1 hour. The temperature was quickly dropped to 100 ºC and then cooling rate of 0.2 ºC/h for 12h, then 0.5 ºC/h to 60 ºC, and where after 1 ºC/h to 40 ºC. Altogether, it took about 5 days to grow a large crystal of MAPbI3(Cl) and estimated growth rate around 18 mm3/h, the picture of the crystal depicted in Figure 2. A schematic representation of BSSG process is depicted in Figure 13.


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Figure 13. Schematic illustration of bottom seeded solution growth crystal. 3.7. Temperature lowering method (TLM) Under this method two perovskite crystals, one is MAPbI3 and other one is MASnI3 were reported. A bulk size MAPbI3 crystal reported by Dang et al.77 grown in HI solution. This MAPbI3 single crystal characterized by single crystal X-ray diffraction, UV-Visible and thermogravimetric analysis (TGA). The band gap of the crystal is 1.48 eV, which is close to the theoretical result and smaller than that of thin-film polycrystalline materials. A large size single crystal of MAPbI3 grown by dissolving the CH3NH3I and Pb(CH3COO)2.3H2O precursors in HI solution with continues stirring at 65 ºC. The temperature of reaction mixture were reduced to 40 ºC without stirring, after several days a black and shiny large size crystal were developed, image of the crystal given in Figure 2. A lead free perovskite single crystal of MASnI3 reported by Takahashi et al.89 using this technique. However, the single crystals of MASnI3 prepared by dissolving the SnI2 and MAI precursors in three different solution, such as aqueous HI solution, mixture of aqueous HI and γ-aminobutyric acid, and ethanol solution. The tiny single crystals of MASnI3 presented from both aqueous HI (0.3 mm), and mixture of solution, while 3 mm growth of crystal presented in ethanol solution. The resistivity, conductivity and thermoelectric power measurement with function of temperature were explored using the 21 ACS Paragon Plus Environment


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obtained crystals. 3.8. Bridgman Method (BG) Stoumpos et al.45 reported the single crystals of CsPbBr3 grown by Bridgman method using solid state process at high temperature to evaluate in X-ray and γ-ray photodetector application. However, resulted single crystals of CsPbBr3 showed phase transition at 88 ºC and 130 ºC from orthorhombic (Pnma) to tetragonal (P4/mbm), tetragonal to cubic (Pm3m) system, respectively. The electron and hole mobility of the crystals exhibited nearly equal distribution with high rate value. Depending on photoconductivity, optical absorption and photoluminescence results used for X-ray and γ-ray detection using Ag-source. The single crystals of CsPbBr3 grown by Bridgeman method via grinding equi-molar mixture of CsBr and PbBr2 transferred into a fused silica tube while carefully evacuated to 10-4 mbar and followed by tube was sealed. This sealed tube was placed in a furnace and attached to the clock mechanism to completion of reaction. The temperature of the furnace was slowly heated to 600 ºC for about 6 hours and then slowly cool to room temperature. The orange, transparent crystals of CsPbBr3 were developed, images of the crystal presented in Figure 2. 3.9. Solvothermal growth Method (SG) Two reports are available one is with different mixed halide and other one is single halide perovskite crystals under this technique. Zhang et al.

90

reported three different mixed

halide (Br/Cl) single crystals of MAPbBr1-xClx using this growth method, where x is 0, 0.15 and 0.25. Optical absorption studies of the crystals were suggested towards blue shift and also band-gap increases with increasing of Cl¯ ion in the reaction mixture. Furthermore, the powder X-ray diffraction of the crystals exhibited contraction of unit cell length and increase of 2θ value while increasing chloride ion in the mixture. However, the crystals of MAPbBr122 ACS Paragon Plus Environment

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xClx

(x = 0, 0.15 and 0.25) grown by dissolving different molar ration of precursors in DMF

solution in a closed vials and then followed by heating at 50 ºC without evaporation of solvent for about 5 hours. Fang et al.

41

also reported various crystals of single halide and

mixed halide perovskite of MAPbBr3−xClx and MAPbI3−xBrx using this method, where x indicates different halide ratio. By careful observation of these two compositions one can notice that the possibility of incorporation Cl¯ ion in the lattice of Br¯, while Br¯ ion in the lattice of I¯ but not vice versa. Using all these single and mixed halide crystals were constructed different device for photodetection. Performance of device presented covering of entire of UV-Visible region (from blue to red colour region) by incorporation of various halide ions. In addition, the optical absorption studies suggested blue shift by incorporation of Cl¯ and Br¯ ions in the lattice of MAPbBr3 and MAPbI3 respectively, while powder X-ray diffraction showed increase of 2θ value. Precursor solution prepared by mixing methylamine, single or mixed haloidic acid with different halide ratios, and lead(II) acetate to form a supersaturated aqueous solution at 100 °C. All these single crystals grown via the temperature of precursor solution gradually lowering and the images of crystals depicted in Figure 14.

Figure 14. Photographs of single-halide and mixed-halide perovskite single crystals with different halide compositions. Reproduced with permission.41 Copyright 2015, Nature Publishing Group.

Stoumpos et al.91 prepared various iodide based perovskite single crystals; MAPbI3, FAPbI3, MASnI3, FASnI3, CsPbI3, CsSnI3, CsSnI6 and MASn1-xPbxI3 using precursors of MAI, FAI, CsI, PbI2 and SnI2. Therefore, all the different iodide based perovskite single 23 ACS Paragon Plus Environment


crystals grown by four different procedures, such as growth from solution, sealed tube predation, open tube preparations and at room temperature solid state preparations (grinding). Structural phase transition were also observed but successfully determined the single crystals structure by varying temperature from 100 to 400 K. The chemical and physical properties of the crystals strongly depends on synthesis methods. The nature of the resulting materials is discussed in terms of their thermal stability, optical and electronic properties. The band gap of all the single crystals exhibited in the range of 1.25 to 1.75 eV calculated from optical absorption measurements, and photoluminescence emission exhibited in near IR-region from 700 nm to 1000 nm. Moreover, the behaviour of crystals either p-type or n-type significantly depends on synthetic procedure. The solution method grown crystals act as p-type, while obtained from solid state procedure act as n-type materials.

4. Optical absorption and photoluminescence properties Halogen based hybrid perovskites exhibiting strong optical absorption band covering from visible region to near-IR region either altering by cation or anion. Moreover, this perovskite materials present appropriate direct bandgap between valance band and conduction band and leading to exhibit clear-cut broad absorption from visible to near IR region (Figure 15). A typically direct bandgap is possible when the crystal moment or Kvector of maximum energy state of valence band and minimum energy state of conduction band will be same in brillouin zone condition as shown in Figure. 15a. The investigation of electronic transition MAPbI3 using DFT calculations were suggested that direct bandgap π-π transition.92 In addition, were also suggested about density of states, the conduction band minimum (CBM) located at p-orbital of lead and valance band maximum (VBM) located at halide p-orbital, while MA+ cation was located far-away from CBM and VBM only just it was maintain the charge balance. However, optical absorption of perovskite crystal exhibited clear-cut sharp band edge with no excitonic signature than that of thin-film polycrystalline 24 ACS Paragon Plus Environment

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perovskite materials. Therefore, it indicating that the single crystals are predominantly free from grain boundaries or structural defects and low-trap densities. We have collected almost all the available perovskite crystal absorption band peak maxima and provided in Table 2. It is clear that the substitution of halide part in APbX3 (where, A = MA and FA; X = Cl, Br and I) leads to dramatic changes in absorption from low region (Cl) to high region (I). Similarly, replacement of Pb2+ with Sn2+ also extended the wavelength further in longer region. The photoluminescence properties of perovskite materials also covering form visible region to near-IR region with sharp narrower band edge (Figure 15). In general, results of emission could be red-shift than the corresponding absorption band, but virtually all the reported emission band (given in Table 2) of single crystals are lower or blue shift with narrow peak. The blue-shifted and narrower emission peak which indicate significantly a lower trap density and separation of excitons into free charges in the material.41,69,87 Depending on this concept frequently were reported from various research groups.93 It should be noted that all the reported bandgap values of single crystals substantially narrower, while observed wavelength shifted into longer region of optical absorption and photoluminescence than their corresponding microcrystalline and thin-film materials.

(a)

(b)



(c)

Page 26 of 60

(d)

Figure 15. (a) Energy vs crystal momentum for a semiconductor with a direct band gap, (b) UVVisible spectra of MAPb(I1-xBrx)3, (c) UV-Visible and (d) photoluminescence spectra of MAPbX3 (X = Cl-, Br- and I-), (e) colloidal solutions of CsPbX3 in toluene under UV lamp (λ= 365 nm), (f) representative PL spectra (g) typical optical absorption and PL spectra, (h) CIE chromaticity diagram (black data points) of CsPbX3 NCs, color gamut spectra of CsPbX3 NCs (solid black triangle), liquid crystal display TV (dashed white triangle) and NTSC TV (solid white triangle). Reproduced with permission.69 Copyright 2015, Wiley-VCH. Reproduced with permission.94 Copyright 2015, American Chemical Society. Reproduced with permission.95 Copyright 2013, American Chemical Society.

Table 2. Optical absorption and photoluminescence maxima as well as band-gap values of halide based perovskite single crystals. Perovskite UV-Vis. (nm) PL (nm) Band-gap (eV) Method Ref. MAPbI3 " " " " " " " " MAPbBr3 " " "

815 760 850 840 ---836 830 821 836 550 570 570 560

790 820 770 ---775 ---790 820 784 570 550 ---545

1.52 1.51 1.45 1.47 1.51 1.48 1.49 1.51 1.53 2.21 2.17 2.17 2.26


SG AVS TSSC BSSC ITC MITC ITC ITC TLM AVS SG ITC MITC

91 72 46 40 79 69 82 66 77 72 41 80 87

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" " " MAPbCl3 " " FAPbI3 " " " FAPbBr3 " CsPbBr3 " " " MASnI3 FASnI3 MAPbTI2 (NH4)3Sb2I9

568 550 574 440 435 431 870 850 880 900 557 580 550 560 551 560 1078 880 790 645

574 ---537 420 440 402 812 820 843 ---587 ------540 535 556 ------702 639

2.18 2.25 2.24 2.81 2.85 2.97 1.49 1.45 1.41 1.4 2.15 2.13 2.25 2.21 2.25 2.21 1.15 1.40 1.56 1.92

ITC SG MITC SG ITC MITC MITC MITC ITC ITC ITC ITC ITC AVS BG MITC TSSC TSSC SE AVS

66 90 69 41 39 69 71 83 81 68 79 68 67 73 45 70 75 75 78 74

5. Carrier lifetime, carrier mobility and diffusion length The halide based perovskite single crystals directly use in solar cell as well as other appropriate applications, it is important to know the potential quantity of carrier life time, carrier mobility and carrier diffusion length of the materials. Particularly, carrier life-time of electrons and holes of perovskite materials in photovoltaic process play an important role, when excited state lifetime is longer the power conversion efficiency is high, while lifetime is shorter the power conversion efficiency is low. However, the carrier lifetime of the materials depends on the nature, dimension and purity of the materials. Therefore, the single crystal of perovskite life-time is much longer than the corresponding thin-film polycrystalline, which indicates that the single crystal have much lower quantity of defects. All the reported carrier lifetime of halide based perovskite single crystals presented in Table 3, whereas given twoexponential decay numbers, one is fast and other one is slow. The shorter carrier life-time indicate high trap density related to the crystal surface condition, while the longer carrier lifetime represents carrier transportation in the crystal with miner defects70,72,83.



Page 28 of 60

Generally, the carrier mobility of electrons and holes of the perovskite materials derived from various techniques such as space charge limit current (SCLC), Time-of-flight (TOF), Hall effect measurement etc. Apart from various method, SCLC method extremely used to determine the carrier mobility of perovskite materials. Using SCLC method find out dark current-voltage (I-V) traces characteristics under applied bias by sandwiching a single crystal of perovskite between two semi-transparent metal electrodes with outer contacts, as shown in Figure 16. It is clearly seen that the three different regions of characteristic, such as namely ohmic region, trap fill and child regions. First ohmic region is a lower bias, which increases linearly with respect to voltage, while second and third regions are trap-filling and child or trap-free regime, respectively. The trap-density of the materials will be calculate from trap-filling region using equation 2

(2) where L is the thickness of the crystal, VTFL is trap-filled limit voltage, ε is relative dielectric constant of the material and ε0 is the vacuum permittivity. While the carrier mobility of the materials calculated using Mott−Gurney law

(3) Where Jd is the current density and V is the applied voltage. All the reported carrier mobility and trap-density of the perovskite single crystals presented in Table 3. It is worth noting that observed for all cases of perovskite single crystals dramatically reduce trap-density while large value of carrier mobility than that of thin-film polycrystalline materials. Moreover, the key quantity of carrier diffusion length of perovskite materials also play significant role in optoelectronic applications. The longer carrier diffusion length of 28 ACS Paragon Plus Environment

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perovskite can find direct application predominantly in x-ray, gamma-ray sensing and photodetection as well as radiation energy harvesting. Diffusion length of material depends on corresponding carrier life time and carrier mobility of the material.

Therefore, the

diffusion length can be derive using the following relation

(4) Where KB is the Boltzmann constant and T is the sample temperature. By substitute the value of carrier mobility and carrier lifetime. Diffusion length of all reported perovskite crystals presented Table 3. It is clearly seen that the two values, one is longer which obtained from longer carrier lifetime, while other one is shorter length obtained from shorter carrier lifetime. Moreover, the diffusion length of single crystal very large (more than 2 order of magnitude) than that of thin-film polycrystalline material.42,46

Figure 16. Dark current−voltage (I-V) measurements according to the SCLC model. Reproduced with permission.71 Copyright 2016, Wiley-VCH.



Page 30 of 60

Table 3. Carrier lifetime, carrier mobility and diffusion length of halogen based perovskite single crystals. Lifetime (µs)

Mobility (cm2/VS)

Diffusion length (µm)

Fast

Electrons

longer

Slow

Holes

Shorter

Trap-density (cm-3)

Method

Ref.

ITC

66

Electrons Holes

MAPbI3 0.02

0.57

67.2

----

----

----

34

82

95

24.8

164

0.02

1

----

2.5

----

----

----

----

167 * 66

----

10.0

1.3

----

---175 *

1.4x1010 * 4.8×10 10

1.8x10 9

MITC

69

4.5× 1010

3.6× 1010

TSSC

46

17x103

3x102

3.3×1010 *

AVS

72

----

----

1.8×109 *

AVS

72

----

----

----

SG

91

3 x 1010 *

ITC

66

MITC

69

AVS

72

AVS

42

MITC

87

MITC

69

ITC

39

MITC

71

MAPbBr3 0.03

0.30

----

----

0.04

0.35

----

----

0.09

0.37

24.0 * ----

4.36 38 *

190

4.3

1.8

----

----

8x102

2x102

217 23.7 *

190 * ----

1.1x10 11

2.6x10 10

5.8 × 109 * 3 × 106

7 × 107

2.5×1010 *

---MAPbCl3

----

----

0.08

0.66

179

---42 *

----

----

8.5

3.0

----

---3.1×1010 *

FAPbI3 ----

----

0.03

0.48

0.03

0.48

40 4.4 *

----

35

1.34x1010 ----

----

----

2.2

0.5

6.2×10 11 *

MITC

83

6.6

1.7

1.13x1010 *

ITC

81

SG

91

MASnI3 ----

----

2320

322

----

----

----

FASnI3


----

Page 31 of 60 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60


----

----

103

----

----

----

----

----

SG

91

ITC

81

FAPbBr3 0.05

0.41

----

62

19

9.6×109 *

10.5 CsPbBr3

0.02

0.23

52

11

5.5

2.5

1.1×1010 4.2×1010

MITC

70

0.004

0.03

----

----

----

----

----

----

AVS

73

----

----

SG

91

----

----

AVS

74

CsSnI3 ----

----

536

----

----

---(NH4)3Sb2I9

----

----

4.8

12.3

----

----

Note: * Mention only one value it may be belongs to either electron or holes.

6. Device fabrication using as grown single crystals of perovskite materials 6.1. Architecture, working principle of solar cell and photodetector device

(b) (a) Figure 17. (a) Schematic architecture and principle of perovskite solar cell device and (b) photodetector device with demonstration of electron and hole transportation.



A perovskite solar cells consists of Al2O3 recombination blocking thin layer was deposited on a transparent conducting oxide (TCO) glass and then mesoporous TiO2 was deposited, which act as electron transport material (ETM) (Figure 17). The most commonly used substrate glass is coated with fluorine or indium-doped tin oxide (FTO or ITO). In addition, perovskite crystal were deposited on TiO2 layer and then followed by a hole transport material (HTM), generally used 2,2',7,7'-tetrakis (N,N-di-p-methoxyphenylamine) 9,9'-spirobifluorene (spiro-OMeTAD), and finally deposited a layer of counter electrode which made by Au or Ag metal. When the device is illuminate with sun light the perovskite material absorbs light. After absorption of sun light generates the electrons and holes in the materials simultaneously. The generated electrons ejects into the conduction band (CB) of porous TiO2 (energy gap 3.2 eV), while the holes are capture by HTM layer. Finally, both the outer layers to be contacted by a external load. The schematic architecture of the perovskite solar cell as depicted in Figure 17a. A photodetector device fabricate by sandwiching the single crystal of perovskite between two semi-transparent electrodes, one is act as cathode while the other one is act as anode. Usually, Au metal used as a cathode and Ga or Pt metal used as an anode. The schematic device of photodetector as presented Figure 17b. The working principle of photodetector, when the sun light strike on device, under external field material generates holes, and electrons. The generated charges moves through the contact towards external load of diode. Despite, the excellent potential properties of halide based perovskite single crystals to use in various applications, nevertheless come to the practical uses of single crystals reported with limited applications such as solar cell and various range photodetector (from UV- NIR, X-ray detector and γ-ray detector). However, first we begin to start in explaining about the fabricated solar cell device and then followed by photodetector devices of halide based perovskite single crystals. Rao et al.87 constructed a solar cell device using 16 µm laminar 32 ACS Paragon Plus Environment

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single crystal of MAPbBr3. The PCE of the cell exhibited 7.11 % with excellent stability of preserving 93% initial PCE after 1000h aging. The solar cell device construction follow as FTO/TiO2/PVK/HTM/Au (PVK=laminar MAPbBr3 SC). Bakr and co-workers developed a monocrystalline film of MAPbBr3 perovskite on the surface of various substrates by applying a very short ultrasonic pulse (~1) to the solution via a designed method based on a cavitationtriggered asymmetrical crystallization (CTAC) strategy.96 However, they constructed different types of solar cell devices (without any ETM and HTM, with ETM layer) by varying thickness of films, more details are presented in Table 4. A simple solar cell (without any

layer;

ITO/MAPbBr3/Au)

and

p-n

junction

solar

cell

(with

ETM

layer;

ITO/TiO2/MAPbBr3/Au) exhibited PCE of 5.49% and 6.53% respectively, both the devices are fabricated using 1µm monocrystalline film, as depicted in Figure 18a. In addition, stability of both devices show higher than that of polycrystalline devices at ambient condition for about 48 hr. Huang and co-workers grown a series of thickness controlled (0.5µm to 200µm) MAPbI3 crystals via diffusion facilitated space-confined method and constructed a solar cell devices.97 The device fabrication follow as ITO/PTAA/MAPbI3/PCBM/C60/BCP/Cu (where PTAA; poly(bis(4-phenyl) (2,4,6-trimethylphenyl)amine, PCBM; phenyl-C61-butyric acid methyl ester, BCP; bathocuproine, Cu; copper), as depicted in Figure 18b. Where PTAA allow the quick diffusion of ions in the confined space. Although, the PCE of 16.1% obtained when the crystal thickness diameter is 10µm. Moreover, the PCE of 17.8% obtained when the surface of thin crystal spin coated by MAI. It was mentioned that the grown thin single crystals may have large surface charge traps. In addition, Huang and co-workers were also developed a solar cell device using a π-conjugated Lewis base (n-type semiconductor organic molecule) interlayer between thin single crystal perovskite and cathode.98 This n-type organic molecule exhibited multi roles such as, electron transport layer, decreasing the grain boundaries, avoid the thermal annealing process and enhancing the device stability by 33 ACS Paragon Plus Environment


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passivation (co-ordination with Pb ions) of the perovskite surface layer, as given in Figure 18c. A Lewis adduct of MAPbI3 and π-conjugated Lewis base existed by the interaction of Pb and π-conjugated base, where organic n-type π-conjugated molecules can extract the electrons generated from MAPbI3 and then transport them into the device cathode. The solar cell device fallow as ITO/PTAA/MAPbI3/IDIC/C60/BCP/Cu (where IDIC abbreviated as indacenodithiophene end-capped with 1.1-dicyanomethylene-3-indanone and which working as a hole transporting layer), which show the PCE of 19.5% with area of 7.5 mm2. However, similar PCBM passivated solar cell were also reported, but the PCEs limited to 17%18%.99,100 Table 4. Photovoltaic parameters extracted from the illuminated J–V curves (reverse scanned) of monocrystalline solar cells with various MAPbBr3 film thicknesses. Reproduced with permission.96 Copyright 2016, Wiley-VCH.

Device Structure ITO/perovskite/Au

Film thickness (µm) 1 4 7 12 60 FTO/TiO2/perovskite/Au 1

Voc (V) 1.25 1.24 1.11 1.03 0.94 1.36

Jsc (mAcm-2) 7.39 7.42 7.19 7.09 2.27 6.96

(b) (a)


FF 0.59 0.58 0.46 0.39 0.31 0.69

PCE (%) 5.49 5.37 3.70 2.82 0.65 6.53

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(c) Figure 18. (a) Band alignment of i) ITO/MAPbBr3/Au and ii) FTO/TiO2/MAPbBr3/Au, iii) FTO/TiO2 based monocrystalline solar cells; (b) Solar cell device fabricated using thin single-crystal of MAPbI3 (c) i) Schematic of the interaction of the π-conjugated Lewis base and Pb, ii) diagram of formation of a dative covalent bond between two atoms and iii) passivation of trap states. Reproduced with permission.96 Copyright 2016, Wiley-VCH. Reproduced with permission.97 Copyright 2017, Nature Publishing Group. Reproduced with permission.98Copyright 2017, Wiley-VCH.

The various photodetector (UV to IR, X-ray and γ-ray) devices were fabricated using different single crystals of organic-inorganic (MAPbI3,40,102,103,108,111,112 MAPbBr3101,109 MAPbCl3,39 FAPbI371,113 and MAPbBr3−xClx110 and MAPbI3−xBrx41) and all-inorganic (CsPbBr370 and Cs2AgBrBr6116) lead halide perovskite. Among all, the organic-inorganic single crystal photodetectors of MAPbI3 and mixed MAPbBr3-xClx perovskite exhibited high sensitivity detector and leading to narrow band spectra with less than 20 nm FWHMs under reverse bias (-1 V) of device the schematic illustration of mixed halide device and resulting narrow band spectra as depicted in Figure 19a. Huang and co-workers developed a vertical structured p–i–n photodetector devices using thin single crystal of MAPbBr3 and MAPbI3.101 However, these thin single crystals of both perovskite obtained using diffusion facilitated space-confined method. The performance of both thin single crystal photodetectors show 2.0 x 10−9 and 1.8 x 10−7 A cm−2 for MAPbBr3 and MAPbI3 devices at −0.3 V. Moreover, both devices are exhibited a high photoresponsivity, high specific detectivity, and high response 35 ACS Paragon Plus Environment


speed

under

ultra-low

dark

current.

The

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device

composition

are

ITO/PTAA/perovskite/C60/BCP/Cu, as depicted in Figure 19b. The layer of PTAA act as nonwetting in the crystal growth process, while C60 and BCP act as electron transport and hole-blocking layer, respectively. In addition, as seen in the literature, remarkable performance of solution processed perovskite photodetector devices developed by various research group.102-107 Especially, Huang and co-workers made significant report in the field of photovoltaic device either solar cell or photodetector (from UV to γ-ray ) using perovskite materials. However, Huang and co-workers were developed photodetectors devices using solution process perovskite, and are exhibited superior performance to detect from UV to near-IR region under applied low V, as depicted in Figure 19c.102 A hybrid perovskite/polymer

device

(ITO/PTAA/MAPbI3/PDPPTDTPT:PCBM/BCP/Cu)

(where

PDPPTDTPT is Poly {2,5-bis(2-hexyldecyl)-2,5-dihydropyrrolo[3,4-c]pyrrole-1,4-dione-3,6di(5-thiophen-2-yl)yl-alt-N-(2-ethylhexyl)-dithieno-[3,2-b:2,3-d]pyrrole-2,6-diyl}

exhibited

ultrafast response speed of 5 ns from UV (350 nm) to near-IR (1050 nm) region under low noise with bias ranging from −0.3 to 1.3 V. While the other one solution process photodetector of perovskite exhibited a sub-nanosecond response time with operation at zerobias.103Although, this device (ITO/PTAA/MAPbI3/C60/BCP/Cu) stands for the first time developed a low cost solution processed perovskite photodetector. Moreover, this device also performed under forward and reverse scanning between −0.3 and 1.6 V. The exhibited dark current density was 1.4 × 10−5 mA cm−2 under −0.3 V, which was low enough to resolve light as weak as a sub-picowatt per square centimetre. This may be occur that the C60 layer completely covered the perovskite layer and effectively reduced the current leakage. Liu et al.108 constructed a photodetector device for mass production by using thickness-controllable ultrathin perovskite wafers of MAPbI3 crystal. A series of thickness-controllable (150µm, 330µm, 670µm, and 1440µm) MAPbI3 perovskite wafers crystals grown via a proper 36 ACS Paragon Plus Environment

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geometry-regulated dynamic-flow reaction system. However, the fabricated photodetector devices of perovskite wafers single crystals exhibited much higher photocurrent response about 350 times higher than that of microcrystalline thin-film across the measurement range from 1 to 3 V. Briefly; the measured current response (illumination with an AM 1.5G solar simulator (100 mW cm−2) at a series of bias voltages: 1, 1.5, 2, 2.5, and 3 V) of both thin crystal and polycrystalline (constructed to comparison) photodetectors results are depicted in Figure 19d. When the light was turned on, the photocurrent of the single crystal wafer device rose to as high as 700µA at 2V bias (Figure 19c), while the increase of the microcrystalline thin film device was very limited to only 2µA (Figure 19d), which tells that about 350 times smaller. In addition, on a piece of thin single crystal perovskite fabricated using 100 photodetectors (Figure 19a) and demonstrated the feasibility of mass production of ICs on the perovskite wafer. Rao et al.109 were also constructed a photodetector device for narrow band response using thin film single crystal of MAPbBr3 perovskite. The extremely large area (120 cm2) of MAPbBr3 perovskite thin film (range of 0.1 to 0.8 mm) single crystals developed by using space limited inverse temperature crystallization (SLITC) method (Figure 9) directly on FTO glass. The photodetector devices (FTO/MAPbBr3/Au) based on such perovskite crystal film exhibited significant performance with linear response within the incident light power density range from 10−4 to 102 mW cm−2, wavelength selectivity (61.3 dB), and cut-off frequency (110 kHz) under low bias of −1 V. Moreover, the photodetector device made using 0.1 mm MAPbBr3 perovskite crystal exhibited broad light response range. The EQE wavelength of about 580 nm to short wavelength region, which can be regarded as a broadband photodetector. While increasing thickness diameter of perovskite film to 0.2 mm, the response to short-wavelength light radiation below 530 nm is decreased and an obvious peak at 544 nm observed. In addition, the photodetector devices of 0.4 and 0.8 mm perovskite crystal exhibit further declined weak response at short wavelength region, the device detail 37 ACS Paragon Plus Environment


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and its results depicted in Figure 20a. It was suggested that the 0.8 mm perovskite device exhibited high performance narrower band response and such high performance filterless narrowband perovskite photodetector can be potentially crucial for imaging, machine vision, optical communications, etc. applications. A self-photodetector device of all-inorganic single crystal under dark current at 0 V bias and white current at 10 mW cm-2 fabricated by sandwiching a high quality single crystal of CsPbBr3 between Pt and Au contacts, as presented Figure 20b. Under dark-current at 0 V bias exhibited 10 pA, which indicating significant result for photodetectors to achieve high signal-to-noise ratio and operational reliability, while under white light illumination, the zero-bias photocurrent increases by five orders of magnitude to ≈1µA. Moreover, suggested that the high photoresponse of the present CsPbBr3 photodetector enabled an ON/OFF ratio as high as 105 at zero bias, which is one of the highest for solution-processed self-biased photodetectors by the metal–semiconductor– metal structure, schematic diagrams presented in Figure 20b.

(a)

(c) (b)


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(d) Figure 19. (a) Schematic picture of device and its narrower band results from various single crystals of single halide and mixed halide perovskite. (b) Schematic illustration of the photodetector based on thin-film single crystal of perovskite with a vertical p–i–n structure. (c) Schematic illustration of hybrid perovskite/polymer photodetector. (d) i) Photograph of 100 photodetectors fabricated on an single crystal wafer, with each sensor consisting of a pair of interdigitated gold (Au) wire electrodes; ii) Light- and dark-current–voltage (I–V) curves of the photodetectors made of with single crystal wafer; iii) and iv) Photocurrent response measured (light intensity: 100 mW cm−2) to compare sensors made of the single crystal perovskite wafer and its thin film; v) and vi) Photoresponsivity of a detector made of perovskite single crystal wafer and thin film when the incident power densities changed from 0.33 to 1.11 mW cm−2; vii) and viii) EQE dependence on light irradiance for a photodetector made of single crystal perovskite wafer and perovskite thin film. Reproduced with permission.41 Copyright 2015, Nature Publishing Group. Reproduced with permission.101 Copyright 2017, Wiley-VCH. Reproduced with permission.102 Copyright 2017, The Royal Society of Chemistry. Reproduced with permission.108 Copyright 2017, Wiley-VCH.



(a)

(b) Figure 20. (a) i) and ii) Schematic of the device structure and its mechanism for narrowband photodetector; iii) Normalized external quantum efficiency (EQE) spectra of the laminar MAPbBr3 crystal photodetectors with different thicknesses of 0.1, 0.2, 0.4, and 0.8 mm under a bias of −1 V; iv) EQE spectra of 0.4 mm thick device under various biases of −1, −2, and −4 V. (b) Photodetector results; i) dark light I-V curves and ii) current stability measured under continuous illumination. Reproduced with permission70,109. Copyright 2017, Wiley-VCH.

Stoumpos et al.45 fabricated a device by using single crystal of CsPbBr3 for X-ray and γ-ray noise detection. The measurement was carried out by employing a positive bias of 450 V with illumination of unfiltered Ag source for about 5 minutes and a CZT detector. The preliminary results of photodetector significantly exhibited X-ray detect response. Wei et al.42 were constructed the devices for application of photodetector (UV-Vis) and X-ray detector, both the devices are made by using as grown 2 mm single crystal of MAPbBr3. The performance of UV-Vis photodetector device at reverse bias of -0.1 V exhibited a small dark40 ACS Paragon Plus Environment

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current density of 29 nA cm-2. Similarly, the device applied for X-ray detection under Amptek Mini-X tube with X-ray energy 50 keV and peak intensity 22 keV. The performance of device attenuated almost all of the X-rays within the energy range of the X-ray source used. The collection efficiency charge of device indicated up to 33-42% of UV-light and 16.4% of hard X-ray photons at a zero bias condition. Direct conversion of high-energy X-ray flux in charges show high sensitivity of 80 µCGy-1air cm–2 and a lowest detectable of 0.5 µCGy-1air cm–2, which indicating that the practical use of diagnostic rate much more larger than this detector. A high energy detector of γ-rays device fabricated using single crystal of CsPbBr3 by Dirin et al.67 The experiment was carried out under the single crystal cooling at 221K by applying 20 V bias. A high count rate could be detected using a

241

Am source

detector. While increasing the bias from 20 V to 40 V, notably shifts the photo peak to higher channels of the same multichannel analyzer and slightly improves the energy resolution. The schematic and fabrication device of CsPbBr3 with dimension 5x5x2 mm as depicted in Figure 21.

Figure 21. CsPbBr3 single crystal orientation in electronic measurements. The flux of visible light was directed from top to the larger facet shown (shown by green colour), whereas gamma-irradiation was directed from the side of one of the contacts (blue arrow). Reproduced with permission.67 Copyright 2016, American Chemical Society.

Huang and co-workers were made a significant report by constructing the γ –ray photodetector device using dopant mixed halide perovskite single crystal for the next generation of radiation detector.110 However, a high quality dopant single crystal of MAPbBr2.94Cl0.06 perovskite with different size grown via ITC method. This dopant single 41 ACS Paragon Plus Environment


crystal exhibited three fold improvement of mobility (560 cm2V-1s-1) and 10 time reduction of dark current as well as large µτ product value (1.8 x 10-2 cm2 V-1) than that of pure MAPbBr3 single crystals. A well-defined

137

Cs energy spectrum was obtained with the fabricated

devices of using MAPbBr2.94Cl0.06 single crystals (whereas made three different devices and named as I, II and II, which have only difference in crystal dimensions) under a small electric field of 1.8Vmm-1 at room temperature, as presented in Figure 22. Consequently, the obtained energy spectrum demonstrated a comparable or better resolution than that of a standard scintillator detector. The resolution of MAPbBr2.94Cl0.06 detectors is around 12%, while the best MAPbBr2.94Cl0.06 device has a resolution of 6.50% (Figure 22d). In comparison, the resolutions of full-energy peaks are 2.27%, and 7.51% for CZT and NaI(Tl), respectively (Figure 22e). Therefore, it tells that the perovskite is capable to obtaining a better resolution than that obtained through a typical NaI(Tl) scintillator detector while being much more economical than standard semiconductor detectors used in industry. In addition, γ-ray and Xray energy-resolved photodetector have also been demonstrated successfully using similar single crystals of MAPbI3 as well as with other FAPbI3 and Cs0.1FA0.9PbI2.8Br0.2.44,111,112 Despite its great success, the lead halide perovskites has tremendous scope to use in various application. Due to toxicity of core component Pb lugging back, which causes several brainrelated symptoms such as memory problems and intellectual disability.113 Therefore, to overcome the drawback of Pb, development of Pb free X-ray photodetector using single crystal of Cs2AgBiBr6 recently came into the existance.114 The high average atomic number, adequate µτ product, low ionization energy and high resistivity together render Cs2AgBiBr6 a suitable semiconductor to directly convert X-rays into electrical signals. The fabricated device (Au/Cs2AgBiBr6/Au) exhibited a high sensitivity of 105 µCGyair−1 cm−2 and a low detection limit of 59.7 nGyair s−1 under an external bias of 5 V. It is suggested that the obtained value being much lower than the best MAPbBr3 detector (2.1 x 104 µCGyair−1cm–2 42 ACS Paragon Plus Environment

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to 8 keV X-ray photons), and four times higher than that of α-Se detectors (20 µCGyair−1cm−2) operating at a much higher field of 10 Vµm−1.

Figure 22. (a) Top view of the guard ring electrode side of the detector. (b) Top view of the anode side of the detector. (c) Side view of a MAPbBr2.94Cl0.06 single-crystal detector, and electrode sides were encapsulated with epoxy. (d) Enlarged photopeak region of the 137Cs energy spectrum obtained by device II and MAPbBr3 single-crystal detectors. FWHM, full width at half maximum, and (e) 137Cs energy spectrum obtained by device I, CZT and NaI(Tl) detectors. Reproduced with permission.110 Copyright 2017, Nature Publishing Group.

7. Conclusions and future outlook In summary, we have presented a compressive description of perovskite crystal growth using various techniques and their key quantity of basic properties, such as carrier lifetime, carrier mobility, carrier diffusion length and trap-density, which are directly effect to optoelectronic application. Among all the various crystal growth techniques, faster growth rate of crystal showed by ITC method. Due to its faster growth rate phenomena of ITC method vast majority of crystals were reported. Best results of potential quantity reported by AVS method grown crystal of MAPbBr3, which indicating high quality of the crystal.42 However, many researchers are limited to grow only large size crystals, but there remain several factors that are not clearly understood, and large barriers still to overcome in terms of stability and toxicity for large-scale application. High quality with large size crystals 43 ACS Paragon Plus Environment


will not only cover the way to understand the intrinsic properties of these perovskite materials, but devices based on single crystals with different dimensions will also be an attractive research area. Recently, significant development of thin film single crystal of halide based perovskite materials by various techniques (brief explanation given in section 6) have been developed. These thin-film single crystal of perovskite exhibited high diffusion length, high µτ product and low trap-density, which are indicating that the thin film single crystals are free from grain boundaries and more stable. In addition, the fabricated devices of thin-film single crystals exhibited excellent performance in various photodetectors (UV to near-IR, X-ray and γ-ray) and solar cell devices owing to exist for mass production. However, the major effort of crystal growth (including thin-film single crystal) have been done with lead halide perovskite materials, while observe very less report with lead free crystals. The main component of Pb is highly toxic and required to replace the Pb with less or non-toxic metal. In addition, single crystal growth process in the toxic solvent, such as DMF, DMSO and GBL, which can easily penetrate into human body. Moreover, the volatile solvent can easily diffuse into atmosphere and it may cause global environmental pollution, which is difficult to solve due to its poor solubility in less toxic solvents. Therefore, it is significantly required to use of eco-friendly solvents for crystal growth and also required to develop crystals in solid state reactions. Direct application of grown crystals were limited to only few areas and it is required to explore into various applications.

Acknowledgements Authors are thankful to department of science & technology under major projects DST-UK (‘APEX II’) and DST-SERI for their financial support. Authors show their gratitude to all the researchers who contributed to the work cited in this article.


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For Table of Contents Use Only Recent

Advances

in

Halide-based

Perovskite

Crystals

and

Its

Optoelectronic Applications Ramavath Babu, Lingamallu Giribabu, and Surya Prakash Singh

Hybrid halide perovskite material demonstrated remarkable progress in the field of optoelectronic application. Recently, to investigate the key parameters of this materials were developed high quality and large size various single crystals using different methods. In addition, constructed devices of photodetector (UV to γ-ray) and solar cell using single crystal of perovskite exhibited superior performance than that of polycrystalline thin-film devices.


Recent Advances in Halide-Based Perovskite Crystals and Their

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