Limits...
High-quality bulk hybrid perovskite single crystals within minutes by inverse temperature crystallization.

Saidaminov MI, Abdelhady AL, Murali B, Alarousu E, Burlakov VM, Peng W, Dursun I, Wang L, He Y, Maculan G, Goriely A, Wu T, Mohammed OF, Bakr OM - Nat Commun (2015)

Bottom Line: The process is based on our observation of the substantial decrease of MAPbX3 solubility, in certain solvents, at elevated temperatures.The crystals can be both size- and shape-controlled by manipulating the different crystallization parameters.The phenomenon of inverse or retrograde solubility and its correlated inverse temperature crystallization strategy present a major step forward for advancing the field on perovskite crystallization.

View Article: PubMed Central - PubMed

Affiliation: Division of Physical Sciences and Engineering, Solar and Photovoltaics Engineering Research Center, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Kingdom of Saudi Arabia.

ABSTRACT
Single crystals of methylammonium lead trihalide perovskites (MAPbX3; MA = CH3NH3(+), X = Br(-) or I(-)) have shown remarkably low trap density and charge transport properties; however, growth of such high-quality semiconductors is a time-consuming process. Here we present a rapid crystal growth process to obtain MAPbX3 single crystals, an order of magnitude faster than previous reports. The process is based on our observation of the substantial decrease of MAPbX3 solubility, in certain solvents, at elevated temperatures. The crystals can be both size- and shape-controlled by manipulating the different crystallization parameters. Despite the rapidity of the method, the grown crystals exhibit transport properties and trap densities comparable to the highest quality MAPbX3 reported to date. The phenomenon of inverse or retrograde solubility and its correlated inverse temperature crystallization strategy present a major step forward for advancing the field on perovskite crystallization.

No MeSH data available.


Related in: MedlinePlus

Crystal growth process and powder X-ray diffraction.(a) Schematic representation of the ITC apparatus in which the crystallization vial is immersed within a heating bath. The solution is heated from room temperature and kept at an elevated temperature (80 °C for MAPbBr3 and 110 °C for MAPbI3) to initiate the crystallization. (b,c) MAPbI3 and MAPbBr3 crystal growth at different time intervals. (d,e) Powder X-ray diffraction of ground MAPbBr3 and MAPbI3 crystals. Insets: pictures of the corresponding crystals grown within a non-constraining vessel geometry.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
getmorefigures.php?uid=PMC4544059&req=5

f1: Crystal growth process and powder X-ray diffraction.(a) Schematic representation of the ITC apparatus in which the crystallization vial is immersed within a heating bath. The solution is heated from room temperature and kept at an elevated temperature (80 °C for MAPbBr3 and 110 °C for MAPbI3) to initiate the crystallization. (b,c) MAPbI3 and MAPbBr3 crystal growth at different time intervals. (d,e) Powder X-ray diffraction of ground MAPbBr3 and MAPbI3 crystals. Insets: pictures of the corresponding crystals grown within a non-constraining vessel geometry.

Mentions: Consequently, DMF was chosen for MAPbBr3 ITC. Through studying the solubility of MAPbBr3 in DMF, we observed that it drops markedly from 0.80±0.05 g ml−1 at room temperature to 0.30±0.05 g ml−1 at 80 °C. This inverse solubility phenomenon was used to crystallize MAPbX3 rapidly in hot solutions as illustrated in Fig. 1a. Through balancing both temperature and concentration of precursors in DMF, only a few crystals were formed. For instance, by setting the temperature of the heating bath at 80 °C usually <5 crystals are formed in case of 1 M solution of PbBr2 and MABr (Supplementary Fig. 1). Inspired by this observation, we repeated the same procedure and studied different solvents that could lead to the same effect in MAPbI3. Unlike MAPbBr3, ITC of MAPbI3 was only possible in GBL solution, while no precipitates were observed in the case of DMF or DMSO.


High-quality bulk hybrid perovskite single crystals within minutes by inverse temperature crystallization.

Saidaminov MI, Abdelhady AL, Murali B, Alarousu E, Burlakov VM, Peng W, Dursun I, Wang L, He Y, Maculan G, Goriely A, Wu T, Mohammed OF, Bakr OM - Nat Commun (2015)

Crystal growth process and powder X-ray diffraction.(a) Schematic representation of the ITC apparatus in which the crystallization vial is immersed within a heating bath. The solution is heated from room temperature and kept at an elevated temperature (80 °C for MAPbBr3 and 110 °C for MAPbI3) to initiate the crystallization. (b,c) MAPbI3 and MAPbBr3 crystal growth at different time intervals. (d,e) Powder X-ray diffraction of ground MAPbBr3 and MAPbI3 crystals. Insets: pictures of the corresponding crystals grown within a non-constraining vessel geometry.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4544059&req=5

f1: Crystal growth process and powder X-ray diffraction.(a) Schematic representation of the ITC apparatus in which the crystallization vial is immersed within a heating bath. The solution is heated from room temperature and kept at an elevated temperature (80 °C for MAPbBr3 and 110 °C for MAPbI3) to initiate the crystallization. (b,c) MAPbI3 and MAPbBr3 crystal growth at different time intervals. (d,e) Powder X-ray diffraction of ground MAPbBr3 and MAPbI3 crystals. Insets: pictures of the corresponding crystals grown within a non-constraining vessel geometry.
Mentions: Consequently, DMF was chosen for MAPbBr3 ITC. Through studying the solubility of MAPbBr3 in DMF, we observed that it drops markedly from 0.80±0.05 g ml−1 at room temperature to 0.30±0.05 g ml−1 at 80 °C. This inverse solubility phenomenon was used to crystallize MAPbX3 rapidly in hot solutions as illustrated in Fig. 1a. Through balancing both temperature and concentration of precursors in DMF, only a few crystals were formed. For instance, by setting the temperature of the heating bath at 80 °C usually <5 crystals are formed in case of 1 M solution of PbBr2 and MABr (Supplementary Fig. 1). Inspired by this observation, we repeated the same procedure and studied different solvents that could lead to the same effect in MAPbI3. Unlike MAPbBr3, ITC of MAPbI3 was only possible in GBL solution, while no precipitates were observed in the case of DMF or DMSO.

Bottom Line: The process is based on our observation of the substantial decrease of MAPbX3 solubility, in certain solvents, at elevated temperatures.The crystals can be both size- and shape-controlled by manipulating the different crystallization parameters.The phenomenon of inverse or retrograde solubility and its correlated inverse temperature crystallization strategy present a major step forward for advancing the field on perovskite crystallization.

View Article: PubMed Central - PubMed

Affiliation: Division of Physical Sciences and Engineering, Solar and Photovoltaics Engineering Research Center, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Kingdom of Saudi Arabia.

ABSTRACT
Single crystals of methylammonium lead trihalide perovskites (MAPbX3; MA = CH3NH3(+), X = Br(-) or I(-)) have shown remarkably low trap density and charge transport properties; however, growth of such high-quality semiconductors is a time-consuming process. Here we present a rapid crystal growth process to obtain MAPbX3 single crystals, an order of magnitude faster than previous reports. The process is based on our observation of the substantial decrease of MAPbX3 solubility, in certain solvents, at elevated temperatures. The crystals can be both size- and shape-controlled by manipulating the different crystallization parameters. Despite the rapidity of the method, the grown crystals exhibit transport properties and trap densities comparable to the highest quality MAPbX3 reported to date. The phenomenon of inverse or retrograde solubility and its correlated inverse temperature crystallization strategy present a major step forward for advancing the field on perovskite crystallization.

No MeSH data available.


Related in: MedlinePlus