Crystal system: monoclinic
| a: | 8.7537 (±0.00019) |
| b: | 7.95502 (±0.00016) |
| c: | 19.5038 (±0.0005) |
| α: | 90° |
| β: | 93.806 (±0.002)° |
| γ: | 90° |
Starting materials: (S)-(−)-1-(1-naphthyl)ethylamine (>99%, Sigma Aldrich), lead bromide (PbBr2, 99.99%, TCI chemicals) , and hydrobromic acid (HBr) (48 wt% in H2O, >99.99%, Sigma Aldrich)
Product: [S-(−)-1-(1-naphthyl)ethylammonium]2PbBr4
Description: To grow S-NPB perovskite crystals, stoichiometric amounts of PbBr2 (90 mg, 0.24 mmol) and (S)-(−)-1- (1-naphthyl)ethylamine (78 µL, 0.48 mmol) were dissolved in aq. HBr (1.0 mL) and deionized water (2.4 mL) in a sealed vial at 95 °C. The hot solution was slowly cooled to room temperature (21 °C) over a period of 24 h in a water bath, resulting in the formation of colorless plate-like S-NPB single crystals.
Method: Differential Scanning Calorimetry
Description: DSC: Differential Scanning Calorimetry: DSC measurements were performed using a TA Discovery DSC instrument using various ramping rates and temperature ranges (as described in the main text) using a hermetically sealed aluminum pan and lid. Prior to experiments, the DSC setup was calibrated with metallic indium (melting temperature: 156.6 °C; enthalpy of melting: 28.71 J g−1), which upon repeating the experiment showed an acceptable temperature offset of 0.2 °C and melting enthalpy offset of 0.04%. Calibration and the above measurement were carried out at a ramp rate of 5 °C min−1. DSC analyses of crystalline S-NPB and rac-NPB perovskites were carried out by hermetically sealing corresponding crystals (≈5.0 mg) in aluminum pan/lid, and ramping temperature from 25 to 250 °C at a ramp rate of 5 °C min−1. For measurement of S-NPB and R-NPB glasses, samples were prepared by melting S-/R-NPB crystals (≈5.0 mg) in an open aluminum pan and quickly placing it on a metallic steel bench to quench to room temperature. After hermetic sealing, the glassy samples were exposed to a heating cycle with ramp rates of 5°C min−1 over a temperature range from 25 to 185 °C and heated isothermally at 185 °C for a minute, before cooling back to room temperature at ramp rates of 1, 5, and 20 °C min−1. Since the glass transition occurred over a temperature range, the Tg was determined using the midpoint halfheight method. The Tx, Tm, and Td temperatures were calculated using the intersection between the corresponding DSC peak onset with its horizontal baseline. For Tm, the onset temperature signifies the melting temperature of the sample under consideration, whereas the peak temperature corresponds to complete melting of the sample inside the apparatus. The enthalpy of crystallization and melting were calculated by measuring the area under the curve relating heat flow (W g−1)/ramp rate (°C s−1) and temperature. Thermogravimetric Analysis: TGA measurements were performed on a TA Q50 instrument using a 5 °C min−1 ramping rate from 25 to 300 °C under nitrogen gas flow (40 mL min−1) with samples (≈4.5 mg) of single crystals of S-NPB and rac-NPB perovskite. Glassy S-NPB perovskite sample (3.9 mg) for TGA measurement was prepared by scratching off the melt-quenched glass prepared on soda lime glass substrates
Starting materials: (S)-(−)-1-(1-naphthyl)ethylamine (>99%, Sigma Aldrich), lead bromide (PbBr2, 99.99%, TCI chemicals) , and hydrobromic acid (HBr) (48 wt% in H2O, >99.99%, Sigma Aldrich)
Product: [S-(−)-1-(1-naphthyl)ethylammonium]2PbBr4
Description: To grow S-NPB perovskite crystals, stoichiometric amounts of PbBr2 (90 mg, 0.24 mmol) and (S)-(−)-1- (1-naphthyl)ethylamine (78 µL, 0.48 mmol) were dissolved in aq. HBr (1.0 mL) and deionized water (2.4 mL) in a sealed vial at 95 °C. The hot solution was slowly cooled to room temperature (21 °C) over a period of 24 h in a water bath, resulting in the formation of colorless plate-like S-NPB single crystals.
Method: Differential Scanning Calorimetry
Description: DSC: Differential Scanning Calorimetry: DSC measurements were performed using a TA Discovery DSC instrument using various ramping rates and temperature ranges (as described in the main text) using a hermetically sealed aluminum pan and lid. Prior to experiments, the DSC setup was calibrated with metallic indium (melting temperature: 156.6 °C; enthalpy of melting: 28.71 J g−1), which upon repeating the experiment showed an acceptable temperature offset of 0.2 °C and melting enthalpy offset of 0.04%. Calibration and the above measurement were carried out at a ramp rate of 5 °C min−1. DSC analyses of crystalline S-NPB and rac-NPB perovskites were carried out by hermetically sealing corresponding crystals (≈5.0 mg) in aluminum pan/lid, and ramping temperature from 25 to 250 °C at a ramp rate of 5 °C min−1. For measurement of S-NPB and R-NPB glasses, samples were prepared by melting S-/R-NPB crystals (≈5.0 mg) in an open aluminum pan and quickly placing it on a metallic steel bench to quench to room temperature. After hermetic sealing, the glassy samples were exposed to a heating cycle with ramp rates of 5°C min−1 over a temperature range from 25 to 185 °C and heated isothermally at 185 °C for a minute, before cooling back to room temperature at ramp rates of 1, 5, and 20 °C min−1. Since the glass transition occurred over a temperature range, the Tg was determined using the midpoint halfheight method. The Tx, Tm, and Td temperatures were calculated using the intersection between the corresponding DSC peak onset with its horizontal baseline. For Tm, the onset temperature signifies the melting temperature of the sample under consideration, whereas the peak temperature corresponds to complete melting of the sample inside the apparatus. The enthalpy of crystallization and melting were calculated by measuring the area under the curve relating heat flow (W g−1)/ramp rate (°C s−1) and temperature. Thermogravimetric Analysis: TGA measurements were performed on a TA Q50 instrument using a 5 °C min−1 ramping rate from 25 to 300 °C under nitrogen gas flow (40 mL min−1) with samples (≈4.5 mg) of single crystals of S-NPB and rac-NPB perovskite. Glassy S-NPB perovskite sample (3.9 mg) for TGA measurement was prepared by scratching off the melt-quenched glass prepared on soda lime glass substrates
Starting materials: (S)-(−)-1-(1-naphthyl)ethylamine (>99%, Sigma Aldrich), lead bromide (PbBr2, 99.99%, TCI chemicals) , and hydrobromic acid (HBr) (48 wt% in H2O, >99.99%, Sigma Aldrich)
Product: [S-(−)-1-(1-naphthyl)ethylammonium]2PbBr4
Description: To grow S-NPB perovskite crystals, stoichiometric amounts of PbBr2 (90 mg, 0.24 mmol) and (S)-(−)-1- (1-naphthyl)ethylamine (78 µL, 0.48 mmol) were dissolved in aq. HBr (1.0 mL) and deionized water (2.4 mL) in a sealed vial at 95 °C. The hot solution was slowly cooled to room temperature (21 °C) over a period of 24 h in a water bath, resulting in the formation of colorless plate-like S-NPB single crystals.
Method: Differential Scanning Calorimetry
Description: DSC: Differential Scanning Calorimetry: DSC measurements were performed using a TA Discovery DSC instrument using various ramping rates and temperature ranges (as described in the main text) using a hermetically sealed aluminum pan and lid. Prior to experiments, the DSC setup was calibrated with metallic indium (melting temperature: 156.6 °C; enthalpy of melting: 28.71 J g−1), which upon repeating the experiment showed an acceptable temperature offset of 0.2 °C and melting enthalpy offset of 0.04%. Calibration and the above measurement were carried out at a ramp rate of 5 °C min−1. DSC analyses of crystalline S-NPB and rac-NPB perovskites were carried out by hermetically sealing corresponding crystals (≈5.0 mg) in aluminum pan/lid, and ramping temperature from 25 to 250 °C at a ramp rate of 5 °C min−1. For measurement of S-NPB and R-NPB glasses, samples were prepared by melting S-/R-NPB crystals (≈5.0 mg) in an open aluminum pan and quickly placing it on a metallic steel bench to quench to room temperature. After hermetic sealing, the glassy samples were exposed to a heating cycle with ramp rates of 5°C min−1 over a temperature range from 25 to 185 °C and heated isothermally at 185 °C for a minute, before cooling back to room temperature at ramp rates of 1, 5, and 20 °C min−1. Since the glass transition occurred over a temperature range, the Tg was determined using the midpoint halfheight method. The Tx, Tm, and Td temperatures were calculated using the intersection between the corresponding DSC peak onset with its horizontal baseline. For Tm, the onset temperature signifies the melting temperature of the sample under consideration, whereas the peak temperature corresponds to complete melting of the sample inside the apparatus. The enthalpy of crystallization and melting were calculated by measuring the area under the curve relating heat flow (W g−1)/ramp rate (°C s−1) and temperature. Thermogravimetric Analysis: TGA measurements were performed on a TA Q50 instrument using a 5 °C min−1 ramping rate from 25 to 300 °C under nitrogen gas flow (40 mL min−1) with samples (≈4.5 mg) of single crystals of S-NPB and rac-NPB perovskite. Glassy S-NPB perovskite sample (3.9 mg) for TGA measurement was prepared by scratching off the melt-quenched glass prepared on soda lime glass substrates
Starting materials: (S)-(−)-1-(1-naphthyl)ethylamine (>99%, Sigma Aldrich), lead bromide (PbBr2, 99.99%, TCI chemicals) , and hydrobromic acid (HBr) (48 wt% in H2O, >99.99%, Sigma Aldrich)
Product: [S-(−)-1-(1-naphthyl)ethylammonium]2PbBr4
Description: To grow S-NPB perovskite crystals, stoichiometric amounts of PbBr2 (90 mg, 0.24 mmol) and (S)-(−)-1- (1-naphthyl)ethylamine (78 µL, 0.48 mmol) were dissolved in aq. HBr (1.0 mL) and deionized water (2.4 mL) in a sealed vial at 95 °C. The hot solution was slowly cooled to room temperature (21 °C) over a period of 24 h in a water bath, resulting in the formation of colorless plate-like S-NPB single crystals.
Method: Differential Scanning Calorimetry
Description: DSC: Differential Scanning Calorimetry: DSC measurements were performed using a TA Discovery DSC instrument using various ramping rates and temperature ranges (as described in the main text) using a hermetically sealed aluminum pan and lid. Prior to experiments, the DSC setup was calibrated with metallic indium (melting temperature: 156.6 °C; enthalpy of melting: 28.71 J g−1), which upon repeating the experiment showed an acceptable temperature offset of 0.2 °C and melting enthalpy offset of 0.04%. Calibration and the above measurement were carried out at a ramp rate of 5 °C min−1. DSC analyses of crystalline S-NPB and rac-NPB perovskites were carried out by hermetically sealing corresponding crystals (≈5.0 mg) in aluminum pan/lid, and ramping temperature from 25 to 250 °C at a ramp rate of 5 °C min−1. For measurement of S-NPB and R-NPB glasses, samples were prepared by melting S-/R-NPB crystals (≈5.0 mg) in an open aluminum pan and quickly placing it on a metallic steel bench to quench to room temperature. After hermetic sealing, the glassy samples were exposed to a heating cycle with ramp rates of 5°C min−1 over a temperature range from 25 to 185 °C and heated isothermally at 185 °C for a minute, before cooling back to room temperature at ramp rates of 1, 5, and 20 °C min−1. Since the glass transition occurred over a temperature range, the Tg was determined using the midpoint halfheight method. The Tx, Tm, and Td temperatures were calculated using the intersection between the corresponding DSC peak onset with its horizontal baseline. For Tm, the onset temperature signifies the melting temperature of the sample under consideration, whereas the peak temperature corresponds to complete melting of the sample inside the apparatus. The enthalpy of crystallization and melting were calculated by measuring the area under the curve relating heat flow (W g−1)/ramp rate (°C s−1) and temperature. Thermogravimetric Analysis: TGA measurements were performed on a TA Q50 instrument using a 5 °C min−1 ramping rate from 25 to 300 °C under nitrogen gas flow (40 mL min−1) with samples (≈4.5 mg) of single crystals of S-NPB and rac-NPB perovskite. Glassy S-NPB perovskite sample (3.9 mg) for TGA measurement was prepared by scratching off the melt-quenched glass prepared on soda lime glass substrates
Starting materials: (S)-(−)-1-(1-naphthyl)ethylamine (>99%, Sigma Aldrich), lead bromide (PbBr2, 99.99%, TCI chemicals) , and hydrobromic acid (HBr) (48 wt% in H2O, >99.99%, Sigma Aldrich)
Product: [S-(−)-1-(1-naphthyl)ethylammonium]2PbBr4
Description: To grow S-NPB perovskite crystals, stoichiometric amounts of PbBr2 (90 mg, 0.24 mmol) and (S)-(−)-1- (1-naphthyl)ethylamine (78 µL, 0.48 mmol) were dissolved in aq. HBr (1.0 mL) and deionized water (2.4 mL) in a sealed vial at 95 °C. The hot solution was slowly cooled to room temperature (21 °C) over a period of 24 h in a water bath, resulting in the formation of colorless plate-like S-NPB single crystals.
Method: Thermogravimetric Analysis
Description: Thermogravimetric Analysis: TGA measurements were performed on a TA Q50 instrument using a 5 °C min−1 ramping rate from 25 to 300 °C under nitrogen gas flow (40 mL min−1) with samples (≈4.5 mg) of single crystals of S-NPB and rac-NPB perovskite. Glassy S-NPB perovskite sample (3.9 mg) for TGA measurement was prepared by scratching off the melt-quenched glass prepared on soda lime glass substrates.