LETTERS PUBLISHED ONLINE: 16 MARCH 2014 | DOI: 10.1038/NMAT3911
Low-temperature solution-processed wavelength-tunable perovskites for lasing Guichuan Xing1†, Nripan Mathews2,3,4*†, Swee Sien Lim1,3, Natalia Yantara2,3, Xinfeng Liu1, Dharani Sabba2,3, Michael Grätzel3,5, Subodh Mhaisalkar2,3 and Tze Chien Sum1* Low-temperature solution-processed materials that show optical gain and can be embedded into a wide range of cavity resonators are attractive for the realization of on-chip coherent light sources. Organic semiconductors and colloidal quantum dots are considered the main candidates for this application. However, stumbling blocks in organic lasing1–4 include intrinsic losses from bimolecular annihilation and the conflicting requirements of high charge carrier mobility and large stimulated emission; whereas challenges pertaining to Auger losses and charge transport in quantum dots5–7 still remain. Herein, we reveal that solution-processed organic–inorganic halide perovskites (CH3 NH3 PbX3 where X = Cl, Br, I), which demonstrated huge potential in photovoltaics8–11 , also have promising optical gain. Their ultra-stable amplified spontaneous emission at strikingly low thresholds stems from their large absorption coefficients, ultralow bulk defect densities and slow Auger recombination. Straightforward visible spectral tunability (390–790 nm) is demonstrated. Importantly, in view of their balanced ambipolar charge transport characteristics8 , these materials may show electrically driven lasing. Organic–inorganic halide perovskites have recently emerged as a new class of photovoltaic materials with high efficiencies driven by the large absorption coefficients and long-range balanced electron and hole transport lengths8–11 . Surprisingly, we found that they also exhibit excellent coherent light emission properties. Figure 1a shows the transition from spontaneous emission (SE) to amplified spontaneous emission (ASE) with increasing pump fluence in a 65-nm-thick CH3 NH3 PbI3 film spin-coated on a quartz substrate. At low pump levels, the broad SE (with full width at half maximum (FWHM) ∼50 nm, Fig. 1b) from CH3 NH3 PbI3 increases linearly with increasing pump fluence. Correspondingly, the average transient photoluminescence (PL) lifetimes (τPL ) progressively decrease (Fig. 1b). Above the threshold fluence (12 ± 2 µJ cm−2 ; Fig. 1c), the emission intensity increases superlinearly, with τPL dramatically shortened owing to the occurrence of a new short lifetime (100 ps for carrier diffusion through a few tens of nanometres of the material8 ; and multi-particle loss mechanisms (such as bimolecular recombination in organic thin films or Auger recombination in QDs; refs 1–7). Following photo-excitation across the CH3 NH3 PbI3 bandgap (at low pump fluence where Auger recombination is not dominant), the excited charge carriers could either relax through bandedge emission or trap-mediated non-radiative pathways. The former gives rise to SE with a lifetime (τ0 ) of 4.5 ± 0.3 ns (Fig. 1b). An estimate of the bulk and surface trap densities can be made under these conditions where trap state recombination is much slower than bandedge radiative recombination. The photogenerated charge carrier density (nC (t)) after photoexcitation can be described with a set of differential equations (Supplementary Information). The model reveals the presence of two types of trap in these CH3 NH3 PbI3 thin films, with the bulk (surface) traps exhibiting fast (slow) trapping times8,21,22 . The bulk trap density is nFTP ∼ 5 × 1016 cm−3 whereas the surface trap density is nSTP ∼ 1.6 × 1017 cm−3 . The trap densities measured in CH3 NH3 PbI3 are comparable to defect densities in highly ordered organic crystals (1015 –1018 cm−3 )23 and superior to those of solutionprocessed organic thin films (1019 cm−3 )24 . Solution-deposited, high-temperature annealed Cu–In–Ga–S/Se (CIGS) chalcogenide layers25 also exhibit comparable defect densities to that reported here (1016 cm−3 ). These low bulk defect densities in perovskite are also consistent with the high solar cell efficiencies in this material8–11 . To examine the effects of the more prevalent surface traps on the carrier dynamics and ASE, PL measurements on bare CH3 NH3 PbI3 were compared against CH3 NH3 PbI3 /([6,6]-phenylC61-butyric acid methyl ester (PCBM), C60 ) bilayers to mimic the presence of infinite interfacial electron trap states. Selective excitation of the CH3 NH3 PbI3 layer (∼65 nm thick for both cases) was performed with 600 nm laser pulses. The presence of the PCBM 2
layer (∼45 nm) is expected to severely quench the SE from the CH3 NH3 PbI3 layer; see Fig. 2a for the PL spectra and Fig. 2b for the PL decay transients. Such efficient PL quenching originates from the long-range electron diffusion in the CH3 NH3 PbI3 film, where the diffusion-limited electron trapping time by the surface states can be estimated to be ∼0.40 ns (ref. 8). Surprisingly, under high pump fluence excitation, the ASE is impervious to the presence of the PCBM layer, which acts as a perfect electron quencher. Figure 2b clearly shows that the carrier avalanche proceeds at a much faster timescale than the carrier trapping at the surface states. Thus the surface states will not affect the ASE processes, only the fast bulk traps. Indeed, the ASE threshold fluence for the CH3 NH3 PbI3 /PCBM film is measured to be 10 ± 2 µJ cm−2 (Fig. 2c). This value is slightly smaller than that of the bare CH3 NH3 PbI3 film (12 ± 2 µJ cm−2 ) because of the better light confinement and propagation due to the presence of the PCBM cladding layer which improves gain buildup (Supplementary Information). Remarkably, ASE can also be observed in functional photovoltaic devices (η = 11.4%; Device structure: FTO/TiO2 compact layer/ TiO2 mesoporous layer/ CH3 NH3 PbI3 / Spiro-OMeTAD/ Au) with optical excitation; see Supplementary Information. The presence of the Spiro-OMeTAD layer, which acts as a perfect hole quencher, has no effect on the ASE from CH3 NH3 PbI3 —further exemplifying its exceptional gain properties. Although a low bulk defect density is favourable for obtaining reduced ASE thresholds, a critical criterion for achieving ASE is suppressed multi-particle non-radiative recombination rates (for example, bimolecular recombination noted in organics or Auger recombination in inorganic semiconductors). Bimolecular recombination (which is a limiting process in organic lasing) has been reported to be extremely low in CH3 NH3 PbI3 —defying the Langevin recombination limit by at least four orders of magnitude17 . These low bi-molecular charge recombination constants are consistent with our findings of low bulk defect densities as discussed earlier. The Auger recombination process in perovskite, which manifests under high pump fluence (nonlinear regime), typically yields Auger lifetimes (τ Auger ) from a few ps to ns, depending on the photo-generated charge carrier density6 . The Auger recombination in CH3 NH3 PbI3 is efficient (τAuger ∼ 300 ps) compared with SE
NATURE MATERIALS | ADVANCE ONLINE PUBLICATION | www.nature.com/naturematerials
© 2014 Macmillan Publishers Limited. All rights reserved.
NATURE MATERIALS DOI: 10.1038/NMAT3911
LETTERS
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Figure 2 | Effects of surface/interfacial traps on the coherent light emission. a, Time-integrated PL spectra of CH3 NH3 PbI3 (black) and CH3 NH3 PbI3 /PCBM (red). b, Time-resolved PL (TRPL) decay transients for quartz/CH3 NH3 PbI3 (65 nm) (black, ∼1.3 µJ cm−2 ) and quartz/CH3 NH3 PbI3 (65 nm)/PCBM (red, ∼1.3 µJ cm−2 ; blue, ∼17 µJ cm−2 ) films in vacuum following excitation at 600 nm (1 kHz, 150 fs). Through modifying the surface/interfacial trap density, these measurements reveal that, whereas SE is strongly quenched by the surface/interfacial traps, ASE—which occurs on a much faster timescale—could effectively compete with these carrier trapping processes. The solid lines in b are the single-exponential fits of the PL decay transients. c, The pump fluence-dependent PL spectra and PL intensity (inset) of quartz/CH3 NH3 PbI3 (65 nm)/PCBM film. In the inset, the black and red lines represent the linear fits to experimental data in the two linear regimes of SE and ASE, respectively.
(4.5 ± 0.3 ns) because of the long-range electron-hole diffusion lengths within them8 . However, the timescale for the occurrence of ASE (
Low-temperature solution-processed wavelength-tunable perovskites for lasing Guichuan Xing1†, Nripan Mathews2,3,4*†, Swee Sien Lim1,3, Natalia Yantara2,3, Xinfeng Liu1, Dharani Sabba2,3, Michael Grätzel3,5, Subodh Mhaisalkar2,3 and Tze Chien Sum1* Low-temperature solution-processed materials that show optical gain and can be embedded into a wide range of cavity resonators are attractive for the realization of on-chip coherent light sources. Organic semiconductors and colloidal quantum dots are considered the main candidates for this application. However, stumbling blocks in organic lasing1–4 include intrinsic losses from bimolecular annihilation and the conflicting requirements of high charge carrier mobility and large stimulated emission; whereas challenges pertaining to Auger losses and charge transport in quantum dots5–7 still remain. Herein, we reveal that solution-processed organic–inorganic halide perovskites (CH3 NH3 PbX3 where X = Cl, Br, I), which demonstrated huge potential in photovoltaics8–11 , also have promising optical gain. Their ultra-stable amplified spontaneous emission at strikingly low thresholds stems from their large absorption coefficients, ultralow bulk defect densities and slow Auger recombination. Straightforward visible spectral tunability (390–790 nm) is demonstrated. Importantly, in view of their balanced ambipolar charge transport characteristics8 , these materials may show electrically driven lasing. Organic–inorganic halide perovskites have recently emerged as a new class of photovoltaic materials with high efficiencies driven by the large absorption coefficients and long-range balanced electron and hole transport lengths8–11 . Surprisingly, we found that they also exhibit excellent coherent light emission properties. Figure 1a shows the transition from spontaneous emission (SE) to amplified spontaneous emission (ASE) with increasing pump fluence in a 65-nm-thick CH3 NH3 PbI3 film spin-coated on a quartz substrate. At low pump levels, the broad SE (with full width at half maximum (FWHM) ∼50 nm, Fig. 1b) from CH3 NH3 PbI3 increases linearly with increasing pump fluence. Correspondingly, the average transient photoluminescence (PL) lifetimes (τPL ) progressively decrease (Fig. 1b). Above the threshold fluence (12 ± 2 µJ cm−2 ; Fig. 1c), the emission intensity increases superlinearly, with τPL dramatically shortened owing to the occurrence of a new short lifetime (100 ps for carrier diffusion through a few tens of nanometres of the material8 ; and multi-particle loss mechanisms (such as bimolecular recombination in organic thin films or Auger recombination in QDs; refs 1–7). Following photo-excitation across the CH3 NH3 PbI3 bandgap (at low pump fluence where Auger recombination is not dominant), the excited charge carriers could either relax through bandedge emission or trap-mediated non-radiative pathways. The former gives rise to SE with a lifetime (τ0 ) of 4.5 ± 0.3 ns (Fig. 1b). An estimate of the bulk and surface trap densities can be made under these conditions where trap state recombination is much slower than bandedge radiative recombination. The photogenerated charge carrier density (nC (t)) after photoexcitation can be described with a set of differential equations (Supplementary Information). The model reveals the presence of two types of trap in these CH3 NH3 PbI3 thin films, with the bulk (surface) traps exhibiting fast (slow) trapping times8,21,22 . The bulk trap density is nFTP ∼ 5 × 1016 cm−3 whereas the surface trap density is nSTP ∼ 1.6 × 1017 cm−3 . The trap densities measured in CH3 NH3 PbI3 are comparable to defect densities in highly ordered organic crystals (1015 –1018 cm−3 )23 and superior to those of solutionprocessed organic thin films (1019 cm−3 )24 . Solution-deposited, high-temperature annealed Cu–In–Ga–S/Se (CIGS) chalcogenide layers25 also exhibit comparable defect densities to that reported here (1016 cm−3 ). These low bulk defect densities in perovskite are also consistent with the high solar cell efficiencies in this material8–11 . To examine the effects of the more prevalent surface traps on the carrier dynamics and ASE, PL measurements on bare CH3 NH3 PbI3 were compared against CH3 NH3 PbI3 /([6,6]-phenylC61-butyric acid methyl ester (PCBM), C60 ) bilayers to mimic the presence of infinite interfacial electron trap states. Selective excitation of the CH3 NH3 PbI3 layer (∼65 nm thick for both cases) was performed with 600 nm laser pulses. The presence of the PCBM 2
layer (∼45 nm) is expected to severely quench the SE from the CH3 NH3 PbI3 layer; see Fig. 2a for the PL spectra and Fig. 2b for the PL decay transients. Such efficient PL quenching originates from the long-range electron diffusion in the CH3 NH3 PbI3 film, where the diffusion-limited electron trapping time by the surface states can be estimated to be ∼0.40 ns (ref. 8). Surprisingly, under high pump fluence excitation, the ASE is impervious to the presence of the PCBM layer, which acts as a perfect electron quencher. Figure 2b clearly shows that the carrier avalanche proceeds at a much faster timescale than the carrier trapping at the surface states. Thus the surface states will not affect the ASE processes, only the fast bulk traps. Indeed, the ASE threshold fluence for the CH3 NH3 PbI3 /PCBM film is measured to be 10 ± 2 µJ cm−2 (Fig. 2c). This value is slightly smaller than that of the bare CH3 NH3 PbI3 film (12 ± 2 µJ cm−2 ) because of the better light confinement and propagation due to the presence of the PCBM cladding layer which improves gain buildup (Supplementary Information). Remarkably, ASE can also be observed in functional photovoltaic devices (η = 11.4%; Device structure: FTO/TiO2 compact layer/ TiO2 mesoporous layer/ CH3 NH3 PbI3 / Spiro-OMeTAD/ Au) with optical excitation; see Supplementary Information. The presence of the Spiro-OMeTAD layer, which acts as a perfect hole quencher, has no effect on the ASE from CH3 NH3 PbI3 —further exemplifying its exceptional gain properties. Although a low bulk defect density is favourable for obtaining reduced ASE thresholds, a critical criterion for achieving ASE is suppressed multi-particle non-radiative recombination rates (for example, bimolecular recombination noted in organics or Auger recombination in inorganic semiconductors). Bimolecular recombination (which is a limiting process in organic lasing) has been reported to be extremely low in CH3 NH3 PbI3 —defying the Langevin recombination limit by at least four orders of magnitude17 . These low bi-molecular charge recombination constants are consistent with our findings of low bulk defect densities as discussed earlier. The Auger recombination process in perovskite, which manifests under high pump fluence (nonlinear regime), typically yields Auger lifetimes (τ Auger ) from a few ps to ns, depending on the photo-generated charge carrier density6 . The Auger recombination in CH3 NH3 PbI3 is efficient (τAuger ∼ 300 ps) compared with SE
NATURE MATERIALS | ADVANCE ONLINE PUBLICATION | www.nature.com/naturematerials
© 2014 Macmillan Publishers Limited. All rights reserved.
NATURE MATERIALS DOI: 10.1038/NMAT3911
LETTERS
PL intensity (a.u.)
a
700
750 800 Wavelength (nm)
PL intensity (a.u.)
b
850
0.01
0.1
c
1 Time (ns)
10
PL intensity (a.u.)
Increasing pump fluence
PL intensity (a.u.)
CH3NH3Pbl3/PCBM
ASE
Pth = 10 ± 2 µJ cm−2
2
750
4 6 8 10 Pump fluence (µJ cm−2)
800 850 Wavelength (nm)
900
12
950
Figure 2 | Effects of surface/interfacial traps on the coherent light emission. a, Time-integrated PL spectra of CH3 NH3 PbI3 (black) and CH3 NH3 PbI3 /PCBM (red). b, Time-resolved PL (TRPL) decay transients for quartz/CH3 NH3 PbI3 (65 nm) (black, ∼1.3 µJ cm−2 ) and quartz/CH3 NH3 PbI3 (65 nm)/PCBM (red, ∼1.3 µJ cm−2 ; blue, ∼17 µJ cm−2 ) films in vacuum following excitation at 600 nm (1 kHz, 150 fs). Through modifying the surface/interfacial trap density, these measurements reveal that, whereas SE is strongly quenched by the surface/interfacial traps, ASE—which occurs on a much faster timescale—could effectively compete with these carrier trapping processes. The solid lines in b are the single-exponential fits of the PL decay transients. c, The pump fluence-dependent PL spectra and PL intensity (inset) of quartz/CH3 NH3 PbI3 (65 nm)/PCBM film. In the inset, the black and red lines represent the linear fits to experimental data in the two linear regimes of SE and ASE, respectively.
(4.5 ± 0.3 ns) because of the long-range electron-hole diffusion lengths within them8 . However, the timescale for the occurrence of ASE (
