# Patent

## Title
Emission source and method of forming the same

## Abstract

In various embodiments, an emission source may be provided. The emission source may also include a gain medium including a halide semiconductor material. The emission source may further include a pump source configured to provide energy to the gain medium. The halide semiconductor material may include a lead-free perovskite material.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part application of U.S. patent application Ser. No. 14/484,927 filed Sep. 12, 2014, which in turn claims the benefit of priority of US application No. 61/876,940 filed Sep. 12, 2013, the contents thereof being hereby incorporated by reference in their entirety for all purposes. This application also claims the benefit of priority of Singapore application No. 10201508060R filed Sep. 28, 2015, the contents thereof being hereby incorporated by reference in their entirety for all purposes.


TECHNICAL FIELD
Various aspects of this disclosure relate to emission sources and methods of forming the same.
BACKGROUND
A laser (acronym for light amplification by stimulated emission of radiation) emits coherent light through a process of optical amplification via the stimulated emission of electromagnetic radiation. Lasers or coherent light sources have many important applications which form the cornerstones of our modern society. These range from fast information processing and telecommunications; optical data storage; bio-imaging; medical diagnostic and phototherapy to scientific research and defense applications. The demands for such applications continue to grow with Mankind's relentless pursuit of sustainable growth.
The heart of a laser is its gain medium—a material that makes light stronger or permits optical amplification to occur. Optical amplification, also known as gain occurs when the gain material transfers part of its energy to light and makes the light more intense and in phase. Typical gain media include crystals (e.g., neodymium-doped yttrium aluminum garnet (Nd:YAG), titanium doped aluminum oxide (Ti:Sapphire) and neodymium-doped yttrium orthovanadate (Nd:YVO4) etc.) and high quality semiconductors (e.g. gallium arsenide (GaAs) and aluminum gallium arsenide (AlxGa(1-x)As) etc). These gain media typically operate in the infrared (IR) region of the electromagnetic spectrum. To obtain wavelengths in the ultraviolet (UV) or visible (VIS) region, wavelength conversion of IR photons with nonlinear crystals is performed. For example, in the modest hand-held laser pointer, the green light is generated indirectly—beginning with an AlGaAs laser diode (808 nm) pumping a NdYVO4 crystal to generate 1064 nm photons which are then frequency doubled by a KTP crystal to 532 nm. It is important to note the stringent conditions needed to prepare the high quality, crystalline gain materials, which involve costly high temperature growth and processing. For example, GaAs and AlxGa(1-x)As heterostructures require expensive elevated temperature and high vacuum growth techniques such as chemical vapor deposition (CVD) and molecular beam epitaxy (MBE).
SUMMARY
In various embodiments, an emission source may be provided. The emission source may also include a gain medium including a halide semiconductor material. The emission source may further include a pump source configured to provide energy to the gain medium. The halide semiconductor material may include a lead-free perovskite material.
In various embodiments, a method of forming an emission source may be provided. The method may include providing a gain medium including a halide semiconductor material. The method may also include providing a pump source configured to provide energy to the gain medium. The halide semiconductor material may include a lead-free perovskite material.



BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be better understood with reference to the detailed description when considered in conjunction with the non-limiting examples and the accompanying drawings, in which:
FIG. 1 is a schematic showing a cross-sectional side view of an emission source according to various embodiments.
FIG. 2A is a schematic showing a cross-sectional side view of an emission source according to various embodiments.
FIG. 2B shows a schematic showing a cross-sectional side view of an emission source according to various embodiments.
FIG. 2C shows a schematic showing a cross-sectional side view of an emission source according to various alternate embodiments.
FIG. 2D shows a schematic showing a perspective view an emission source according to various alternate embodiments.
FIG. 2E shows a schematic showing a cross-sectional side view of the emission source of FIG. 2D according to various embodiments.
FIG. 2F shows a schematic showing a cross-sectional side view of an emission source according to various other embodiments.
FIG. 2G shows a schematic showing a cross-sectional side view of an emission source according to various other embodiments.
FIG. 2H shows a schematic showing a cross-sectional side view of an emission source according to various other embodiments.
FIG. 2I shows a schematic showing a cross-sectional side view of an emission source according to various other embodiments.
FIG. 3 shows a schematic of a method of forming an emission source according to various embodiments.
FIG. 4A is a plot of a comparison of the amplified spontaneous emission (ASE) profile in relation to the absorption and spontaneous emission (SE)/photoluminescence profile for CH3NH3PbI3.
FIG. 4B shows a plot of a typical time resolved photoluminescence (TRPL) decay transients following photo-excitation with pump fluence below ( ̃10 μJ cm−2) and above ( ̃13 μJ cm−2) the ASE threshold (i.e., 12±2 μJ cm−2).
FIG. 4C is a streak camera image 400c of spectrum against time (collected over a time window of 460 ps) for below ASE threshold fluence.
FIG. 4D is a streak camera image 400d of spectrum against time (collected over a time window of 460 ps) for above ASE threshold fluence.
FIG. 5A is a plot showing the real part (n) and imaginary part or extinction coefficient (k) of the complex refractive index.
FIG. 5B shows a schematic of the of a gain medium under simulation conditions according to various embodiments.
FIG. 5C is a schematic showing intensity distributions in the y-z plane of structures of light polarized parallel to the structure surface.
FIG. 6A is a plot of pump fluence dependent photoluminescence (PL) spectra at 6K.
FIG. 6B is a plot of pump fluence dependent photoluminescence (PL) intensity at 6K.
FIG. 6C is a plot showing time resolved photoluminescence (TRPL) TRPL decay transients for quartz/CH3NH3PbI3 (65 nm) and quartz/CH3NH3PbI3 (65 nm)/PCBM (45 nm) films in vacuum following excitation at 600 nm (1 KHz, 150 fs,  ̃1 μJ cm−2).
FIG. 7A is a schematic of a solar cell according to various embodiments.
FIG. 7B is a plot showing the current density J (mA cm−2) under A 1.5 (100 mW/cm2) illumination.
FIG. 7C is a plot of photoluminescence (PL) intensity (arbitrary units) as a function of pump fluence (μJ cm−2) showing amplified spontaneous emission (ASE) threshold of the solar cell configuration.
FIG. 7D is a plot of the ASE spectrum.
FIG. 7E is a plot showing ASE photostability measured under ambient conditions of the device (Excited with 600 nm, 1 KHz, 50 fs laser pulses,  ̃20 μJ cm−2).
FIG. 7F is a photo showing a demonstration of green ASE from CH3NH3PbBr3 deposited on PET substrates pumped using two-photon absorption at 800 nm.
FIG. 8A is a plot showing steady-state photoluminescence (PL) emission spectra from a 65-nm-thick CH3NH3PbI3 film photoexcited using 600 nm, 150 fs and 1 kHz pump pulses with increasing pump fluence (per pulse).
FIG. 8B is a plot showing the corresponding time resolved photoluminescence (TRPL) intensity measured at 788±10 nm.
FIG. 8C is a plot full width at half maximum (FWHM) of the emission peak and average transient photoluminescence lifetime (τPL) as a function of the pump fluence.
FIG. 8D is a plot showing photoluminescence intensity as a function of pump fluence.
FIG. 9A is a plot showing photoluminescence quantum yield (PLQY) (in percentage or %) dependence on pump fluence (in μJ cm−2).
FIG. 9B is a plot showing room temperature variable stripe length (VSL) measurements of the CH3NH3PbI3 films and fitted using the respective methods used for solution processed colloidal quantum dots thin films.
FIG. 9C is a plot showing room temperature variable stripe length (VSL) measurements of the CH3NH3PbI3 films and fitted using the respective methods used for organic thin films.
FIG. 10A is a plot showing room temperature lasing from CH3NH3PbI3 single crystals from dropcasted films.
FIG. 10B is an optical micrograph of the crystal.
FIG. 10C is a plot showing the lasing data fitted to 5 peaks.
FIG. 10D is a plot showing photoluminescence (PL) intensity as a function of photon-generated exciton density within the low pump fluence range.
FIG. 11A is a plot showing the time-integrated PL spectra of CH3NH3PbI3 and CH3NH3PbI3/([6,6]-phenyl-C61-butyric acid methyl ester (PCBM).
FIG. 11B is a plot showing the time-resolved photoluminescence (TRPL) decay transients for quartz/CH3NH3PbI3 (about 1.3 μJ cm−2), quartz/CH3NH3PbI3/PCBM (about 1.3 μJ cm−2 and about 17 μJ cm−2) films in vacuum following excitation at 600 nm (1 kHz, 150 fs).
FIG. 11C is a plot of the pump fluence-dependent photoluminescence spectra of quartz/CH3NH3PbI3 (65 nm)/PCBM film.
FIG. 11D is a plot of the photoluminescence intensity of quartz/CH3NH3PbI3 (65 nm)/PCBM film.
FIG. 12A is a plot showing shot-dependent ASE intensity of the solution-processed CH3NH3PbI3 film with over 9×107 laser excitation shots at 600 nm (1 kHz, 50 fs,  ̃18 μJ cm−2) performed at room temperature.
FIG. 12B is a plot showing shot-dependent ASE intensity of the solution processed CH3NH3PbI3 and CH3NH3PbI3/PCBM films over 7×106 at 600 nm (1 KHz, 50 fs, 14 μJ/cm2) under room temperature.
FIG. 12C is a plot showing the PL spectrum at 10 K. The dotted lines are the deconvolved Gaussian peaks.
FIG. 12D is a plot showing wide wavelength tunability of ASE wavelengths from low-temperature solution-processed organic-inorganic halide semiconductor films fabricated by mixing the precursor solutions.
FIG. 13A is a plot showing the time-integrated PL spectra measured at 760±10 nm for quartz/CH3NH3PbI3 (65 nm), quartz/CH3NH3PbI3 (65 nm)/PCBM (indicated by 1304a), quartz/CH3NH3PbI3 (65 nm)/Spiro-OMeTAD films in vacuum following excitation at 600 nm (1 KHz, 150 fs, 1.3 μJ/cm2).
FIG. 13B is a plot showing TRPL decay transients measured at 760±10 nm for quartz/CH3NH3PbI3 (65 nm), quartz/CH3NH3PbI3 (65 nm)/PCBM, quartz/CH3NH3PbI3 (65 nm)/Spiro-OMeTAD films in vacuum following excitation at 600 nm (1 KHz, 150 fs, 1.3 μJ/cm2).
FIG. 13C is a plot of exciton diffusion length as a function of PL lifetime quenching ratios.
FIG. 14A is an illustration showing the absorbance and transmission spectra of CH3NH3PbI3, CH3NH3PbI3/PCBM, CH3NH3PbI3/Spiro-OMeTAD.
FIG. 14B is an illustration 1400b showing normalized bleaching kinetics for films in vacuum following excitation at 600 nm (1 KHz, 150 fs, 1.3 μJ/cm2).
FIG. 15A is an illustration of normalized bleaching kinetics in short time range showing the inter-valence band hot hole cooling for CH3NH3PbI3 (in vacuum) following excitation.
FIG. 15B is a schematic illustrating the hot hole cooling and charge recombination within CH3NH3PbI3 and charge separation at the CH3NH3PbI3/PCBM and CH3NH3PbI3/Spiro-OMeTAD interfaces.
FIG. 16 is a schematic of the energy levels of the heterojunctions and depiction of the exciton generation, diffusion and quenching processes in the respective bilayers.
FIG. 17 is a plot showing step profiles of the thickness of the CH3NH3PbI3, CH3NH3PbI3/PCBM and CH3NH3PbI3/Spiro-OMeTAD films.
FIG. 18 is a cross-sectional transmission electron microscopy image of a typical trilayer showing the clear interfaces between the perovskite and the electron and hole acceptor layers.
FIG. 19 is a plot of absorption coefficient of CH3NH3PbI3 as a function of wavelength.
FIG. 20 is a schematic showing 4 possible scenarios for the two peaks (480 nm and 760 nm) observed in the linear absorption and TA spectra.
FIG. 21 is a plot showing normalized probe wavelength dependent kinetics for CH3NH3PbI3 film in vacuum following excitation at 600 nm (0.7 μJ/cm2).
FIG. 22 is a plot showing normalized pump fluence dependent kinetics at 760 nm for CH3NH3PbI3 film vacuum following excitation at 600 nm.
FIG. 23 is an illustration showing pump fluence dependent dynamics for CH3NH3PbI3 and CH3NH3PbI3 in vacuum.
FIG. 24 is a plot showing pump fluence dependent relative PL quantum yield with 600 nm, 150 fs and 1 KHz laser pulse excitation.
FIG. 25 is a table showing relative photoluminescence (PL) quantum yield (çPL), PL decay time (τPL), TA decay time (τTA) and the estimated charge transfer time (τCT) from the TA results.
FIG. 26A is a plot of intensity (arbitrary units or a.u.) as a function of 2θ (degrees) showing the X-ray diffraction (XRD) spectra of CsSnI3 thin films doped with different concentration SnF2 according to various embodiments on quartz substrates.
FIG. 26B is a schematic showing a perovskite structure according to various embodiments.
FIG. 26C is a plot of emission intensity (arbitrary units or a.u.) as a function of wavelength (nanometers or nm) showing normalized emission at low pump fluence (open circles,  ̃1 μJ/cm2) and high pump fluence (solid lines,  ̃70 μJ/cm2) of CsSnI3 with different molar concentrations of SnF2 treatment according to various embodiments.
FIG. 26D is a plot of emission intensity (arbitrary units or a.u.) as a function of pump fluence (micro-joules per square centimeter or μJ/cm2) showing the variable fluence measurements which reveal the amplified spontaneous emission (ASE) thresholds of the SnF2-treated samples according to various embodiments.
FIG. 27A is a plot of photoluminescence (PL) intensity (arbitrary units or a.u.) as a function of wavelength (nanometers or nm) showing steady-state photoluminescence (PL) emission spectra from the CsSnI3 thin films (with various concentrations of SnF2 added) according to various embodiments.
FIG. 27B is a plot of photoluminescence intensity (arbitrary units or a.u.) as a function of time (picoseconds or ps) showing typical time-resolved photoluminescence (TRPL) decay transients of the CsSnI3 film with 20% SnF2 addition according to various embodiments following photo-excitation with pump fluence below and above the ASE threshold.
FIG. 28A is a plot of quantum yield (percent or %) as a function of pump fluence (micro-Joules per square centimeter or μJ/cm2) showing room-temperature photoluminescence quantum yield (PLQY) of 20% SnF2 treated CsSnI3 film according to various embodiments at different pump fluence.
FIG. 28B is a plot of photoluminescence (PL) intensity (arbitrary units or a.u.) as a function of strip length (centimeters or cm) showing variable strip length films according to various embodiments at a pump fluence of 20 μJ/cm2.
FIG. 29A is an image of an optical micrograph of a butterfly scale from the white part of the wing, while the inset shows the butterfly.
FIG. 29B are images of (i) scanning electron microscopy (SEM) showing lamellae (vertical structures) in the scale (left); and (ii) simulated electric field distribution at resonant cavity mode with embedded CsSnI3 (right) according to various embodiments.
FIG. 29C is a plot of emission intensity (arbitrary units or a.u.) as a function of wavelength (nanometers or nm) showing a comparison of the photoluminescence, amplified spontaneous emission (ASE), and single mode lasing of CsSnI3 (20% SnF2) according to various embodiments.
FIG. 29D is a two-dimensional pseudo-colour plot of pump fluence (micro-Joules per square centimeter or μJ/cm2) as a function of wavelength (nanometer or nm) showing the single model lasing emission spectra from the butterfly wing embedded with 20% SnF2 doped CsSnI3 according to various embodiments as a function of pump fluence.
FIG. 30A is a plot of intensity (arbitrary units or a.u.) as a function of wavelength (nanometers or nm) showing the measured white light scattering spectrum from white area of the butterfly wing according to various embodiments.
FIG. 30B is a plot of intensity (arbitrary units or a.u.) as a function of wavelength (nanometers or nm) showing the stimulated scattering spectrum with the finite-difference time-domain (FDTD) method according to various embodiments.
FIG. 31A is a plot of photoluminescence (PL) intensity (arbitrary units or a.u.) as a function of time (nanoseconds or ns) showing photoluminescence decay transients of 20% SnF2-added CsSnI3 film according to various embodiments with varying pump fluence over the entire band emission range.
FIG. 31B is a plot of (i) initial photoluminescence intensity (IPL[t=0]) (arbitrary units or a.u.) as a function of pump fluence (micro-Joules per square centimeter or μJ/cm2) showing pump fluence dependence of the initial time photoluminescence (PL) intensity of the film according to various embodiments; and (ii) lifetime (nanoseconds or ns) as a function of pump fluence (micro-Joules per square centimeter or μJ/cm2) showing the pump fluence dependence of photoluminescence lifetime of the film according to various embodiments.
FIG. 32A is a plot of photoluminescence (PL) intensity (arbitrary units or a.u.) as a function of time (nanoseconds or ns) showing the transient photoluminescence (TRPL) decay of CsSnI3 films with SnF2 addition (integrated over the spectrum) following 650 nm pulses (1 KHz, 50 fs,  ̃4 μJ/cm2) excitation at room temperature according to various embodiments. Solid lines represent fits with first and second order decay functions.
FIG. 32B is a table showing the charge-carrier decay rates of CsSnI3 with SnF2 addition in different concentration according to various embodiments.
FIG. 33A is a plot of wavelength (nanometers or nm) as a function of time (picoseconds or ps) showing a two dimensional (2D) transient absorption (TA) image in short time scale according to various embodiments.
FIG. 33B is a plot of normalized change in absorption ΔA (arbitrary units or a.u.) as a function of delay time (picoseconds or ps) showing photobleaching (PB) dynamics at about 850 nm and about 950 nm as indicated to illustrate the hot carrier cooling process according to various embodiments.
FIG. 33C is a plot of change in absorption ΔA (arbitrary units or a.u.) as a function of delay time (picoseconds or ps) showing the pump fluence dependent early time dynamics of photobleaching (PB) at about 950 nm according to various embodiments.
FIG. 33D is a plot of hot charge carrier cooling time (τHCC) as a function of pump fluence (micro-Joules per square centimeter or μJ/cm2) exhibited by the 20% SnF2 doped CsSnI3 film according to various embodiments.
FIG. 34A is a pseudo color transient absorption (TA) plot wavelength (nanometers or nm) as a function of time (picoseconds or ps) showing the change in absorption ΔA (arbitrary units or a.u) as a function of probe wavelength and probe delay time for the CsSnI3 samples with different SnF2 treatment according to various embodiments.
FIG. 34B is a plot of change in absorption ΔA (arbitrary units or a.u.) as a function of wavelength (nanometer or nm) showing the transient absorption (TA) of 4 samples according to various embodiments at 5 pico-seconds (ps) probe delay time (extracted from the transient absorption (TA) in FIG. 34A) overlaid for comparison.
FIG. 34C is a pseudo color transient absorption (TA) plot of wavelength (nanometers or nm) as a function of time (picoseconds or ps) showing the change in absorption (ΔA) as a function of probe wavelength and probe delay time for the 30% SnF2-treated CsSnI3 film according to various embodiments.
FIG. 34D is a plot of change in absorption ΔA (arbitrary units or a.u.) as a function of wavelength (nanometer or nm) showing the transient absorption (TA) shown in FIG. 34B replotted with the transient absorption (TA) of the 30% SnF2-treated sample according to various embodiments for comparison.
FIG. 35A is a plot of change in absorption ΔA (arbitrary units or a.u.) as a function of time (picoseconds or ps) showing normalized bleaching kinetics at about 950 nm for the SnF2 treated CsSnI3 films according to various embodiments in an optical cryostat under vacuum following excitation at 650 nm (1 KHz, 50 fs,  ̃2 μJ/cm2).
FIG. 35B is a schematic illustrating the origins of the various transient absorption (TA) of photobleaching (PB) and photoinduced absorption (PIA) present in the films according to various embodiments.
FIG. 36 are plots of initial photoluminescence intensity (IPL[t=0]) (arbitrary units or a.u.) as a function of pump fluence (micro-Joules per square centimeter or μJ/cm2) showing pump fluence dependence of the initial time photoluminescence (PL) intensity for the pristine, the 5% SnF2-added, and the 10% SnF2-added CsSnI3 according to various embodiments.
FIG. 37A is a plot of amplified spontaneous emission (ASE) (arbitrary units or a.u.) as a function of time (hours or hrs) showing time-dependent amplified spontaneous emission intensity of the 5% SnF2-treated CsSnI3 film according to various embodiments with a pump fluence of 70 μJ/cm2 (600 nm, 50 fs, 1 KHz) under excitation for about 20 hours performed at room temperature. High stability is evident even for the lowest SnF2 addition.
FIG. 37B is a plot of photoluminescence (PL) intensity (arbitrary units or a.u.) as a function of wavelength (nanometers or nm) showing the photoluminescence (PL) spectra from 77 to 300 K for the SnF2 doped CsSnI3 according to various embodiments.
FIG. 37C is a plot of photoluminescence (PL) intensity (arbitrary units or a.u.) as a function of temperature (Kelvins or K) showing integrated photoluminescence intensity exhibited by treated and untreated samples according to various embodiments as a function of temperature.
FIG. 38A is a plot of photoluminescence (PL) intensity (arbitrary units or a.u.) as a function of time (nanoseconds or ns) showing the time-resolved photoluminescence (PL) decay transients for untreated CsSnI3 (0% SnF2) according to various embodiments.
FIG. 38B is a plot of photoluminescence (PL) intensity (arbitrary units or a.u.) as a function of time (nanoseconds or ns) showing the time-resolved photoluminescence (PL) decay transients for 5% SnF2 added CsSnI3 according to various embodiments.
FIG. 38C is a plot of photoluminescence (PL) intensity (arbitrary units or a.u.) as a function of time (nanoseconds or ns) showing the time-resolved photoluminescence (PL) decay transients for 10% SnF2 added CsSnI3 according to various embodiments.
FIG. 38D is a plot of photoluminescence (PL) intensity (arbitrary units or a.u.) as a function of time (nanoseconds or ns) showing the time-resolved photoluminescence (PL) decay transients for 20% SnF2 added CsSnI3 according to various embodiments.
FIG. 39 is a plot of photoluminescence (PL) intensity (arbitrary units or a.u.)/amplified spontaneous emission ncth (arbitrary units or a.u.) as a function of temperature (kelvins or K) showing normalized temperature dependent ASE thresholds (circles), normalized temperature dependent PL intensities at fixed pump fluence (squares) of SnF2 doped CsSnI3 perovskites according to various embodiments.
FIG. 40 is a plot of bandgap (electron-volts or eV) as a function of atomic volume (cubic angstroms or Å3) showing theoretical predicted band gaps of CsSnBr3, CsSnBr2I, CsSnBrI2 and CsSnI3 according to various embodiments with the Δ-sol method (4002).
FIG. 41 is a plot of emission intensity (arbitrary units or a.u.) as a function of wavelength (nanometers or nm) showing wide photoluminescence (PL) and amplified spontaneous emission (ASE) wavelength tunability from CsSnBrxI(3-x) films according to various embodiments fabricated by facile mixing the precursor solutions.



DETAILED DESCRIPTION
The following detailed description refers to the accompanying drawings that show, by way of illustration, specific details and embodiments in which the invention may be practiced. These embodiments are described in sufficient detail to enable those skilled in the art to practice the invention. Other embodiments may be utilized and structural, and logical changes may be made without departing from the scope of the invention. The various embodiments are not necessarily mutually exclusive, as some embodiments can be combined with one or more other embodiments to form new embodiments.
In order that the invention may be readily understood and put into practical effect, particular embodiments will now be described by way of examples and not limitations, and with reference to the figures.
Various embodiments relate to low temperature, solution processable high crystallinity gain media. Various embodiments not only reduce the production costs but also permit application of such solution processable gain media to a much wider range of resonator designs compatible for on-chip integration.
FIG. 1 is a schematic 100 showing an emission source according to various embodiments. The emission source may also include a gain medium 102, the gain medium 102 including a halide semiconductor material. The emission source may further include a pump source 104 configured to provide energy to the gain medium 102.
In other words, the emission source may include a gain medium 102 made of a halide semiconductor material. The emission source may further include a pump source 104 to provide energy to the gain medium 102.
The halide semiconductor material may also be referred to as a halide semiconductor. The halide semiconductor material may be or may include a halide perovskite material. The halide perovskite material may include an organic-inorganic perovskite material. The halide perovskite material may be or may include a three dimensional halide perovskite material. The halide perovskite material may also be referred to as perovskite material. In general, the halide semiconductor material may be or may include a three dimensional halide semiconductor material.
The halide semiconductor material may include or be a lead-free perovskite material. In other words, the halide semiconductor material may be or may include a perovskite material that does not contain lead. The lead-free perovskite material may include a cation of CsSn3+. The lead-free perovskite material may include one or more halide anions selected from a group consisting of F−, I−, Cl− and Br−. The lead-free perovskite material may include CsSnI3.
The gain medium 102 may further include one or more additives to control trap density. The one or more additives may be or may include SnF2. The weight concentration of SnF2 may be equal to or below 20%, e.g. 5%, 10%, or 20%. In other words, the weight of SnF2 relative to the weight of the gain medium may be equal to or below 20%, e.g. 5%, 10% or, 20%. The gain medium 102 may be treated or doped with the one or more additives. The word “treated” used in the current context may have the same meaning as the word “doped”.
FIG. 2A is a schematic 200a showing a cross-sectional side view an emission source according to various embodiments. The emission source may also include a gain medium 202, the gain medium 202 including a halide semiconductor material such as a halide perovskite material. The emission source may further include a pump source 204 configured to provide energy to the gain medium 202.
In various embodiments, the emission source may be a source for providing amplified spontaneous emission (ASE). In addition, the emission may additionally or alternatively provide spontaneous emission (SE), and/or stimulated emission (laser).
The pump source 204 may be configured to supply energy to the gain medium through a process called pumping. In various embodiments, the pump source 204 may be or may include an optical source configured to provide light as energy to the gain medium 202. The optical source may a flash lamp or by a laser. The optical source may emit light of a wavelength different from the light which the emission source generates or emit.
In various alternate embodiments, the pump source 204 may be or may include an electrical source configured to provide electrical energy to the gain medium 202. The electrical source may be configured to supply a current to the gain medium 202.
As shown in FIG. 2A, the emission source may include a resonant cavity 206. The gain medium 202 may be arranged within the resonant cavity 206. The resonant cavity 206 may be an open cavity. In other words, the gain medium 202 may be arranged to couple with a resonant cavity 206. In various embodiments, the resonant cavity 206 may be defined by a first reflective structure 208a and a second reflective structure 208b. The gain medium 202 may be arranged between the first reflective structure 208a and the second reflective structure 208b along an optical axis. The resonant cavity 206 may also be referred to as an optical cavity.
The first reflective structure 208a may be arranged to reflect light incident on the first reflective structure 208a towards the second reflective structure 208b along the optical axis and the second reflective structure 208b may be arranged to reflect light incident on the second reflective surface 208b towards the first reflective surface 208a along the optical axis. In other words, light may bounce between the first reflective structure 208a and the second reflective structure 208b, passing through the gain medium 204 after each reflection. As the light passes through the gain medium 204, a wavelength or range of wavelengths of the light is amplified by stimulated emission.
The first reflective structure 208a and the second reflective structure 208b may be arranged substantially parallel to each other.
The first reflective structure 208a may be partially transparent so that light incident in the first reflective structure 208a may be partially transmitted through the first reflective structure 208a and partially reflected towards the second reflective structure 208b along the optical axis. The first reflective structure 208a may be referred to as an optical coupler. The second reflective structure 208b may be a highly reflective mirror. The resonant cavity 206 may be defined or may include other suitable arrangements of reflective surfaces. The halide semiconductor material may be represented by the general formula AMX3, where A may be a monopositive organic or inorganic ion (e.g. an organic group or organic cation or a metal cation or element), M may be a divalent metal cation or element, and X may be a halogen anion or element. Examples may include CH3NH3PbI3, CH3NH3PbBr3, CH3NH3PbBr2I, CsSnIh, CsPbI3, NH2CH═NH2PbI3. The halide semiconductor material may be alternatively represented by A2MX6, where A may be a monopositive organic or inorganic ion (e.g. an organic group or organic cation or a metal cation or element), M may be a tetravalent metal cation or element, and X may a halogen anion or element. Examples may include Cs2SnI6, (CH3NH3)2SnI6. The halide semiconductor material may also have the general formula A2+mMmX3m+2, where A may be a monopositive organic or inorganic ion (e.g. an organic group or organic cation or a metal cation or element), M may be a divalent metal cation or element, and X may an halogen anion or element (m greater or equal to 1). Examples may include (CH3NH3)3SnI5, (NH2CH═NH2)2CH3NH3SnI5, (NH2CH═NH2)2CH3NH3SnI2Br3. The halide semiconductor may instead be represented by the formula A3n-1MnX3n+1, where A may be a monopositive organic or inorganic ion (e.g. an organic group or organic cation or a metal cation or element), M may be a divalent metal cation or element, and X may an halogen anion or element (n greater or equal to 1). An example may be (CH3NH3)2CuCl3Br. In various embodiments, the halide semiconductor material may include an organic ammonium cation or organic ammonium cation group. The organic group may be the organic ammonium cation or group. The organic ammonium group may be selected from a group consisting of an ammonium group, a hydroxylammonium group, a methylammonium group, a hydrazinium group, a azetidinium group, a formamidinium group, an imidazolium group, a dimethylammonium group, an ethylammonium group, a guanidinium group, a group with formula [CnH2n+1 NH3] where 2<n<20 or a long chain group such as phenethylammonium group [(C6H5—C2H4)NH3] and combinations thereof. The organic ammonium cation may be selected from a group consisting of an ammonium ion [NH4]+, a hydroxylammonium ion [H3NOH]+, a methylammonium ion [(CH3)NH3]+, a hydrazinium ion [H3N—NH2]+, an azetidinium ion [(CH2)3NH2]+, a formamidinium ion [NH2(CH)NH2]+, an imidazolium ion [C3N2H5]+, a dimethylammonium ion [(CH3)2NH2]+, an ethylammonium ion [(C2H5)NH3]+, a guanidinium ion [C(NH2)3]+, a cation with formula [CnH2n+1 NH3]+ where 2<n<20 or a long chain ion such as phenethylammonium ion [(C6H5—C2H4)NH3]+ and combinations thereof. In various alternate embodiments, the halide semiconductor material may include a metal cation such as Cs+, K+, Rb+. The halide semiconductor material may include a metal such as Cs, K or Rb.
The one or more metal elements may be selected from Group 14 of the periodic table. The halide semiconductor material may include one or more metal elements selected from a group consisting of Cu, Pb, Sn, Ge, Eu, Cr, Mn, Ni, Zn, Pd, Cd, Hg, Ba and Sr. The halide semiconductor material may include one or more metal cations selected from the cationic 2+ group (e.g. Cu2+, Pb2+, Sn2+, Ge2+, Eu2+, Cr2+, Mn2+, Ni2+, Zn2+, Pd2+, Cd2+, Hg2+, Ba2+ and Sr2+).
The one or more halogen elements may be selected from Group 17 of the periodic table. The halide semiconductor material may include one or more halogen elements selected from a group consisting of F, I, Cl and Br. The halide semiconductor material may include one or more halide anions selected from a group consisting of F−, I−, Cl− and Br−.
Examples of halide semiconductor materials may for instance include HNC(NH2)2SnF3, C2H5NH3Pb0.5Sn0.5Cl3, and CH3NH3SnFCl2.
Various embodiments relate to halide semiconductor materials as a gain medium. Various embodiments relate to the use or the application of low temperature solution processed halide semiconductor materials as coherent light emission gain medium that could be driven by photons and/or electrons.
The emission source may be configured to generate light, i.e. amplified spontaneous emission, spontaneous emission, and/or laser beam. The emission source may be configured to generate or emit coherent light. A coherent light may mean a polarized electromagnetic wave at a frequency whose phase is correlated over a relatively large distance (the coherence length) along the beam. The coherence length may be more than 10 cm or more than 15 cm or more than 20 cm or more than 50 cm or more than 1 m. The emission source may be configured to generate the amplified spontaneous emission and/or laser beam when energy is supplied or pumped into the gain medium 202 by the pump source 204.
In the present context, light may be any electromagnetic waves or combination of electromagnetic waves. In various embodiments, the emission source may be configured to generate light of a wavelength or range of wavelengths from a range of 250 nm to about 1 mm, e.g. about 380 nm to about 1 mm, e.g. from about 390 to about 790 nm. The emission source may be configured to generate visible light and/or infrared light. In other words, lasing wavelengths spanning from the visible to the infrared may be achieved using this class of materials.
Halide semiconductor materials may have a low trap density. The gain medium 202 may have a trap density below 1018 cm−3, e.g. below 0.5×1018 cm−3, e.g. below 1017 cm−3, e.g. below 0.5×1017 cm−3, e.g. below 1016 cm−3. The gain medium may be configured to achieve amplified spontaneous emission (ASE) at a pump fluence substantially equal to or below 50 μJ cm−2, e.g. substantially equal to or below 20 μJ cm−2, e.g. substantially equal to or below 15 μJ cm−2, substantially equal to or below 14 μJ cm−2, e.g. substantially equal to or below 12 μJ cm−2, substantially equal to or below 10 μJ cm−2. The threshold pump fluence may be dependent on the quality of the cavity. The emission source may be configured to generate light via amplified spontaneous emission (ASE).
The low trap density of halide semiconductor materials may allow amplified spontaneous emission (ASE) in bare films (i.e. without any cavity or optical feedback) to be achieved with the ultralow threshold pump fluence.
In various embodiments, the halide semiconductor material may have a ASE threshold carrier density below 1019 cm−3, e.g. below 5×1018 cm−3, e.g. below 2×1018 cm−3 e.g. about 1.7×1018 cm−3.
Halide semiconductor materials may also exhibit high optical stability and durability. Halide semiconductor materials may have long range balanced electron and hole diffusion lengths that makes it possible to achieve efficient electrical-driven lasing.
In various embodiments, the gain medium 202 may have a bulk trap density below or about 1017 cm−3, e.g. below or about 6×1016 cm−3, below or about 6×1016 cm−3.
Further, the gain medium may include halide semiconductor materials (e.g. halide perovskite materials) that are solution processable.
A solution processable gain medium has much greater versatility than traditional gain media for integration with existing silicon based technologies. The halide semiconductor materials may be applied to a much wider range of optical cavity designs and substrates by methods such as spin-coating, dip-coating or dropcasting. Further, halide semiconductor materials exhibit broadband gain profile. In various embodiments, the gain medium may have undergone a post film treatment. In various embodiments, the gain medium may further include one or more additives to control trap density. The one or more additives may include metal halides with a generic structure MI2, where M represents a metal cation and I represents the iodide anion. More generally, the one or more additives may include metal halides with a generic structure MH2, where M represents a metal cation and H represents the halide anion. Non-limiting examples include PbI2, SnI2 and SnF2. The weight concentration of the additive, e.g. SnF2, may be equal to or below 20%, e.g. 5%, 10% or, 20%. In other words, the weight of the additive, e.g. SnF2, relative to the weight of the gain medium 202 may be equal to or below 20%, e.g. 5%, 10%, or, 20%. The one or more additives may be configured to control metal vacancies/oxidation states. Other further additives to improve film formation properties may include acids such as HCl, HI or other halide derivatives such as CH3NH3Cl.
Facile substitution of the metal element and organic component may allow a wide choice of lasing wavelengths. For instance, the material may be or may include CH3NH3PbCl3, CH3NH3PbCl1.5Br1.5 and/or CH3NH3PbCl2Br. In various embodiments, the halide semiconductor material may include more than one organic cation or group. The halide semiconductor material may include more than one metal cation. The halide semiconductor material may include more than one halide anion. The gain medium 202 may include more than one halide semiconductor materials. For instance, the gain medium 202 may include a mixture of CH3NH3PbCl3, CH3NH3PbCl1.5Br1.5 and CH3NH3PbCl2Br.
The material may alternatively include or be a lead-free perovskite material. The lead-free perovskite material may include a cation of CsSn3+. The lead-free perovskite material may include one or more halide anions selected from a group consisting of F−, I−, Cl− and Br−. The lead-free perovskite material may include CsSnI3. Lead-free perovskites may be a less toxic and greener alternative over lead halide perovskites such as CH3NH3PbX3, where X is Cl, Br or I. While lead-free perovskite materials may have poorer photovoltaic performances, lead-free perovskite materials such as CsSnI3 may possess outstanding performances comparable to their leaded counterparts. This may be attributed to higher free electron-hole bimolecular recombination constants of lead-free perovskite materials, especially when the lead-free perovskite materials are treated with additives such as SnF2. The higher free electron-hole bimolecular recombination constants of SnF2-treated CsSnI3 perovskites may be about 2 or 3 times higher than that of CH3NH3PbI3.
In various embodiments, the halide semiconductor material layer may on a substrate such as a quartz substrate. In various embodiments, the emission source may include a layer such as CH3NH3PbI3/[6,6]-phenyl-C61-butyric acid methyl ester (PCBM) on or in contact with the halide semiconductor material layer. In various embodiments, the gain medium may include a substrate and a halide semiconductor material layer on the substrate. In various embodiments, the gain medium may further include a layer such as CH3NH3PbI3/[6,6]-phenyl-C61-butyric acid methyl ester (PCBM) on the halide semiconductor material layer.
Various embodiments may find applications in areas such as telecommunication, quantum computing, data storage and reading out (CD, DVD), laser pointer, barcode readers, laser printers, image scanners, laser surgery, industrial laser machining, directed energy weaponry, laser medicine, etc.
FIG. 2B shows a schematic 200b showing a cross-sectional side view of an emission source according to various embodiments. The emission source may also include a gain medium 212, the gain medium 212 including a halide semiconductor material such as a halide perovskite material. The emission source may further include a pump source 214 configured to provide energy to the gain medium 212.
The emission source may be or may include an optical pumped bulk perovskite laser according to various embodiments. The halide semiconductor material may be or may include a three-dimensional perovskite gain material 212 such as CH3NH3PbX3(X═Cl, Br, I or their combinations), a lead-free perovskite material such as CsSnI3(SnF2)x, or any other suitable perovskite material. The perovskite gain materials may be contained in an optical cavity such as a self formed optical cavity or formed by other optical elements such as partially transmission mirror 218a and mirrored element 218b. The elements 218a, 218b may be the reflective structures. The mirrored element 218b may be disposed at one end of the gain material 212 and the partially transmission mirror 218a may be disposed at the other end. A suitable pumping source 214 such as a Ti:sapphire laser may provide a pumping energy (e.g. at a wavelength of 400 nm). The energy may be transmitted through lens 215 and mirror 218b to energize the perovskite material. The laser output beam 220 may exit through the partially reflective mirror 218a. 
FIG. 2C shows a schematic 200c showing a cross-sectional side view of an emission source according to various alternate embodiments. The emission source may also include a gain medium 222, the gain medium 222 including a halide semiconductor material such as a halide perovskite material, e.g. a lead-free perovskite material. The emission source may further include a pump source 224a. 224b configured to provide energy to the gain medium 222. The pump source 224a, 224b may include a first flash tube 224a and a second flash tube 224b arranged on opposing sides of the gain medium 222. The emission structure may further include partially transmission mirror 228a and mirrored element 228b. The elements 228a, 228b may be the reflective structures.
The emission source shown in FIG. 2C may be referred to as a flash tube side pumped perovskite laser. The gain medium 222 may be side pumped using flash tubes 224a, 224b. 
FIG. 2D shows a schematic 200d showing a perspective view an emission source according to various alternate embodiments. FIG. 2E shows a schematic 200e showing a cross-sectional side view of the emission source of FIG. 2D according to various embodiments. The emission source may also include a gain medium 232, the gain medium 232 including a halide semiconductor material such as a halide perovskite material, e.g. a lead-free perovskite material. The emission source may further include a pump source 234 configured to provide energy to the gain medium 232. The gain medium 232 may be a perovskite waveguide.
Although we only show bulk lasers with perovskite used as the gain material in the earlier figures, various embodiments may relate also to perovskite channel waveguide laser as shown in FIG. 2D. The perovskite channel waveguide laser may be conveniently formed on a substrate 235a (including a material such as silica or aluminum oxide). The perovskite waveguide 232 may be formed for example, using a suitable lithographic approach. The channel perovskite waveguide 232 may be covered with an overcoating or cladding layer 235b, the overcoating or cladding layer 235b including a suitable polymer or dielectric material with refractive index lower than the perovskite material. The perovskite waveguide 232 may include two mirrored ends 238a, 238b as reflective structures. Laser beam 240 may exit the less reflective end 238a. 
FIG. 2F shows a schematic 200f showing a cross-sectional side view of an emission source according to various other embodiments. The emission source may also include a gain medium 242, the gain medium 242 including a halide semiconductor material such as a halide perovskite material, e.g. a lead-free perovskite material. The emission source may further include a pump source 244 configured to provide energy to the gain medium 242. The gain medium 242 may be a perovskite waveguide. The emission source may be or may include a top optical pumped bulk perovskite Distributed Bragg Reflector (DBR) laser.
The perovskite DBR laser may be on a substrate 245 with periodic structures 248a, 248b serving as gratings to provide optical feedback for the emission in the perovskite gain medium 242. Laser beam 250 exits from the top 248a. 
FIG. 2G shows a schematic 200g showing a cross-sectional side view of an emission source according to various other embodiments. The emission source may also include a gain medium 252, the gain medium 252 including a halide semiconductor material such as a halide perovskite material, e.g. a lead-free perovskite material. The emission source may further include a pump source 254 configured to provide energy to the gain medium 252. The gain medium 252 may be a perovskite waveguide. The emission source may be or may include a perovskite Distributed Feedback (DFB) laser.
The emission source may include a substrate 255a, a diffraction grating 255c on the substrate 255a. The emission source may further include a laser element 255a on the diffraction grating 255c. The diffraction grating 255c may include the gain medium 255c and be configured to reflect light to and from the gain medium 255c to generate laser beam 260. In other words, a periodic structure such as a diffraction grating 255c may be integrated into the active perovskite gain medium 252. The diffraction grating 255c may provide optical feedback for the emission. The whole structure may be supported by a substrate 255a with a laser element 255c on top of it. Laser beam 260 may exit from the side.
FIG. 2H shows a schematic 200h showing a cross-sectional side view of an emission source according to various other embodiments. The emission source may also include a gain medium 262, the gain medium 262 including a halide semiconductor material such as a halide perovskite material, e.g. a lead-free perovskite material. The emission source may further include a pump source 264 configured to provide energy to the gain medium 252. The pump source 264 may be or may include an electrical source, such as a power supply 264. The emission source may be or may include an electrically pumped perovskite laser (side emitting). The emission source may include a gain medium 262 between a first laser element 265a and a second laser element 265b. A first electrode 267a may be on the first laser element 265a and a second electrode 267b may be on the second laser element 265b. The electrical source 264 may be electrically coupled to the first electrode 267a and the second electrode 267b. Electrical energy may be supplied by the electrical source 264 to generate laser beam 270. In other words, the perovskite laser may also be pumped electrically by connecting an electrical power source 264 across two electrodes 267a and 267b and the electrons and holes are transported through laser elements 265a and 265b to provide an electric field across the perovskite gain material 262 and provide the necessary population inversion to result in the lasing action that produces output beam 270. The beam 270 may travel in a direction perpendicular to a direction from the first electrode 267a to the second electrode 267b. 
FIG. 2I shows a schematic 200i showing a cross-sectional side view of an emission source according to various other embodiments. The emission source may also include a gain medium 272, the gain medium 272 including a halide semiconductor material such as a halide perovskite material, e.g. a lead-free perovskite material. The emission source may further include a pump source 274 configured to provide energy to the gain medium 252. The pump source 274 may be or may include an electrical source, such as a power supply 274. The emission source may be or may include an electrically pumped perovskite DBR laser (top emitting). The emission source may include a gain medium 272 between a first laser element 275a and a second laser element 275b. A first electrode 277a may be on the first laser element 275a and a second electrode 277b may be on the second laser element 275b. The electrical source 274 may be electrically coupled to the first electrode 277a and the second electrode 277b. Electrical energy may be supplied by the electrical source 274 to generate laser beam 280. The first laser element 275a may be a first Distributed Bragg Reflector (DBR) and the second laser element 275b may be a second Distributed Bragg Reflector (DBR). The laser may be pumped electrically by connecting an electrical power source 274 across two electrodes 277a, 277b and the electrons and holes may be transported through laser elements 277a, 277b to provide an electric field across the perovskite gain material 272 and provide the necessary population inversion to result in the lasing action. The Distributed Bragg Reflectors 277a, 277b may determine the lasing wavelength and the laser beam 280 exits from the less reflective end 277a. The laser beam may travel in a direction parallel to a direction from electrode 277b to electrode 277a. 
FIG. 3 shows a schematic 300 of a method of forming an emission source according to various embodiments. The method may include, in 302, providing a gain medium including a halide semiconductor material. The method may also include, in 304, providing a pump source configured to provide energy to the gain medium.
In other words, a method of fabricating a emission source may include providing a gain medium including a halide semiconductor material and arranging a pump source so that the pump source is able to provide energy, e.g. electrical energy and/or optical energy to the gain medium.
In various embodiments, the gain medium may be arranged within a resonant cavity. The gain medium may be arranged within the cavity by arranging the gain medium between a first reflective structure and a second reflective structure along an optical axis.
In various embodiments, the first reflective structure may be arranged to reflect light incident on the first reflective structure towards the second reflective structure along the optical axis and the second reflective structure may be arranged to reflect light incident on the second reflective surface towards the first reflective surface along the optical axis.
In various embodiments, the first reflective structure may be partially transparent so that light incident in the first reflective structure may be partially transmitted through the first reflective structure and partially reflected towards the second reflective structure along the optical axis.
In various embodiments, the halide semiconductor material may be formed by reacting a metal halide (e.g. PbI2, SnCl2, CaBr2) with an organic ammonium halide. The metal halide may be caused to react with the organic or inorganic halide such as an ammonium halide (e.g. CH3NH3I, CH3NH3F, HNC(NH2)2Br etc.) by mixing the metal halide with the organic ammonium halide in a suitable solvent.
While only selected examples are mentioned in the experimental section of halide semiconductor material, these examples are not intended to be limiting and other halide semiconductor materials may show similar results.
In various embodiments, the halide semiconductor material may be formed by dropcasting or spincoating or any other solution-based methods. The halide semiconductor material may be formed by printing processes, (e.g. dropcasting or spincoating etc.), physical deposition methods (e.g. thermal evaporation, sputtering etc.) or combinations thereof.
The halide semiconductor material, e.g. organic-inorganic perovskite films may be prepared by simple solution deposition processes such as dropcasting and spincoating. The solution may include CH3NH3X and PbX2 (where X may be a halogen such as I, Cl, Br and F or mixtures of them) dissolved in an appropriate solvent such as DMF (Dimethyl formamide) or GBL (Gamma butyrylactone). The wt % of the solute (CH3NH3X+PbX2) may be as high as 40%, or as high as 35%. Upon deposition and mild heating, the deposited film may transform into crystalline CH3NH3PbX3. Heating temperature may be a temperature less than 100° C., e.g. less than 80° C., e.g. less than 50° C. Another solution based technique may include the spincoating of PbX2 on a substrate followed by dipping it in a CH3NH3X solution to complete its transformation to CH3NH3PbX3. Other non-solution based techniques such as evaporative deposition may also possible.
Solution processed organic-inorganic perovskite materials may provide simple and inexpensive alternatives to traditional semiconductor gain mediums which were produced with expensive gas-phase methods. Various embodiments may be easily integrated with existing silicon based electronics. If compared with traditional semiconductor gain mediums, various embodiments may also provide better temperature stability of the ASE occurring threshold. The low temperature of processing may also enable integration of these materials on to flexible substrates.
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 lasing 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 dots still remain. Herein, we reveal that halide semiconductors such as solution-processed organic-inorganic halide perovskites (CH3NH3PbX3 where X D Cl, Br, I) may demonstrate huge potential in photovoltaics and may have promising optical gain. Their ultra-stable amplified spontaneous emission at strikingly low thresholds may stem 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 characteristics, these materials may show electrically driven lasing.
Experimental Section
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 lengths. Surprisingly, we found that they may also exhibit excellent coherent light emission properties.
The CH3NH3PbI3 films on quartz substrates were prepared by spin-coating 10 vol % solutions in DMF. [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) layers were spin-coated from a solvent mixture (10 mg ml−1) of anhydrous chlorobenzene and anhydrous chloroform (1:1 v/v).
The samples were put in vacuum for more than three days to get rid of any residual solvent before the optical measurements. Mixed halides were prepared by blending appropriate molar ratios of CH3NH3PbI3, CH3NH3PbBr3 and CH3NH3PbCl3 solutions. The solar cells were fabricated using the sequential deposition procedure, as previously reported and characterized under simulated air mass 1.5 global (AM1.5G) solar irradiation in the dark.
Optical spectroscopy. For femtosecond optical spectroscopy, the laser sources were a Coherent Legend regenerative amplifier (150 fs, 1 kHz, 800 nm) seeded by a Coherent Vitesse oscillator (100 fs, 80 MHz) and a Coherent Libra regenerative amplifier (50 fs, 1 kHz, 800 nm) seeded by a Coherent Vitesse oscillator (50 fs, 80 MHz). 800 nm wavelength laser pulses were from the regenerative amplifier's output whereas 400 nm wavelength laser pulses were obtained with a BBO doubling crystal. 600-nm laser pulses were generated from the Coherent TOPAS-C and Coherent OPerA-Solo optical parametric amplifiers. The laser pulses (circular spot, diameter 1.5 mm) were directed to the films under vacuum in a cryostat. The emission from the samples was collected at a backscattering angle of 150 by a pair of lenses into an optical fibre that was coupled to a spectrometer (Acton, Spectra Pro 2500i) and detected by a charge coupled device (Princeton Instruments, Pixis 400B). Time-resolved PL (TRPL) was collected using an Optronis Optoscope streak camera system which has an ultimate temporal resolution of about 10 ps. All optical measurements were performed at room temperature, except for ASE from CH3NH3PbCl3 (at 150 K). Room-temperature photoluminescence quantum yield (PLQY) of the perovskite thin films was measured using an integrating sphere. The samples were excited with 600 nm pulses generated from the Coherent OPerA-Solo. The emission was corrected for CCD and grating responsivity. Room-temperature gain measurements were carried out using standard VSL methods. The excitation stripe was focused by a cylindrical lens (with focal length f=20 cm) to a stripe and the emission collection configuration was the same as described above. The excitation stripe length was varied through an adjustable slit actuated by a micrometer which was placed at the focal line of the cylindrical lens.
After spincoating, a clear optically flat film of CH3NH3PbI3 was obtained with thickness of about 65 nm. FIG. 4A is a plot 400a of a comparison of the amplified spontaneous emission (ASE) profile (indicated by 1402) in relation to the absorption (indicated by 1404) and spontaneous emission (SE)/photoluminescence profile (indicated by 1406) for CH3NH3PbI3. The ASE develops at the wavelength where the optical gain and absorption are balanced—the ASE peak is red-shifted with respect to the photoluminescence (PL) peak. The CH3NH3PbI3 film has strong absorbance ( ̃104 cm−1) from UV to near infrared (800 nm) with two distinct peaks located at 480 nm and 760 nm, which are consistent with previous publications. The broad strong absorbance is a good indication of its excellent light harvesting capabilities. The second absorption peak (760 nm) is attributed to the direct gap transition from the first valence band maximum to the conduction minimum. The first absorption peak (480 nm) is attributed to the transition from lower valence band to the conduction band minimum. The strong band edge PL peaks at 770 nm. Absorbance is measured in cm−1 while PL intensity/SE and amplified spontaneous emission are in arbitrary units (a.u.). Absorbance, PL intensity/SE and amplified spontaneous emission are plotted against wavelength (nm).
FIG. 4B shows a plot 400b of a typical time resolved photoluminescence (TRPL) decay transients following photo-excitation with pump fluence below ( ̃10 μJ cm−2, indicated by 1406) and above ( ̃13 μJ cm−2, indicated by 1410) the ASE threshold (i.e., 12±2 μJ cm−2). FIG. 4B shows the variation of PL intensity in arbitrary units (a.u.) against time (in ps). The lifetime data presented in FIG. 4B is collected over a time window of 18 ns to allow consistent comparison with the longer-lived SE dynamics. FIG. 4C is a streak camera image 400c of spectrum against time (collected over a time window of 460 ps) for below ASE threshold fluence. FIG. 4D is a streak camera image 400d of spectrum against time (collected over a time window of 460 ps) for above ASE threshold fluence.
FIG. 8A is a plot 800a showing steady-state photoluminescence (PL) emission spectra from a 65-nm-thick CH3NH3PbI3 film photoexcited using 600 nm, 150 fs and 1 kHz pump pulses with increasing pump fluence (per pulse). FIG. 8A illustrates the transition from spontaneous emission (SE) to amplified spontaneous emission (ASE) with increasing pump fluence at 1.2 μJ cm−2, 10 μJ cm−2, 11 μJ cm−2 13 μJ cm−2, 15 μJ cm−2 the CH3NH3PbI3 film, which is spin-coated on a quartz substrate.
FIG. 8B is a plot 800b showing the corresponding time resolved photoluminescence (TRPL) intensity measured at 788±10 nm. FIG. 8B shows the TRPL intensity at a pump fluence of 1.2 μJ cm−2, 10 μJ cm−2, 11 μJ cm−2, 13 μC cm−2.
FIG. 8C is a plot 800c full width at half maximum (FWHM) of the emission peak (indicated by 802) and average transient photoluminescence lifetime (τPL) (indicated by 804) as a function of the pump fluence. τPL may be defined as the time taken for the intensity to decrease to 1/e of its initial value. At low pump levels, the broad spontaneous emission (SE) (with FWHM about 50 nm) from CH3NH3PbI3 increases linearly with increasing pump fluence. Correspondingly, the average transient photoluminescence (PL) lifetimes (τPL) progressively decrease.
FIG. 8D is a plot 800d showing photoluminescence intensity as a function of pump fluence. The arrows indicate the trap state saturation threshold fluence (Pthtrap) and the ASE threshold fluence (PthASE). Line 806 and line 808 represent the linear fits to experimental data in the two linear regimes of SE and ASE, respectively. The dashed vertical lines 810a, 810b in FIGS. 8C and 8D respectively indicate the onset of ASE.
Above the threshold fluence (12±2 μJ cm−2), the emission intensity may increase superlinearly (as shown in FIG. 8D), with PL dramatically shortened owing to the occurrence of a new short lifetime (<10 ps) dynamical process. Concurrently, the emission band may collapse to yield a sharp peak at 788 nm (as shown in FIG. 8A). These may provide clear signatures of optical amplification of the SE from CH3NH3PbI3, i.e. ASE behaviour. The balance between optical gain and self-absorption may give rise to a red-shifted ASE peak that is located near the tail of the absorption edge (as shown in FIG. 4A).
The intrinsic gain properties of perovskites are investigated by examining the ASE behaviour in a cavity-free configuration. The ASE values provide a better benchmark for comparing different material sets on their intrinsic suitability for gain applications.
From the measured threshold fluence (12±2 μJ cm−2 and absorption coefficient (á=5.7×104 cm−1 at 600 nm), the ASE threshold carrier density may be calculated to be about 1.7×1018 cm−3. The threshold carrier density may correspond to the ease with which a material can attain net gain through optical or electrical generated means. Comparatively, for highly crystalline high-temperature-grown ZnSe and CdS nanowires (with similar α=105 cm−1 at the excitation wavelengths), the typical threshold carrier densities are nearly one order larger under similar measurement conditions.
Similarly, the typical ASE threshold carrier density for solution-processed organic thin films may be approximately one order larger. As a point of comparison, state-of-the-art cavity-free solution-processed polymer films such as poly[9,9-dioctylfluorene-co-9,9-di(4-methoxyphenyl)-fluorene] (F8DP) and Super Yellow exhibited an ASE threshold of about 6 μJ cm−2 (calculated from reported threshold pump energy of 0.1 μJ per pulse; excitation stripe about 400 μm×about 4 mm) and about 36 μJ cm−2 (calculated from the reported values of 315 nJ/pulse over a rectangular spot of length about 2.5 mm and width about 350 μm) respectively.
The results on CH3NH3PbI3 also compare favourably to reported CdSe/ZnCdS core/shell colloidal quantum dot (QD) films having an ASE threshold of 90 μJ cm−2.
Photoluminescence quantum yield (PLQY) values approaching 20% at pump fluence above the ASE thresholds have also measured using an integrating sphere. FIG. 9A is a plot 900a showing photoluminescence quantum yield (PLQY) (in percentage or %) dependence on pump fluence (in μJ cm−2). The PLQY measurements are carried out for CH3NH3PbI3 films at various pump fluence at room temperature using an integrating sphere. The samples were excited with 600 nm pulses generated from the Coherent OPerA-Solo, an optical parametric amplifier. The emission was corrected for CCD and grating responsivity.
The room temperature gain of the CH3NH3PbI3 sample was assessed using Variable Stripe Length (VSL) measurements. FIG. 9B is a plot 900b showing room temperature variable stripe length (VSL) measurements of the CH3NH3PbI3 films and fitted using the respective methods used for solution processed colloidal quantum dots thin films. FIG. 9C is a plot 900c showing room temperature variable stripe length (VSL) measurements of the CH3NH3PbI3 films and fitted using the respective methods used for organic thin films. FIGS. 9B and 9C show variation of intensity (arbitrary units or a.u.) against stripe length (cm)
The data is fitted using two methods. The method developed by Shaklee and Leheny (Shaklee, K. L. & Leheny, R. F. “Direct determination of optical gain in semiconductor crystals.” Appl. Phys. Lett. 18, 475-477 (1971)), is a straightforward way to determine the gain spectrum of a material over the small signal regime (utilized for inorganic and organic semiconductors in slab geometry).
The equation is provided by:




  
    
      
        
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where Io(z), g, and z are the detected light intensity, gain coefficient and excitation stripe length, respectively; Is is the spontaneous emission rate per unit volume and A is the cross-sectional area of the excited volume.

Another method developed by Chan et al. (Chan, Y. et al., Blue semiconductor nanocrystal laser, Appl. Phys. Lett. 86, 073102 (2005)) for analysis over the entire signal regime (including saturation) and is more commonly used in solution processed colloidal quantum dot films.
The equation is provided by:




  
    
      
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Wherein I, g, and z are the ASE intensity, gain coefficient and excitation stripe length. Respectively; while zo accommodates for possible pump beam inhomogenity and delayed ASE onset. Ia is a parameter that accounts for the saturation in ASE intensity which is defined as the gain lifetime multiplied by the speed of light within the gain medium.

The relatively low yield may be a consequence of the low exciton binding energy (19±3 meV) as well as high electron and hole mobilities. Nonetheless, variable stripe length (VSL) measurements on CH3NH3PbI3 have revealed a gain of about 250 cm−1 (fitted with Chan's method in Chan, Y. et al., Blue semiconductor nanocrystal laser, Appl. Phys. Lett. 86, 073102 (2005), typically used for colloidal QDs, see FIG. 4F) or about 40 cm−1 (fitted with Shaklee and Leheny's method in Shaklee, K. L. & Leheny, R. F. “Direct determination of optical gain in semiconductor crystals.” Appl. Phys. Lett. 18, 475-477 (1971), largely used for films of conjugated polymers, see FIG. 4G) at a pump fluence of 14 μJ cm−2. The gain values obtained from the respective methods compare favourably with those for colloidal quantum dots (Dang, C. et al. Red, “green and blue lasing enabled by single-exciton gain in colloidal quantum dot films.” Nature Nanotech. 7, 335-339 (2012), Liao, Y., Xing, G., Mishra, N., Sum, T. C. & Chan, Y. “Low threshold, amplified spontaneous emission from core-seeded semiconductor nanotetrapods incorporated into a sol-gel matrix.” Adv. Mater. 24, 159-164 (2012)) and conjugated polymer thin films (Lampert, Z. E., Reynolds. C. L. Jr., Papanikolas, J. M. & Aboelfotoh, M. O. “Controlling morphology and chain aggregation in semiconducting conjugated polymers: the role of solvent on optical gain in” MEH-PPV. J. Phys. Chem. B. 116, 12835-12841 (2012)) at comparable excitation intensities.
Various embodiments may show better performance than other solution processed systems. Typical competing non-radiative pathways that can rapidly deplete the carrier population and make ASE unfavourable in other solution-processed semiconductors may not be dominant in various embodiments. The non-radiative pathways may include bulk defects such as vacancies, interstitials, antisites etc.) with fast trapping in the fs and ps timescales, surface traps which typically may require more than 100 ps for carrier diffusion through a few tens of nanometers of the material, and multi-particle loss mechanisms (such as bimolecular recombination in organic thin films or Auger recombination in quantum dots).
Following photo-excitation across the CH3NH3PbI3 bandgap (at low pump fluence where Auger recombination is not dominant), the excited charge carriers may either relax through bandedge emission or trap-mediated non-radiative pathways. The former (relaxing through bandgap emission) may give rise to SE with a lifetime (τ0) of 4.5±0.3 ns (as shown in FIG. 8C). An estimate of the bulk and surface trap densities may be made under these conditions where trap state recombination is much slower than bandedge radiative recombination. The photo-generated charge carrier density (nC(t)) after photoexcitation may be described with a set of differential equations. The model reveals the presence of two types of traps in these CH3NH3PbI3 thin films, with the bulk traps exhibiting fast trapping times and the surface traps exhibiting slow trapping times.
FIG. 10A is a plot 1000a showing room temperature lasing from CH3NH3PbI3 single crystals from dropcasted films. 1002 indicates the lasing data while 1004 indicates the PL data. FIG. 10B is an optical micrograph 1000b of the crystal. FIG. 10C is a plot 1000c showing the lasing data 1002 fitted to 5 peaks (indicated by 1006). The most prominent mode shows a full width half maximum of 1.2 nm. FIGS. 4H, 4J plot PL intensity (in a.u.) against wavelength (nm).
Under low fluence fs laser pulse excitation (where Auger recombination is negligible) and the assumption that trap states recombination is much slower than band edge radiative recombination, the dynamics of photo-generated charge carrier density (nc) can be described with the following set of differential equations:




  
    
      
        
          
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Wherein nTPi (t) is the trap states density and a is the product of the trapping cross section and the carrier velocity. Therefore the first term in equation (3) represents various trap-mediated non-radiative pathways, while the second term denotes the radiative recombination inside the film. Thus the relationship between the integrated bandedge PL intensity (IPL=k∫0∞nc(t)/τ0dt, where k is a constant,) the initial photogenerated charge carrier density nc(0) can be obtained as:





  
    
      
        
          
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Fitting the experimental result with equation (5) yields two types of traps in these CH3NH3PbI3 thin films, with the bulk (surface/interfacial) traps exhibiting fast (slow) trapping times. The bulk trap density nTPF is about 5×1016 cm−3 while the surface/interfacial trap density nTPS is about 1.6×1017 cm−3. This correlates well with a simple estimation of the total trap density (bulk and surface) obtained by the intersection of the linearly extrapolated PL intensity (indicated by line 806) with that of the pump fluence axis from FIG. 8D (i.e. nTP0 ̃2×1017 cm−3). This intersection represents the pump fluence needed to fill all the traps (i.e., the threshold trap pump fluence PthTrap).

FIG. 10D is a plot 1000d showing photoluminescence (PL) intensity as a function of photon-generated exciton density within the low pump fluence range. The experimental data can be well-fitted (R2=0.99) with equation (5) for two types of trapping states.
The bulk trap density (nTPF) is about 5×1016 cm−3 whereas the surface trap density (nTPS) is about 1.6×1017 cm−3. The trap densities measured in CH3NH3PbI3 may be comparable to defect densities in highly ordered organic crystals (1015−1018 cm−3) and superior to those of solution-processed organic thin films (1019 cm−3). Solution-deposited, high-temperature annealed Cu—In—Ga—S/Se (CIGS) chalcogenide layers 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 material.
Finite difference time domain (FDTD) simulations (LumericalTM FDTD software) were performed to evaluate the optical confinement effects of the PCBM layer. The structure includes Quartz (100 nm)/CH3NH3PbI3 (65 nm)/[6,6]-phenyl-C61-butyric acid methyl ester (PCBM) (45 nm−optional)/vacuum (390 nm).
FIG. 5A is a plot 500a showing the real part (n) and imaginary part or extinction coefficient (k) of the complex refractive index. The refractive index of CH3NH3PbI3 was measured using an ellipsometer—nCH3NH3PbI3=2.3 and kCH3NH3PbI3=0.15 at 790 nm while that of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) was extracted from the literature (Hoppe, H., Sariciftci, N. S., & Meissner, D. Optical constants of conjugated polymer/fullerene based bulk-heterojunction organic solar cells, Mol. Cryst. Liq. Cryst. 385, 233-239 (2002)).
FIG. 5B shows a schematic 500b of the of a gain medium 502 under simulation conditions according to various embodiments. The gain medium 502 may be on a quartz film 504. The gain medium 502 may include CH3NH3PbI3 film. A PCBM layer 506 may be on the gain medium 502. A light source 508 (e.g. yellow line) may be introduced in-plane to the gain medium 502 and perfectly matched layers (PML) boundary conditions 510a, 510b may be used to absorb the incident light at the top and bottom edges with minimal reflections. A vacuum 512 may be between the top PML 510a and the structure including the gain medium 502.
FIG. 5C is a schematic 500c showing intensity distributions in the y-z plane of structures of light polarized parallel to the structure surface. 514 shows the intensity distribution of the light in the y-z plane of a structure with quartz film 504, gain medium 502 on quartz film 504 and PCBM layer 506 on the gain medium. 516 shows the intensity distribution of the light in the y-z plane of a structure with quartz film 504 and gain medium 502 on quartz film 504, i.e. without PCBM layer 506.
To examine the effects of the more prevalent surface traps on the carrier dynamics and ASE, PL measurements on bare CH3NH3PbI3 were compared against CH3NH3PbI3/[6,6]-phenyl-C61-butyric acid methyl ester (PCBM), C60) bilayers to mimic the presence of infinite interfacial electron trap states. Selective excitation of the CH3NH3PbI3 layer (about 65 nm thick for both cases) was performed with 600 nm laser pulses.
FIG. 11A is a plot 1100a showing the time-integrated PL spectra of CH3NH3PbI3 (indicated by 1102) and CH3NH3PbI3/([6,6]-phenyl-C61-butyric acid methyl ester (PCBM) (indicated by 1104). FIG. 11B is a plot 1100b showing the time-resolved photoluminescence (TRPL) decay transients for quartz/CH3NH3PbI3 (about 1.3 μJ cm−2, indicated by 1106), quartz/CH3NH3PbI3/PCBM (about 1.3 μJ cm−2, indicated by 1108 and about 17 μJ cm−2, indicated by 1110) 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 FIG. 11B are the single-exponential fits of the PL decay transients. FIG. 11C is a plot 1100c of the pump fluence-dependent photoluminescence spectra of quartz/CH3NH3PbI3 (65 nm)/PCBM film. FIG. 11D is a plot 1100d of the photoluminescence intensity of quartz/CH3NH3PbI3 (65 nm)/PCBM film. The line 1112 represents the linear fit to experimental data in the linear regime of SE. The line 1114 represents the linear to experimental data in the linear regime of ASE.
The presence of the PCBM layer ( ̃45 nm) is expected to severely quench the SE from the CH3NH3PbI3 layer; see FIG. 11A for the PL spectra and FIG. 11B for the PL decay transients. Such efficient PL quenching originates from the long-range electron diffusion in the CH3NH3PbI3 film, where the diffusion-limited electron trapping time by the surface states can be estimated to be about 0.40 ns (Xing, G. et al. Long-range balanced electron- and hole-transport lengths in organic-inorganic CH3NH3PbI3. Science 342, 344-347 (2013).). Surprisingly, under high pump fluence excitation, the ASE is impervious to the presence of the PCBM layer, which acts as a perfect electron quencher.
FIG. 11B 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 CH3NH3PbI3/PCBM film is measured to be 10±2 μJ cm−2 (FIG. 11D).
This value is slightly smaller than that of the bare CH3NH3PbI3 film (12±2 μJ cm−2) (shown in FIG. 8D) because of the better light confinement and propagation due to the presence of the PCBM cladding layer which improves gain buildup.
FIG. 7A is a schematic 700a of a solar cell according to various embodiments. The solar cell may include a substrate 702 such as fluorine doped tin oxide (FTO) glass. The solar cell may further include a blocking layer 704 on the substrate 702. The blocking layer 704 may be a titanium oxide (TiO2) blocking layer. The solar cell may further include a mesoporous layer 706 (e.g. a TiO2 mesoporous layer) on the blocking layer 704. The solar cell may further include a layer including halide perovskite material 708 (e.g. CH3NH3PbI3) on the mesoporous layer 706. The solar cell may additionally include a hole transport layer 710 on layer 708. The solar cell may also include an electrode 712 (e.g. a gold or aluminum electrode) on the hole transport layer 710. FIG. 7B is a plot 700b showing the current density J (mA cm−2) under A 1.5 (100 mW/cm2) illumination. FIG. 7C is a plot 700c of photoluminescence (PL) intensity (arbitrary units) as a function of pump fluence (μJ cm−2) showing amplified spontaneous emission (ASE) threshold of the solar cell configuration. FIG. 7D is a plot 700d of the ASE spectrum. The photoluminescence (PL) intensity (arbitrary units) as a function of wavelength (nm). FIG. 7E is a plot 700e showing ASE photostability measured under ambient conditions of the device (Excited with 600 nm, 1 KHz, 50 fs laser pulses,  ̃20 μJ cm−2). FIG. 7F is a photo 700f showing a demonstration of green ASE from CH3NH3PbBr3 deposited on PET substrates pumped using two-photon absorption at 800 nm.
Remarkably, ASE can also be observed in functional photovoltaic devices (ç=11.4%; Device structure: FTO/TiO2 compact layer/TiO2 mesoporous layer/CH3NH3PbI3/Spiro-OMeTAD/Au) with optical excitation; see FIG. 7A. The presence of the Spiro-OMeTAD layer, which acts as a perfect hole quencher, has no effect on the ASE from CH3NH3PbI3—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 CH3NH3PbI3—defying the Langevin recombination limit by at least four orders of magnitude.
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 (τAuger) from a few ps to ns, depending on the photo-generated charge carrier density. The Auger recombination in CH3NH3PbI3 is efficient (τAuger  ̃300 ps) compared with SE (4.5±0.3 ns) because of the long-range electron-hole diffusion lengths within them. However, the timescale for the occurrence of ASE (<10 ps-limited by the instrument response) signifies that the carrier build-up time for population inversion and the subsequent avalanche, out-competes the Auger processes in these CH3NH3PbI3 thin films (Supplementary Information). In contrast to solution-processed colloidal QDs (typical biexciton τAuger  ̃50 ps for 5 nm diameter CdSe QDs), such an Auger loss mechanism is less dominant in this ‘bulk-like’ CH3NH3PbI3 film.
Temperature dependent studies were also performed to further characterize the solution-processed CH3NH3PbI3 gain medium. FIG. 6A is a plot 600a of pump fluence dependent photoluminescence (PL) spectra at 6K. FIG. 6A plots PL intensity (in arbitrary units or a.u.) against wavelengths (nm). FIG. 6B is a plot 600b of pump fluence dependent photoluminescence (PL) intensity at 6K. FIG. 6B plots PL intensity (in arbitrary units or a.u.) against pump fluence (μJ cm−2).
Due to the limited bound states in the film, the emission intensity of these two peaks exhibit clear saturation behaviors at higher pump fluence. However, the free exciton emission intensity increases continually with increasing pump fluence, finally achieving ASE above a threshold fluence of 10±2 μJ/cm2. This ASE threshold at 6 K is comparable to that at 300 K (i.e., 12±2 μJ cm−2). Comparatively, traditional inorganic semiconductor gain media are highly susceptible to temperature induced effects: strong phonon assisted charge carrier trapping; temperature dependent exciton dissociation and photo-generated charge carrier diffusion and dilution. Hence, the threshold pump fluence for generating coherent light emission from these inorganic semiconductor materials are strongly temperature dependent. However, for CH3NH3PbI3, the ASE threshold is almost temperature-insensitive, which are similar to organic chromophores and quantum dots. The line 602 represents the fit to experimental data in the regime of SE for the 746 nm PL peak. The line 604 represents the fit to experimental data in the regime of ASE for the 746 nm PL peak. Line 606 indicates variation of PL intensity for the 782 nm peak as a function of pump fluence. The temperature-insensitivity of CH3NH3PbI3 ASE threshold stems from its extremely low trap states density and almost temperature invariant charge carrier diffusion as indicated by FIG. 6C.
FIG. 6C is a plot 600c showing time resolved photoluminescence (TRPL) TRPL decay transients for quartz/CH3NH3PbI3 (65 nm) (indicated by 608) and quartz/CH3NH3PbI3 (65 nm)/PCBM (45 nm) (indicated by 610) films in vacuum following excitation at 600 nm (1 KHz, 150 fs,  ̃1 μJ cm−2). The solid lines in FIG. 6C are the single-exponential fits of the PL decay transients.
Our experiments also show that such perovskite gain media have nearly temperature independent threshold pump fluence (carrier density). In contrast, traditional semiconductor gain media have strong temperature dependent threshold pump fluence (carrier density).
The photostability of the CH3NH3PbI3 thin films was assessed by monitoring the ASE intensity as a function of time under laser irradiation at a 1 kHz repetition rate at room temperature.
FIG. 12A is a plot 1200a showing shot-dependent ASE intensity of the solution-processed CH3NH3PbI3 film with over 9×107 laser excitation shots at 600 nm (1 kHz, 50 fs,  ̃18 μJ cm−2) performed at room temperature. The ASE intensity has a standard deviation of 0.2% about the mean intensity for about 26 h of continuous irradiation (that is  ̃108 laser shots in all). FIG. 12B is a plot 1200b showing shot-dependent ASE intensity of the solution processed CH3NH3PbI3 and CH3NH3PbI3/PCBM films over 7×106 at 600 nm (1 KHz, 50 fs, 14 μJ/cm2) under room temperature. Following such a large number of laser pulse excitation events, the near invariance of the output intensity shown in FIGS. 12A-B bear testimony to the excellent optical stability of the low temperature solution processed perovskites as gain media.
This performance compares favourably against the state-of-the-art organic semiconducting thin films (50% drop in output power after about 107 laser shots; Grivas, C. & Pollnau, M. “Organic solid-state integrated amplifiers and lasers”, Laser Photon. Rev. 6, 419-462 (2012)) and colloidal QDs (50% drop in output power after about 106 laser shots; Chan, Y. et al. “Blue semiconductor nanocrystal laser”, Appl. Phys. Lett. 86, 073102 (2005)). The impressive ASE stability of the perovskite layers is also evident from tests of perovskite solar cells irradiated for about 8 h under ambient conditions (FIG. 7E).
FIG. 12C is a plot 1200c showing the PL spectrum at 10 K. The dotted lines are the deconvolved Gaussian peaks. The dashed lines in the false colour temperature-dependent PL map show the evolution of the emission peaks with temperature. FIG. 12D is a plot 1200d showing wide wavelength tunability of ASE wavelengths from low-temperature solution-processed organic-inorganic halide perovskite films fabricated by mixing the precursor solutions.
In the absence of any significant defect concentrations, the SE may originate from the bandedge emission. Because the SE may provide the seed photons for the photon cascade in ASE, the ASE wavelengths may be in turn dependent on the bandgap of the semiconducting film. This is clearly evident from our temperature-dependent studies, where an increase in the bandgap due to a tetragonal to orthorhombic phase transition results in a blue-shifted SE and a corresponding shift in the ASE (FIG. 12C). The orthorhombic phase may give rise to three emission peaks, attributed to two bound exciton emissions (815 nm and 782 nm) and a free exciton emission (746 nm), which yields the low-temperature ASE peak (at a threshold fluence of 10±2 μJ cm−2. Such an intrinsic dependence of the ASE on the bandgap may allow wavelength tunability through halide substitution. By using either mixtures of bromides and iodides or chlorides and iodides, the bandgap may be continuously tunable over the entire visible spectral range (from about 390 to about 790 nm). We realize this through a simple physical mixing of the precursor solutions before spin-coating.
FIG. 12D is a plot 1200d showing the ASE from CH3NH3PbCl3, CH3NH3PbCl1.5Br1.5, CH3NH3PbBr3, CH3NH3PbBrI2 and CH3NH3PbI3 thin films, demonstrating its wide wavelength-tunability. The ability of the perovskites to encompass the full visible spectrum may allow them to address the ‘green gap’ seen in III-nitrides and III-phosphides. Lasing in perovskites may be achieved with a suitably designed cavity resonator (for example, with microspheres as whispering galley mode lasing or with gratings as distributed feedback lasing). Towards this lasing has also been observed from CH3NH3PbI3 single crystals from dropcast thin films (FIGS. 10A-C). This shows that despite the relatively lower PLQY measured, the impressive gain, the large absorption cross-section, low defect densities, low bimolecular recombination and slow Auger recombination in CH3NH3PbI3 enables lasing.
FIG. 13A is a plot 1300a showing the time-integrated PL spectra measured at 760±10 nm for quartz/CH3NH3PbI3 (65 nm) (indicated by line 1302a), quartz//CH3NH3PbI3 (65 nm)/PCBM (indicated by 1304a), quartz/CH3NH3PbI3 (65 nm)/Spiro-OMeTAD (indicated by 1306a) films in vacuum following excitation at 600 nm (1 KHz, 150 fs, 1.3 μJ/cm2). FIG. 13B is a plot 1300b showing TRPL decay transients measured at 760±10 nm for quartz/CH3NH3PbI3 (65 nm) (indicated by line 1302b), quartz/CH3NH3PbI3 (65 nm)/PCBM (indicated by line 1304b), quartz/CH3NH3PbI3 (65 nm)/Spiro-OMeTAD (indicated by line 1306b) films in vacuum following excitation at 600 nm (1 KHz, 150 fs, 1.3 μJ/cm2). The solid lines in FIG. 13B are the single-exponential fits of the PL decay transients. FIG. 13C is a plot 1300c of exciton diffusion length as a function of PL lifetime quenching ratios. FIG. 13C is based on equation (5). Diffusion length is scaled in multiples of CH3NH3PbI3 layer thickness (L=65 nm). A consequence of the low trap density within this perovskite gain medium may include long range balanced electron and hole diffusion lengths, which guarantee the good electron and hole injection. It may therefore possible to achieve efficient electrical-driven lasing in this class of materials.
Various embodiments may be fabricated using a low temperature solution processed approach. In contrast, traditional semiconductor gain media are usually produced at elevated temperatures and using high vacuum growth techniques that require significant infrastructural investments.
Further, a solution processable gain medium according to various embodiments may have much greater versatility than traditional gain media for integration with existing silicon based technologies. It may be applied to a much wider range of optical cavity designs and substrates by simply spin-coating, dip-coating or dropcasting.
The lasing wavelength in these classes of materials may be determined by the band to band transition. The energetic separation between the bands (and hence the lasing wavelength) can be modified by facile substitution of either the metal or the organic component or the halide. This can allow lasing wavelengths from the visible to the infrared.
Our findings show that these organic-inorganic halide semiconductors may be a new class of robust solution-processed gain media with highly desirable characteristics. The low ASE threshold and the long-range balanced charge carrier diffusion length may stem from the low bulk defect density in CH3NH3PbI3 films. The highly crystalline PbX6 three-dimensional network may lend crystalline inorganic character to CH3NH3PbX3 while maintaining its solution processability. Broad wavelength tunability is possible with both cation and anion replacement. Their low-temperature solution processing may be highly compatible with unconventional substrates, printing technologies and monolithic integration with silicon-based electronics. Together with the long-range balanced electron and hole diffusion, high charge carrier mobilities and low bimolecular charge recombination rates, as well as large wavelength range continuously tunable coherent emission, our findings indicate that the simple solution-processed CH3NH3PbX3 may hold the key to realizing electrically driven solution-processed on-chip coherent light sources.
Low temperature solution processed photovoltaics suffer from low efficiencies due to poor exciton/electron-hole diffusion lengths (typically about 10 nanometers). Recent reports of highly efficient CH3NH3PbI3-based solar cells in a broad range of configurations raise a compelling case for understanding the fundamental photophysical mechanisms in these materials. By applying femtosecond transient optical spectroscopy to bilayers that interface this perovskite with either selective electron or selective hole extraction materials, we have uncovered concrete evidence of balanced long-range electron-hole diffusion lengths of at least 100 nm in solution processed CH3NH3PbI3. The high photoconversion efficiencies of these systems stem from the comparable optical absorption length and charge carrier diffusion lengths, transcending the traditional constraints of solution processed semiconductors.
An ideal solar cell material should combine good optical absorption characteristics with efficient charge transport properties. Low temperature solution processed light harvesting films prepared by techniques such as spin coating and chemical bath deposition are typically amorphous or poorly crystalline, consequently suffering from poor charge carrier transport. This limitation necessitates device designs that decouple light absorption and charge carrier transport lengths, including light trapping strategies such as plasmonics as well as the sensitized solar cell architecture. The recent development of organic-inorganic halide perovskite materials such as CH3NH3PbI3 as light harvesters in solid state sensitized solar cells has led to reports of impressive efficiency values of up to 15%. This remarkable material has been employed in a variety of photovoltaic architectures. A configuration employed by Kim et al. (H. S. Kim et al., “Lead iodide perovskite sensitized all-solid-state submicron thin film mesoscopic solar cell with efficiency exceeding 9%”, Scientific Reports 2, 591 (2012)) and Heo et al. (J. H. Heo et al., Efficient inorganic-organic hybrid heterojunction solar cells containing perovskite compound and polymeric hole conductors. Nature Photonics 7, 486 (2013)), sandwiches the thin perovskite layer between a rough mesoporous TiO2 photoanode and a hole transporting layer such as (2,2′,7,7′-tetrakis(N,N-di-p-methoxyphenylamine)-9,9′-spirobi-fluorene (Spiro-OMeTAD). Lee et al. (M. M. Lee, J. Teuscher, T. Miyasaka, T. N. Murakami, H. J. Snaith, “Efficient hybrid solar cells based on meso-superstructured organometal halide perovskites”, Science 338, 643 (2012)) have shown that efficient solar cells can be fabricated by replacing the TiO2 photoanode with an insulating Al2O3 scaffold—implying good electron transport properties. Surprisingly, Etgar et al. (L. Etgar et al., Mesoscopic CH3NH3PbI3/TiO2 heterojunction solar cells. Journal of the American Chemical Society 134, 17396 (2012)) reported an efficiency of 5.5% in a configuration without the hole transporting layer—indicating good hole transport properties. These indications of ambipolar charge transport capabilities are supported by a recent report by Ball et al. (J. M. Ball, M. M. Lee, A. Hey, H. J. Snaith, Low-temperature processed mesosuperstructured to thin-film perovskite solar cells. Energy and Environmental Science 6, 1739 (2013)) which demonstrated that  ̃350 nm thick planar films sandwiched between a TiO2 compact layer and a hole transporting layer can generate short circuit current densities of 15 mA/cm2. These reports together imply that the electron and hole transport lengths within these organic-inorganic hybrid materials are high. Nonetheless, the innate dynamics of the photoexcited electrons and holes in CH3NH3PbI3 driving the high efficiencies in these solar cells are unknown. Herein, through femtosecond transient optical spectroscopy of CH3NH3PbI3 heterojunctions with selective electron and hole extraction, we successfully decouple electron and hole dynamics and show clear evidence of long electron and hole transport lengths (both over 100 nm). Our findings indicate that this class of materials does not suffer from the bottleneck of low collection lengths which handicap typical low temperature solution processed photovoltaic materials.
FIG. 14A is am illustration 1400a showing the absorbance and transmission spectra of CH3NH3PbI3, CH3NH3PbI3/PCBM, CH3NH3PbI3/Spiro-OMeTAD. 1410 shows the absorbance spectra for pure CH3NH3PbI3. 1420 shows the differential transmission spectra for CH3NH3PbI3. 1430 shows the differential transmission spectra for CH3NH3PbI3/PCBM. 1440 shows the differential transmission spectra for CH3NH3PbI3/Spiro-OMeTAD. The films are in vacuum and the spectra are measured at 600 nm (1 KHz, 150 fs, 13 μJ/cm2). Lines 1422, 1432, 1442 are measured at 1 ps. Lines 1424, 1434, 1444 are measured at 100 ps. Lines 1426, 1436, 1446 are measured at 500 ps. Lines 1428, 1438, 1448 are measured at Ins.
FIG. 14B is an illustration 1400b showing normalized bleaching kinetics for films in vacuum following excitation at 600 nm (1 KHz, 150 fs, 1.3 μJ/cm2). 1450 shows the normalized bleaching kinetics at 480 nm while 1460 shows the normalized bleaching kinetics at 760 nm. 1452, 1462 represent the data for CH3NH3PbI3. 1454, 1464 represent the data for CH3NH3PbI3/PCBM. 1456, 1466 represent the data for CH3NH3PbI3/Spiro-OMeTAD.
FIG. 15A is an illustration 1500a of normalized bleaching kinetics in short time range showing the inter-valence band hot hole cooling for CH3NH3PbI3 (in vacuum) following excitation. 1510 shows the early time dynamics following excitation at 400 nm (1 μJ/cm2). 1520 shows the early time dynamics following excitation at 600 nm (1.3 μJ/cm2). 1512, 1522 represent the data at 480 nm while 1514, 1524 represent the data at 760 nm.
FIG. 15B is a schematic 1500b illustrating the hot hole cooling and charge recombination within CH3NH3PbI3 and charge separation at the CH3NH3PbI3/PCBM and CH3NH3PbI3/Spiro-OMeTAD interfaces. The approximate positions of VB1 and VB2 were obtained from the TA measurements.
FIG. 16 is a schematic 1600 of the energy levels of the heterojunctions and depiction of the exciton generation, diffusion and quenching processes in the respective bilayers.
FIG. 17 is a plot 1700 showing step profiles of the thickness of the CH3NH3PbI3, CH3NH3PbI3/PCBM and CH3NH3PbI3/Spiro-OMeTAD films. 1702 shows the step profile of CH3NH3PbI3 film. 1704 shows the step profile of CH3NH3PbI3/PCBM film. 1706 shows the step profile of CH3NH3PbI3/Spiro-OMeTAD film.
FIG. 18 is a cross-sectional transmission electron microscopy image 1800 of a typical trilayer showing the clear interfaces between the perovskite and the electron and hole acceptor layers. FIG. 19 is a plot 1900 of absorption coefficient of CH3NH3PbI3 as a function of wavelength—calculated from equation (6).
FIG. 20 is a schematic 2000 showing 4 possible scenarios for the two peaks (480 nm and 760 nm) observed in the linear absorption and TA spectra.
FIG. 21 is a plot 2100 showing normalized probe wavelength dependent kinetics for CH3NH3PbI3 film in vacuum following excitation at 600 nm (0.7 μJ/cm2). The signals at 640 nm and 700 nm were reversed for better comparison. Note the zero crossing of the signals at timescale below 1 ps for the 700 nm probe. This signature is characteristic of hot charge carrier cooling in the short timescales. 2102 is measured at 480 nm, 2104 is measured at 640 nm. 2106 is measured at 700 nm and 2108 is measured at 760 nm.
FIG. 22 is a plot 2200 showing normalized pump fluence dependent kinetics at 760 nm for CH3NH3PbI3 film vacuum following excitation at 600 nm. 2202 represents a pump fluence of 0.7 μJ/cm2, 2204 represents a pump fluence of 1.3 μJ/cm2, 2206 represents a pump fluence of 2.6 μJ/cm2, and 2208 2204 represents a pump fluence of 6.5 μJ/cm2,
FIG. 23 is an illustration 2300 showing pump fluence dependent dynamics for CH3NH3PbI3 (lines 2314a, 2316a, 2318a, 2322a, 2324a, 2326a, 2328a) and CH3NH3PbI3 (dots 2314b, 2316a, 2318b, 2322b, 2324b, 2326b, 2328b) in vacuum. 2310 shows the pump fluence dependent dynamics at 480 nm while 2320 shows the pump fluence dynamics at 760 nm. 2322a, 2322b are for a pump fluence of 0.7 μJ/cm2. 2314a, 2314b, 2324a, 2324b are for a pump fluence of 1.3 μJ/cm2, 2316a, 2316b, 2326a, 2326b are for a pump fluence of 2.6 μJ/cm2. 2318a, 2318b, 2328a, 2328b are for a pump fluence of 6.5 μJ/cm2.
FIG. 24 is a plot 2400 showing pump fluence dependent relative PL quantum yield with 600 nm, 150 fs and 1 KHz laser pulse excitation. 2402 shows the data for CH3NH3PbI3/PCBM while 2404 shows the data for CH3NH3PbI3/Spiro-OmeTAD.
FIG. 25 is a table 2500 showing relative photoluminescence (PL) quantum yield (çPL), PL decay time (τPL), TA decay time (τTA) and the estimated charge transfer time (τCT) from the TA results.
In this study, electron extraction layers (such as [6,6]-phenyl-C61-butyric acid methyl ester (PCBM), C60) with conduction band levels below that of CH3NH3PbI3 and hole extraction layers (such as Spiro-OMeTAD, poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS)) with valence band levels above CH3NH3PbI3 were interfaced to CH3NH3PbI3 to permit decoupling of the electron and hole dynamics (FIG. 16). Comparing measurements on bare CH3NH3PbI3 against CH3NH3PbI3/hole acceptor bilayers and CH3NH3PbI3/electron acceptor bilayers enables identification of electron and hole signatures in the organic/inorganic halide.
Under identical experimental conditions, the photoluminescence (PL) quantum yield of the 65 nm thick CH3NH3PbI3 is greatly reduced when the perovskite is interfaced with an electron extracting PCBM layer or a hole extracting Spiro-OMeTAD layer (FIG. 13A). The PL intensity is quenched by a factor of 12.5 in the bilayer with Spiro-OMeTAD and by a factor of 50 in the bilayer with PCBM (FIG. 25). Given that the current configurations are ideal layered systems (FIG. 17 and FIG. 18), these high degrees of PL quenching, comparable to closely blended donor/acceptor system, are particularly revealing. Given a linear absorption coefficient of 5.7×104 cm−1 at 600 nm (1410 in FIG. 14A, FIG. 19), near homogenous generation of the charge carriers in these 65 nm CH3NH3PbI3 layers can be ensured. The PL quenching is expected to originate from the charge carrier extraction across the interface.
Efficient PL quenching suggests that the charge carrier diffusion length inside the CH3NH3PbI3 layer is comparable to or longer than the layer thickness (65 nm). Correspondingly, the PL lifetimes were also significantly shortened when CH3NH3PbI3 was interfaced with the PCBM or Spiro-OMeTAD layer (FIG. 13B)—with fitted lifetimes of 4.5 (±0.3) ns, 0.37 (±0.02) ns and 0.64 (±0.03) ns for the CH3NH3PbI3, CH3NH3PbI3/PCBM and CH3NH3PbI3/Spiro-OMeTAD, respectively. The single exponential PL decay indicates the good crystalline quality of the samples. Using the relation (1/τHeterojunction=1/τPerovskite+1/τCT), the charge carrier transfer times τCT (and efficiency) can be estimated to be 0.40 ns (92%) and 0.75 ns (86%) for CH3NH3PbI3/PCBM and CH3NH3PbI3/Spiro-OMeTAD, respectively. The slight variation between the charge carrier transfer efficiencies obtained using steady state PL (FIGS. 13A, 25) and transient PL can be attributed to: (i) extremely fast charge carrier transfer at the interface (that cannot be monitored at the current temporal resolution); and (ii) the dependence of the steady state PL on the light reflection, scattering and refraction by the additional PCBM and Spiro-OMeTAD layers in the heterojunctions. Next, a charge carrier extraction model based on diffusion was employed to estimate the charge carrier diffusion lengths. FIG. 13C shows the dependence of the charge carrier diffusion length on the PL lifetime quenching ratios obtained from the analytical solution of the model. Assuming that charge carrier quenching occurs only at the extraction layer interface with 100% efficiency, minimum estimates of the extracted electron and hole diffusion lengths are 130 nm and 90 nm. By comparison, solution processed organic conjugated materials have typical diffusion lengths about 10 nm; thermally deposited organic molecules have typical diffusion lengths of 10-50 nm; and colloidal quantum dot films have diffusion lengths  ̃30 nm (organic cross-linked) and  ̃80 nm (hybrid surface passivated). Thus the conservatively estimated long diffusion lengths in the low temperature solution processed CH3NH3PbI3 films compare favorably.
To improve the accuracy of these estimated values from the direct PL approach and obtain more details on the photo-excited charge carrier dynamics, complementary transient absorption spectroscopy (TAS) measurements were also performed. Due to the large absorption coefficients and the long charge carrier diffusion lengths, low pump fluence is essential to avoid extensive Auger recombination in CH3NH3PbI3—see FIGS. 21 to 24. 1410 in FIG. 14A shows the linear absorption spectrum of CH3NH3PbI3 spanning the UV to near infrared (800 nm) with two distinct peaks located at 480 nm and 760 nm, in agreement with earlier publications. The second absorption peak (760 nm) is attributed to the direct gap transition from the first valence band maximum (VB1) to the conduction band minimum (CB1). However, the origin of the first absorption peak (480 nm) is still unresolved.
Representative TA spectra of CH3NH3PbI3 and its bilayer counterparts over the same spectral region are shown in 1420, 1430, 1440 (FIG. 14A)—with two pronounced photo-bleaching (PB) bands. These long-lived PB peaks are located at almost the same spectral positions as the two absorption peaks. The PB at 480 and 760 nm are labeled as PB1 and PB2, respectively, and are attributed to state-filling. For 600 nm photo-excitation, it is reasonable to attribute the 760 nm PB2 band to state filling effects (which include the hole population of VB1, the electron population of CB1 and the inter-band stimulated emission).
However, it is not straightforward to assign the transitions associated with the 480 nm PB1 band. Given that the photo-excitation energy (of  ̃2.06 eV for 600 nm wavelength) is smaller than the energy of the PB1 peak (2.58 eV), only one of the two energy states involving this PB transition could be populated. The long-lived nature of this PB band further suggests that the populated energy level should be either VB1 or CB1 (see SM for a more detailed discussion of the assignment).
Upon selective excitation of the CH3NH3PbI3 layer, no new PB or photoinduced absorption bands are observed when the electron or hole extraction layer is present. A comparative study at the respective probe wavelengths of PB1 and PB2 would thus yield detailed information about the charge carrier dynamics. For pure CH3NH3PbI3, the recombination dynamics at different probe wavelengths are relatively invariant over a range of pump fluences where second order effects are insignificant (FIG. 21). All these decay transients are well-fitted with a single exponential time constant of 5.6 (±0.1) ns, which is longer than the measured PL lifetime of 4.5 (±0.3) ns (FIG. 25). As time-resolved PL cannot monitor the recombination dynamics of all the photo-excited carriers, this finding suggests that the PL lifetime in pure CH3NH3PbI3 is limited by the minority carrier lifetime. Correlating these PL lifetimes with the TA lifetimes of the bilayers allows us to identify the minority charge carriers. With the PCBM (electron acceptor) layer present, both PB1 and PB2 bleaching peaks show an additional fast lifetime component of 0.37 (±0.02) ns (FIG. 14B), which is closely matched to the measured PL lifetime. This suggests that electrons are the minority charge carriers in CH3NH3PbI3. Since PB1 and PB2 dynamics are simultaneously affected by the electron extraction layer, the probes monitor the electron population in the CB1. For the CH3NH3PbI3/Spiro-OMeTAD (hole acceptor) samples, only PB2 exhibits an additional fast decay lifetime of 0.59 (±0.03) ns (1450, FIG. 14B), which is slightly faster than the PL lifetime of 0.64 (±0.03) ns (FIG. 25). This indicates that PB2 also reflects the hole population of VB1 (i.e., the transitions between VB1 and CB1). PB1 on the other hand is only related to the electron population in CB1 (i.e., the transitions between the lower valence band (VB2) and CB1) (FIG. 15B). By comparing the PB1 decays between pure CH3NH % PbI3 and CH3NH3PbI3/PCBM, we determined electron extraction time and efficiency values in CH3NH3PbI3/PCBM to be 0.40 ns (±0.05) and 68%. 1450 (FIG. 14B) also shows that about 27% of the photo-generated electrons are possibly trapped, and therefore contribute neither to the electron extraction from CH3NH3PbI3 to PCBM, nor to the radiative recombination. By comparing the decay at PB2 between pure CH3NH3PbI3 and CH3NH3PbI3/Spiro-OMeTAD, we estimate the hole extraction time in CH3NH3PbI3/Spiro-OMeTAD to be 0.66 (±0.05) ns.
However, given that the TA signal at PB2 is a combination of signals from both electrons and holes, it is difficult to estimate the detailed hole extraction efficiency at this stage. The origins of PB1 and PB2 suggest the possibility of hot holes cooling from VB2 to VB1 following excitation of CH3NH3PbI3 across the VB2-CB1 gap. Such hot hole cooling dynamics could be validated through varying the pump wavelengths.
After 3.10 eV (400 nm) excitation, 1510 (FIG. 15) shows a very fast bleach buildup for PB1 which is close to the 150 fs laser pulse duration. Subsequently, hole localization from VB2 to VB1 occurs (within  ̃0.4 ps). The decay of the PB1 transient (indicative of the depopulation of VB2) is well-matched with a concomitant rise of the bleach signal at PB2 (indicative of VB1 being populated)—both at 0.4±0.1 ps. On the other hand, excitations with lower energy photons (e.g. across the VB1-CB1 gap using 2.07 eV (600 nm) pulses), do not excite carriers in VB2 and therefore, such hot hole cooling dynamics are absent (FIG. 3B). This 0.4 ps hot hole cooling is much slower than that in most organic semiconductors ( ̃100 fs). Potentially, these hot hole energies could be efficiently extracted before the hot holes cool down to VB1 through optimizing the device configuration.
From fitting the TA decay dynamics with the diffusion model, the electron and hole diffusion coefficients were found to be 0.036 and 0.022 cm2/s, respectively. Using these values, the electron and hole diffusion lengths (LD) perpendicular to the film surface were calculated to be LDe=130 nm and LDh=110 nm where LD=√{square root over (DτTA)}. As expected, the LDh (majority carrier diffusion length) determined here is longer than that extracted from the more direct PL approach presented earlier, which is sensitive to the minority carrier dynamics. The long transport lengths associated with CH3NH3PbI3 are linked to its crystal structure, which includes corner-connected PbI6 octahedra that form a three-dimensional framework.
Other organic/inorganic halide materials based on Sn have also displayed good charge transport properties. The slightly shorter diffusion length of the holes compared to the electrons is consistent with the hole's larger effective mass and larger positive space charge limited transport. Nonetheless, these values are relatively balanced as compared to typical values reported in bulk heterojunction solar cells where the electron and hole transport lengths (proportional to their mobility) differ by orders of magnitude resulting in space charge limited photocurrents. These balanced long charge carrier diffusion lengths would account for the remarkable performances reported for these CH3NH3PbI3 devices.
These LD values are underestimated mainly because of the assumption that no quenching at the CH3NH3PbI3-quartz or -vacuum interfaces occur. The measured carrier lifetimes, τ0 are more susceptible to the non-ideality of these interfaces in these thinner spincoated CH3NH3PbI3 layers, leading to smaller τ0 and consequently shorter LD. Measurements in more “bulk-like” samples would yield longer τ0 and higher LD(submicron)—FIG. 13C. From the linear absorption coefficients (1410, FIG. 14A), the absorption lengths are La  ̃100 nm (at ë=500 nm). These conservatively estimated carrier diffusion lengths measured in CH3NH3PbI3 are comparable to the optical absorption lengths for λ≦500 nm, but are shorter than the absorption lengths at longer wavelengths. Increasing the optical thickness of these layers through light trapping architectures compensates for this slight mismatch—accounting for the high photoconversion efficiencies reported in these systems.
Methods and Materials. [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) layers were spincoated from a solvent mixture (10 mg/ml) of anhydrous chlorobenzene and anhydrous chloroform (1:1 v/v) while PEDOT:PSS employed in the study was CleviosTM Al 4083) layer. (2,2′,7,7′-tetrakis(N,-di-p-methoxyphenylamine)-9,9-spirobifluorene) (Spiro-OMeTAD) films were prepared by spincoating 20 mg/ml solutions in chlorobenzene. The CH3NH3PbI3 films were prepared by spincoating 10 wt % solutions in anhydrous DMF. The samples were stored in vacuum for more than 3 days to rid them of any residual solvent before the optical measurements. FIG. 16 shows the schematic energy levels of the donor and acceptors materials utilized in this work. The thickness of the studied films was determined with Step-Profile measurements (FIG. 17) and matches well with values extracted from TEM imaging (FIG. 18).
All optical measurements were conducted in an optical cryostat under vacuum. For femtosecond optical spectroscopy, the laser source was a Coherent LegendTM regenerative amplifier (150 fs, 1 KHz, 800 nm) that was seeded by a Coherent VitesseTM oscillator (100 fs, 80 MHz). 800 nm wavelength laser pulses were from the regenerative amplifier's output while 400 nm wavelength laser pulses were obtained through doubling the fundamental 800 nm pulses with a BBO crystal. 600-nm laser pulses were generated from a Light Conversion TOPAS-C optical parametric amplifier. The emission from the samples was collected at a backscattering angle of 150° by a pair of lenses and into an optical fiber that is coupled to a spectrometer (Acton. Spectra Pro 2500i) to be detected by a charge coupled device (CCD) camera (Princeton Instruments, Pixis 400B). Time-resolved PL was collected using an Optronis OptoscopeTM streak camera system which has an ultimate temporal resolution of  ̃10 ps. For femtosecond TA experiments, the samples were pumped at 2.07 eV (or 3.1 eV) and probed with a white-light continuum. The probe pulses (420-820 nm) were generated by focusing a small portion ( ̃5 μJ) of the fundamental 800 nm laser pulses into a 2 mm-thick sapphire plate. The linear polarization of the pump pulse was adjusted to be perpendicular to that of the probe pulse with a polarizer and a half waveplate. The cross-polarization will eliminate any contribution from coherent artifacts at early times. Pump-induced changes of transmission (DT/T) of the probe beam were monitored using a monochromator/PMT configuration with lock-in detection. The pump beam was chopped at 83 Hz and this was used as the reference frequency for the lock-in amplifier.
The optical transmittance and total reflectance spectra of CH3NH3PbI3 on quartz substrate and blank quartz substrate were measured with a UV-VIS-NIR spectrophotometer (Shimadzu UV-3600) with an integrating sphere (ISR-3100). The absorption coefficient of the ultrathin CH3NH3PbI3 film was calculated using the following expression:




  
    
      
        
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where Rsub, Tsub and dsub are the substrate reflectance, transmittance and thickness, respectively. Rtot, Ttot and dtot are reflectance, transmittance and thickness of the substrate/film system, respectively. dfilm is the CH3NH3PbI3 film thickness. With equation (6), the interface effect between substrate and film can be taken into account.

Diffusion Model. The charge carrier diffusion lengths (LD) in the active layer can be estimated using a simple diffusion limited quenching model in a bilayer system. The laser pulse generated charge carrier density in the active layer can be described by a one-dimensional diffusion equation:




  
    
      
        
          
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where n(z, t) is the charge carrier density, D is the charge carrier diffusion coefficient, k is the original charge carrier consumption rate without the acceptor layer. The spatial coordinate z represents the vertical distance of a point in the active layer from the quartz/active layer interface. With fs laser pulse excitation, the initial photo-generated charge carrier distribution in the active layer can be expressed as:

n(z,0)=n(0)e−αz  (8)

where á is the linear absorption coefficient of the active layer at the excitation wavelength. Assuming that the donor/acceptor interface is the only quenching interface with infinite quenching rate, a minimum estimate of LD will be obtained. Solving Equation 7 with the initial charge carrier distribution and boundary conditions yields the time dependent charge carrier distribution (n(z, t)) and total charge number (N(t)) within the active layer:





  
    
      
        
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                            ⁢
                            D
                          
                          
                            L
                            2
                          
                        
                      
                      ⁢
                      
                        
                          (
                          
                            m
                            +
                            
                              1
                              2
                            
                          
                          )
                        
                        2
                      
                      ⁢
                      t
                    
                    )
                  
                
                ⁢
                
                  
                    
                      
                        exp
                        ⁡
                        
                          (
                          
                            
                              -
                              α
                            
                            ⁢
                            
                              
                            
                            ⁢
                            L
                          
                          )
                        
                      
                      ⁢
                      
                        π
                        ⁡
                        
                          (
                          
                            m
                            +
                            
                              1
                              2
                            
                          
                          )
                        
                      
                    
                    +
                    
                      
                        
                          (
                          
                            -
                            1
                          
                          )
                        
                        m
                      
                      ⁢
                      α
                      ⁢
                      
                        
                      
                      ⁢
                      L
                    
                  
                  
                    
                      (
                      
                        
                          
                            (
                            
                              α
                              ⁢
                              
                                
                              
                              ⁢
                              L
                            
                            )
                          
                          2
                        
                        +
                        
                          
                            
                              π
                              2
                            
                            ⁡
                            
                              (
                              
                                m
                                +
                                
                                  1
                                  2
                                
                              
                              )
                            
                          
                          2
                        
                      
                      )
                    
                    ⁢
                    
                      (
                      
                        m
                        +
                        
                          1
                          2
                        
                      
                      )
                    
                  
                
              
              )
            
          
        
      
    
    
      
        (
        10
        )
      
    
  




where L is the active layer thickness.

Interpretation for Photobleaching (PB) Peaks at 480 nm and 760 nm.
From the linear absorption spectrum in FIG. 19, the PB peaks could originate from one of the four possible scenarios as shown in FIG. 20 (A): separate valence bands to separate conduction bands transitions (i.e., VB1→CB1 and VB2→CB2); (B) common valence band to separate conduction bands transitions (i.e., VB1→CB1 and VB1→CB2): (C) separate valence bands to common conduction band transitions (i.e., VB1→CB1 and VB2→CB1); and (D) a mixture of two photo-systems with independent transitions. Energy band alignments could be a type I or type II configuration.
Scenario A: The long-lived nanosecond PB transient measured at 480 nm would exclude this situation because hot carrier relaxation to the lower levels would occur on a much faster picoseconds timescale.
Scenario D: The schematic represents a general situation where the band alignment could be either (a) a type I band alignment where the smaller bandgap system is located within the wider bandgap system: or (b) a type II band alignment where the energy bands of the two systems are staggered. Nonetheless, the following discussion is applicable. For the 600 nm pump pulse to yield two bleaching peaks at PB1 and PB2, a charge transfer from the smaller bandgap system (760 nm) to the larger bandgap system (480 nm) must have taken place. A key signature of such charge transfer is a concomitant decrease in the 760 nm probe signal with a rise in the 480 nm probe signal over the same time frame. This is not observed, thus eliminating Scenario D altogether.
Differentiating Scenario B and C: In Scenario B, the dependence of the dynamics at the two wavelengths could be described by:




  
    
      
        
          
            
              Δ
              ⁢
              
                
              
              ⁢
              T
            
            T
          
          ⁢
          
            (
            
              760
              ⁢
              
                
              
              ⁢
              nm
            
            )
          
        
        =
        
          
            
              k
              1
            
            ⁢
            
              n
              e
            
          
          +
          
            
              k
              2
            
            ⁢
            
              n
              h
            
          
        
      
    
    
      
        (
        11
        )
      
    
  
  
    
      
        
          
            
              Δ
              ⁢
              
                
              
              ⁢
              T
            
            T
          
          ⁢
          
            (
            
              480
              ⁢
              
                
              
              ⁢
              nm
            
            )
          
        
        =
        
          
            k
            3
          
          ⁢
          
            n
            h
          
        
      
    
    
      
        (
        12
        )
      
    
  




where k1, k2 and k3 are proportionality constants and ne and nh are the electron and hole populations at CB1 and VB1. The transition at 480 nm does not depend on ne since the hot electron at CB2 decays within 1 ps.

In Scenario C, the dependence of the dynamics at the two wavelengths could be described by:





  
    
      
        
          
            
              Δ
              ⁢
              
                
              
              ⁢
              T
            
            T
          
          ⁢
          
            (
            
              760
              ⁢
              
                
              
              ⁢
              nm
            
            )
          
        
        =
        
          
            
              k
              1
            
            ⁢
            
              n
              e
            
          
          +
          
            
              k
              2
            
            ⁢
            
              n
              h
            
          
        
      
    
    
      
        (
        13
        )
      
    
  
  
    
      
        
          
            
              Δ
              ⁢
              
                
              
              ⁢
              T
            
            T
          
          ⁢
          
            (
            
              480
              ⁢
              
                
              
              ⁢
              nm
            
            )
          
        
        =
        
          
            k
            3
          
          ⁢
          
            n
            e
          
        
      
    
    
      
        (
        14
        )
      
    
  




where k1, k2 and k3 are proportionality constants and ne and nh are the electron and hole populations at CB1 and VB1.

For the CH3NH3PbI3/PCBM bilayer, the dynamics originating from ne will be affected; while for the CH3NH3PbI3/Spiro-OMeTAD bilayer, the dynamics originating from nh will be affected. Experimentally, both 480 nm (PB1) and the 760 nm (PB2) transients are modulated in the presence of the electron accepting PCBM—indicating that the CB1 is participating in both the transitions. In addition, only the 760 nm transition (PB2) is affected by the presence of the hole accepting Spiro-OMeTAD—indicating that VB2 is participating in this transition. This eliminates Scenario B and confirms Scenario C.
Second Order Effects—Auger Recombination. It was found that these carrier dynamics are strongly pump fluence dependent due to the large light absorption coefficient ( ̃5.7×104 cm−1 at 600 nm (FIG. 19) and long charge carrier diffusion length in CH3NH3PbI3. For pump fluence≦1.3 μJ/cm2, multi-particle Auger recombination process in CH3NH3PbI3 is insignificant and the TA decay transients are identical to those presented earlier (FIGS. 21, 22). However, for a pump fluence>2.6 μJ/cm2 (i.e., photo-generated exciton density >3.7×1017/cm3), Auger recombination will dominate over the linear recombination, resulting in a shortening of the TA lifetimes. The existence of Auger recombination under these relatively low exciton densities points towards an extremely long exciton-exciton or exciton-charge interaction length ( ̃μm) in CH3NH3PbI3—consistent with the long carrier diffusion lengths determined in this work. Under high pump fluence, the lifetime shortening induced by the interface charge carrier extraction in the bilayers will be overshadowed by the lifetime shortening caused by Auger recombination (FIG. 23). Therefore, careful regulation of the pump fluence in the ultrafast optical spectroscopy of CH3NH3PbI3 is essential for uncovering its intrinsic properties. As shown in FIG. 24, the relative PL quantum yields (ηPL) of CH3NH3PbI3/PCBM and CH3NH3PbI3/Spiro-OMeTAD to CH3NH3PbI3 layer are strongly dependent on the pump fluence used. At relative low pump fluence (where Auger recombination is insignificant), ηPL is independent of the pump fluence. However, when Auger effects become more dominant, ηPL increases with pump fluence. The variation of ηPL with pump fluence is more obvious for CH3NH3PbI3/Spiro-OMeTAD than for CH3NH3PbI3/PCBM. This is attributed to the slower hole diffusion compared to the electron diffusion in CH3NH3PbI3—consistent with the hole's larger effective mass and larger space charge limited transport. All our PL measurements were performed in the linear range with low pump fluence.
The development of near infrared laser with low band gap semiconductors may typically be limited by the low quantum efficiency (QE) of the gain materials and magnified Auger losses with decreasing bandgap. Auger recombination is a type of non-radiative process that becomes significant for high injected carrier densities (N) in semiconductors. In an inorganic semiconductor, the Auger process may involve a three-particle interaction where the energy and momentum from the recombination of an electron and hole are transferred to a third particle (electron or hole). This nonradiative process at high carrier densities may be undesirable for ASE as it may impede gain buildup and may increase the ASE threshold. The Auger process in semiconductors may be quantified by auger recombination rate (Ra) or its auger coefficient (C) where it can be expressed as follows:

Ra═CN3  (15)

The auger coefficient may vary among bulk semiconductors and may be highly dependent on several intrinsic properties, such as bandgap and temperature. Its dependence on bandgap (Eg) may be derived using Fermi's golden rule, Bloch functions and a series of approximations. The resulting expression of Ra may provide more insights and may be expressed as:





  
    
      
        
          R
          a
        
        ∝
        
          
            n
            2
          
          ⁢
          p
          ⁢
          
            
          
          ⁢
          
            e
            
              -
              
                
                  B
                  ⁢
                  
                    
                  
                  ⁢
                  
                    E
                    g
                  
                
                
                  
                    K
                    B
                  
                  ⁢
                  T
                
              
            
          
        
      
    
    
      
        (
        16
        )
      
    
  




where KB is the Boltzmann constant, T is the temperature, n and p are the electron and hole concentration respectively and B is a constant. The exponential relation shown in Equation (16) suggests that auger recombination is more severe for small band gap semiconductor and may be challenging to realize near-infrared (NIR) ASE or lasing. In quantum confined systems (e.g. quantum dot, quantum well, quantum wires etc), the spatial confinement of the photo-generated charge carriers may drastically increase the Auger rates. In the case of organic semiconductors with typical Frenkel excitons of large exciton binding energy, the dominant non-radiative process affecting ASE and lasing is the exciton-exciton annihilation process, which may also be particularly strong in small bandgap organic semiconductors. Further stumbling blocks may include intrinsic losses from fast nonradiative decay as well as the conflicting requirements of high charge carrier mobility (which require overlap of n-electron systems) and large stimulated emission (which require the chromophores to be well separated).

Inorganic lead-free perovskite (CsSnI3) films may be prepared by a low temperature solution method. Stoichiometric mixed CsI (Sigma-Aldrich, 99.9%) and SnI2 (Sigma-Aldrich, 99.99%) powder with appropriate amount of SnF2 may be dissolved in polar organic solvents (dimethyl sulfoxide (DMSO)) to give transparent yellow solutions (0.6 M) under nitrogen environment at room temperature. Black thin films may be obtained by spincoating the solution (80 μL) on quartz substrates (2 cm×2 cm) with subsequent annealing at 100° C. for 30 minutes. Poly (methyl methacrylate) (PMMA, 15 mg/mL in chlorobenzene) was coated on the CsSnI3 films to avoid degradation of the perovskites during optical measurements. FIG. 26A is a plot 2600a of intensity (arbitrary units or a.u.) as a function of 2θ (degrees) showing the X-ray diffraction (XRD) spectra of CsSnI3 thin films doped with different concentration SnF2 according to various embodiments on quartz substrates. The XRD patterns of the films indicate that perovskites may be crystallized in the orthorhombic (Pnam) structure. With additional SnF2 in the precursor solution, no obvious change in lattice parameters and crystalline phase is observed. However, the two weak peaks originated from non-orthorhombic perovskite phase in the pure CsSnI3 film are totally eliminated with the SnF2 doping. FIG. 26B is a schematic 2600b showing a perovskite structure according to various embodiments. FIG. 26C is a plot 2600c of emission intensity (arbitrary units or a.u.) as a function of wavelength (nanometers or nm) showing normalized emission at low pump fluence (open circles,  ̃1 μJ/cm2) and high pump fluence (solid lines,  ̃70 μJ/cm2) of CsSnI3 with different molar concentrations of SnF2 treatment according to various embodiments.
FIG. 26C shows about 1.3 eV (950 nm) emission from direct bandgap transitions. FIG. 26D is a plot 2600d of emission intensity (arbitrary units or a.u.) as a function of pump fluence (micro-joules per square centimeter or μJ/cm2) showing the variable fluence measurements which reveal the amplified spontaneous emission (ASE) thresholds of the SnF2-treated samples according to various embodiments. As shown in FIG. 26D, above the threshold pump fluence (PThr), the emission intensity increases superlinearly with increasing pump fluence.
FIG. 27A is a plot 2700a of photoluminescence (PL) intensity (arbitrary units or a.u.) as a function of wavelength (nanometers or nm) showing steady-state photoluminescence (PL) emission spectra from the CsSnI3 thin films (with various concentrations of SnF2 added) according to various embodiments. The plots show the transition from spontaneous emission (SE) to amplified spontaneous emission (ASE) in the SnF2 treated samples, but only SE in the untreated film. The samples were photoexcited using 650 nm laser pulses (50 fs, 1 KHz) with increasing pump fluence. FIG. 27B is a plot 2700b of photoluminescence intensity (arbitrary units or a.u.) as a function of time (picoseconds or ps) showing typical time-resolved photoluminescence (TRPL) decay transients of the CsSnI3 film with 20% SnF2 addition according to various embodiments following photo-excitation with pump fluence below (2602, 2604) and above (2606) the ASE threshold. 2602 relates to data obtained at 4 μJ/cm2, 2604 relates to data obtained at 5 μJ/cm2 and 2606 relates to data obtained at 7 μJ/cm2.
The pump fluence dependent photoluminescence (PL) and time-resolved PL (TRPL) clearly show a transition from spontaneous emission (SE) to ASE for the SnF2-treated CsSnI3 films for increasing pump fluence (FIG. 26D). Below the threshold fluence (PThr), SE linearly increases with increasing pump fluence and dominates the light output from the films with a full width at half maximum (FWHM) of  ̃80 nm. Above PThr, the emission bandwidth reduces to less than 25 nm and the emission intensity increases superlinearly with increasing the pump fluence (FIG. 26D). These are clear signatures of optical gain from SnF2 doped CsSnI3 films. However, SE merely increases continually with increasing pump fluence in the untreated CsSnI3 film, without ever achieving population inversion within the limits of its damage threshold ( ̃200 μJ/cm2).
Apart from trap states affecting the gain properties, fast nonradiative recombination from multi-particle effects (e.g., bimolecular recombination and the 3 particle Auger processes as described earlier) may present a major challenge for narrow bandgap materials. Remarkably, we find that the ASE in these SnF2-doped CsSnI3 perovskites may effectively compete with the multi-particle processes. FIG. 27B shows the PL decay transients of the transition from SE to ASE for the 20% SnF2-doped CsSnI3 film.
At a pump fluence just below the ASE threshold ( ̃5 μJ/cm2), the charge carrier radiative recombination decay dynamics exhibit a short lifetime component of  ̃110±5 ps that is dominated by multi-particle recombination (FIG. 27B).
For comparison at very low pump fluence ( ̃1 μJ/cm2), the trap-state dominated single exponential lifetime is 0.9±0.1 ns. Above the ASE threshold fluence ( ̃7 μJ/cm2), a very prominent ultrashort lifetime component of <10 ps appears in addition to the multi-particle dominated decay lifetime (83±2 ps). This ultra-short lifetime component may be attributed to the ASE where the measured 10 ps lifetime is in fact due to the limitations of the streak camera's system temporal response.
Above PThr (FIG. 27B), the PL decay transients also show a clear switch from SE ( ̃110 ps—dominated by the multiparticle interaction) to ASE (<10 ps—dominated by the photon avalanche and limited by the streak camera's temporal response). These are clear signatures of optical gain from SnF2—added CsSnI3 films. FIG. 26D shows that with increasing SnF2 addition (to ≦20%), PThr decreases progressively with values of 16±2, 7±1, 6±1 μJ/cm2 for the 5%, 10% and 20% SnF2-added CsSnI3 films, respectively (i.e. PThr5, PThr10, PThr20). However, SE merely increases continually with increasing pump fluence in the untreated CsSnI3 film, without achieving population inversion within the limits of its damage threshold. Any further increase of SnF2 concentration to beyond the optimal 20% (e.g., up to 30%) may lead to a rise in PThr instead. The PThr of 20% SnF2-doped CsSnI3 film is comparable to that reported for CH3NH3PbI3 under the same experimental conditions. This ultralow threshold of 6±1 μJ/cm2 may be among the lowest reported values for solution-processed organic or inorganic thin films (without any optical feedback cavities).
FIG. 28A is a plot 2800a of quantum yield (percent or %) as a function of pump fluence (micro-Joules per square centimeter or μJ/cm2) showing room-temperature photoluminescence quantum yield (PLQY) of 20% SnF2 treated CsSnI3 film according to various embodiments at different pump fluence. The pump-fluence dependent PL quantum yield (PLQY) of the 20% SnF2-doped CsSnI3 film was measured with an integrating sphere. The samples were excited with 650 nm pulses generated from the optical parametric amplifier (Coherent OPerA-Solo). The emission was corrected for CCD and grating responsivity. At low pump fluence of  ̃4 μJ/cm2, the PLQY is found to be  ̃3.0±0.5%. Comparatively, the pristine and the 0%, 5%, and 10% SnF2-doped CsSnI3 films yielded PLQYs of 0.6±0.1%, 1.1±0.2% and 2.0±0.3%, respectively. As expected, the PLQY increases with increased suppression of the trap states. With increasing pump fluence, the PLQY increases as the optical gain dominates the nonradiative recombination pathways. At pump fluence much larger than the ASE thresholds, a PLQY as large as 13±1% is measured for the 20% SnF2-doped CsSnI3 film. This value may be comparable to that measured for the leaded CH3NH3PbI3 system under the same experimental conditions.
FIG. 28B is a plot 2800b of photoluminescence (PL) intensity (arbitrary units or a.u.) as a function of strip length (centimeters or cm) showing variable strip length films according to various embodiments at a pump fluence of 20 μJ/cm2. With a relatively high PL quantum yield and inconsequential effects from the multi-particle recombination, large optical gain may therefore be observed from these SnF2-doped CsSnI3 films. The room temperature net gains of the CsSnI3 films were assessed using Variable Stripe Length (VSL) measurements. The data is fitted using the method developed by Shaklee and Leheny, i.e. Equation (1), which is a straightforward way to determine the net gain value of a material over the small signal regime (utilized for inorganic and organic semiconductors in slab geometry).
With the above VSL method, net gains of 120±10, 130±10 and 200±10 cm−1 are determined for the 5%, 10% and 20% SnF2-treated CsSnI3 films, respectively.
The gain of the 20% SnF2-treated CsSnI3 film may be comparable with the leaded CH3NH3PbI3 films and CsPbI3 nanocrystal films; and is better than conjugated polymer thin films and traditional colloidal nanocrystals. These results clearly show that the SnF2-treated CsSnI3 lead-free perovskite may be a very promising NIR gain medium.
To further demonstrate the outstanding intrinsic NIR lasing properties of CsSnI3 in a nonconformal and non-planar geometry, 20% SnF2-treated CsSnI3 was dropcasted on a butterfly wing (genus: delias hyparete metarete also known as Painted Jezebel, a common butterfly found in Singapore). Butterfly wings are soaked in ethanol at room temperature for 6 hours to remove impurities on the wings. At the end of 6 hours, the wings are carefully retrieved and rinsed again with ethanol. The excess solvent is subsequently removed by placing the wings in a vacuum chamber for drying. The dried wings are then stored under vacuum prior to perovskite dropcasting.
FIG. 29A is an image 2900a of an optical micrograph of a butterfly scale from the white part of the wing, while the inset shows the butterfly. FIG. 29B are images 2900b of (i) scanning electron microscopy (SEM) showing lamellae (vertical structures) in the scale (left); and (ii) simulated electric field distribution at resonant cavity mode with embedded CsSnI3 (right) according to various embodiments. The white dotted lines indicate the approximate locations of the lamella. Each scale ( ̃100 μm×80 μm) possesses near periodic and parallel corrugations (or lamella) with almost identical interspacing, supported by cross-ribs. Effectively, these scales form natural photonic crystals that may reflect different colours depending on the lamella interspacing. Here, the white part of the butterfly wing had been used. The scales have a lamella interspacing of  ̃2 μm.
FIG. 29C is a plot 2900c of emission intensity (arbitrary units or a.u.) as a function of wavelength (nanometers or nm) showing a comparison of the photoluminescence, amplified spontaneous emission (ASE), and single mode lasing of CsSnI3 (20% SnF2) according to various embodiments. The optical experiments were performed using 650 nm wavelength pump pulses (50 fs, 1 kHz). FIG. 29D is a two-dimensional pseudo-colour plot 2900d of pump fluence (micro-Joules per square centimeter or μJ/cm2) as a function of wavelength (nanometer or nm) showing the single model lasing emission spectra from the butterfly wing embedded with 20% SnF2 doped CsSnI3 according to various embodiments as a function of pump fluence. A narrow lasing peak appears above the threshold ( ̃5 μJ/cm2).
Single-mode, low threshold lasing ( ̃10 μJ/cm2) from the embedded CsSnI3 (20% SnF2) gain medium was achieved under 650 nm laser pulse excitation with an optical microscope.
The cavity lasing modal and spectral simulation were performed using the three dimensional (3D) finite-difference time-domain (FDTD) simulation software (LumericalTM) to understand the optical feedback mechanism that allows laser oscillation in the natural photonic crystal embedded with the 20% SnF2 treated CsSnI3 gain medium. Simulations were performed with the following two steps: i) First determine the effective refractive index of the butterfly wing by comparing the measured micro-area and simulated reflection spectra to determine the effective index (i.e., neff=1.4); and ii) Using neff determined in step (i), simulate the coherent light emission electromagnetic field distribution in the natural photonic cavity embedded with 20% SnF2 doped CsSnI3. FIG. 30A is a plot 3000a of intensity (arbitrary units or a.u.) as a function of wavelength (nanometers or nm) showing the measured white light scattering spectrum from white area of the butterfly wing according to various embodiments. FIG. 30B is a plot 3000b of intensity (arbitrary units or a.u.) as a function of wavelength (nanometers or nm) showing the stimulated scattering spectrum with the finite-difference time-domain (FDTD) method according to various embodiments. Though optimizing the effective refractive index of the butterfly wing, good correspondence between the measurements and the simulation results may be realized.
The refractive index of CsSnI3 is around 3.25 at around 950 nm (n=3.25). When lasing occurs in this perovskite-coated butterfly photonic crystal system, the parallel lamellas serve as the Fabry-Perot cavity and the electric field distributions at around 950 nm are shown in FIG. 29B.
The experimental results in FIGS. 29C-D, 30A correspond well with the results obtained from with the cavity mode simulation in FIGS. 29B, 30B. The laser line exhibits a FWHM of  ̃1.9 nm (limited by the resolution of spectrometer) with a relatively high Q factor (i.e., Q=λ/Δλ≧500, where λ and Δλ are the wavelength and the FWHM of the laser emission). Despite the imperfectness of a natural photonic crystal cavity, this Q value compares favorably with typical values from lithographically-pattered gratings.
The question on whether the gain mechanism in these CsSnI3 films originates from excitonic or electron-hole plasma recombination may have important implications on the laser architecture design. Presently, the origin of the CsSnI3 band edge emission from excitonic recombination or free carrier recombination may still be a matter of debate. Through detailed transient PL, it may be determined that the free carrier mechanism dominates the emission from these Pb-free perovskite gain medium.
FIG. 31A is a plot 3100a of photoluminescence (PL) intensity (arbitrary units or a.u.) as a function of time (nanoseconds or ns) showing photoluminescence decay transients of 20% SnF2-added CsSnI3 film according to various embodiments with varying pump fluence over the entire band emission range. Only selected decays at the pump fluence of 0.2 μJ/cm2 (squares), 0.4 μJ/cm2 (circles), 0.6 μJ/cm2 (up triangles), 0.8 μJ/cm2 (down triangles), 1.6 μJ/cm2 (down triangles) (diamonds), 2.4 μJ/cm2 (left-pointing triangles) and 4.0 μJ/cm2 (right-pointing triangles) are presented.
FIG. 31B is a plot 3100b of (i) initial photoluminescence intensity (IPL[t=0]) (arbitrary units or a.u.) as a function of pump fluence (micro-Joules per square centimeter or μJ/cm2) showing pump fluence dependence of the initial time photoluminescence (PL) intensity of the film according to various embodiments (upper panel); and (ii) lifetime (nanoseconds or ns) as a function of pump fluence (micro-Joules per square centimeter or μJ/cm2) showing the pump fluence dependence of photoluminescence lifetime of the film according to various embodiments (lower panel). The data shows a trap-assisted recombination (linear dependence) at low pump fluence, and a free-carrier bimolecular recombination (quadratic dependence) at high pump fluence. The optical excitation was performed with 650 nm pump pulses (50 fs, 1 KHz).
Based on the bimolecular mechanism, one may expect an increased recombination rate with increasing carrier concentrations at higher pump fluence. Indeed, this behavior may be evident from FIG. 31B (lower panel), where an inverse relation between the effective PL lifetime (defined as IPL(t)=IPL[t=0]/e) and the pump fluence (at >0.6 μJ/cm2) is obtained. On the other hand, IPL[t=0] may be linearly dependent on the pump fluence and may possess a near invariant effective PL lifetime (FIG. 31B) at pump fluence below 0.6 μJ/cm2.
As discussed earlier, pump fluence dependent TRPL measurements clearly show that the light emission from these CsSnI3 perovskite may originate from free carrier recombination (FIG. 31B). The light emission may be dominated by trap-assisted mono-molecular recombination at low pump fluence and by free electron-hole bimolecular recombination at high pump fluence. At much higher pump fluence, the charge carrier dynamics may be strongly influenced by the three-particle Auger process. The transition from trap assisted monomolecular recombination to free electron-hole bimolecular recombination may be dependent on the unintentionally doped charge carrier concentration. In general, the PL decay dynamics may be described with the following differential equation:




  
    
      
        
          
            d
            ⁢
            
              
            
            ⁢
            
              n
              ⁡
              
                (
                t
                )
              
            
          
          
            d
            ⁢
            
              
            
            ⁢
            t
          
        
        =
        
          
            
              -
              
                k
                1
              
            
            ⁢
            n
          
          -
          
            
              k
              2
            
            ⁢
            
              n
              2
            
          
          -
          
            
              k
              3
            
            ⁢
            
              n
              3
            
          
        
      
    
    
      
        (
        17
        )
      
    
  




where n is the photo-generated charge carrier density, k1 is the monomolecular recombination rate, k2 is the bimolecular recombination rate, k3 is the Auger recombination rate.

FIG. 32A is a plot 3200a of photoluminescence (PL) intensity (arbitrary units or a.u.) as a function of time (nanoseconds or ns) showing the transient photoluminescence (TRPL) decay of CsSnI3 films with SnF2 addition (integrated over the spectrum) following 650 nm pulses (1 KHz, 50 fs,  ̃4 μJ/cm2) excitation at room temperature according to various embodiments. Solid lines represent fits with first and second order decay functions. FIG. 32B is a table 3200b showing the charge-carrier decay rates of CsSnI3 with SnF2 addition in different concentration according to various embodiments.
Although FIG. 31B shows that the Auger recombination lifetime is around hundreds of ps, this lifetime component may not be accurately resolved when we collect the PL dynamics over a wide time window of 10 ns. Hence, we only fitted the TRPL decay curves in FIG. 32A with the first and second order decay terms in Equation 17. The extracted decay rates of the four samples are listed in FIG. 32B. It clearly shows that the monomolecular decay rate decreases with increasing SnF2 concentrations. This suggests that the SnF2-treated samples are of higher quality and have lower carrier-trapping centers compared with the untreated film. However, compared to the leaded CH3NH3PbI3 perovskites with typical 1st order coefficients of 10 μs−1 (i.e.,  ̃2 orders lower compared to 1st order coefficient of 20% SnF2-treated CsSnI3 at  ̃720 μs−1), the SnF2-treated CsSnI3 possess much higher trap densities.
However bimolecular recombination constants (of  ̃10−8 cm3s−1) may be 2-3 orders larger than that of their leaded CH3NH3PbI3 counterparts. This larger bimolecular recombination constant may possibly be due to the reduced screening afforded by the Cs+ ions compared to the organic CH3NH3+ cations and further investigations may be warranted. Despite the higher trap concentrations, the larger bimolecular recombination constants for these lead-free perovskites may possibly account for their superior gain properties comparable to CH3NH3PbI3. These results clearly suggest that such lead-free CsSnI3 perovskite may be more suited for light emitting applications rather than for light harvesting.
It is clear that SnF2 addition may have a profound effect on the optical gain. Previously, from thermodynamic analysis, the Sn vacancy formation energy was predicted to increase with SnF2 addition. The trap densities in the treated CsSnI3 film may therefore be expected to be reduced. This may be accompanied by a reduction in the carrier densities in the CsSnI3 film, however no direct evidence of trap reduction was presented. Transient absorption (TA) spectroscopy which allows us to monitor the state-filling of the traps was thus performed. With photon pumping at 1.9 eV (above the band-gap energy), the photo-generated hot charge carriers may rapidly cool down or relax to the band edge or trap states within 0.5±0.1 ps.
FIG. 33A is a plot 3300a of wavelength (nanometers or nm) as a function of time (picoseconds or ps) showing a two dimensional (2D) transient absorption (TA) image in short time scale according to various embodiments. FIG. 33B is a plot 3300b of normalized change in absorption ΔA (arbitrary units or a.u.) as a function of delay time (picoseconds or ps) showing photobleaching (PB) dynamics at about 850 nm and about 950 nm as indicated to illustrate the hot carrier cooling process according to various embodiments. FIG. 33C is a plot 3300c of change in absorption ΔA (arbitrary units or a.u.) as a function of delay time (picoseconds or ps) showing the pump fluence dependent early time dynamics of photobleaching (PB) at about 950 nm according to various embodiments. FIG. 33D is a plot of 3300d of hot charge carrier cooling time (τHCC) as a function of pump fluence (micro-Joules per square centimeter or μJ/cm2) exhibited by the 20% SnF2 doped CsSnI3 film according to various embodiments. The experiments were conducted with 20% SnF2 doped CsSnI3 following 650 nm laser pulses (1 KHz, 50 fs) excitation.
The band-edge photobleaching (PB) valley ( ̃950 nm) may originate from the state-filling of the photo-generated electrons and holes located near the band-edge. The decay of the PB transients may arise from electron-hole recombination and/or trapping to the mid-gap trap states as the band edge states becomes depopulated.
FIG. 34A is a pseudo color transient absorption (TA) plot 3400a of wavelength (nanometers or nm) as a function of time (picoseconds or ps) showing the change in absorption ΔA (arbitrary units or a.u.) as a function of probe wavelength and probe delay time for the CsSnI3 samples with different SnF2 treatment according to various embodiments. The band edge PB valley (950 nm) is absent in untreated film, where this feature gradually becoming more prominent with increasing SnF2 addition. The experiments were conducted with 650 nm pump pulses (50 fs, 1 KHz) at a pump fluence of  ̃2 μJ/cm2. FIG. 34B is a plot 3400b of change in absorption ΔA (arbitrary units or a.u.) as a function of wavelength (nanometer or nm) showing the transient absorption (TA) of 4 samples according to various embodiments at 5 pico-seconds (ps) probe delay time (extracted from the transient absorption (TA) in FIG. 34A) overlaid for comparison. 3402 relates to the untreated sample (i.e. 0% SnF2), 3404 relates to the sample with 5% SnF2, 3406 relates to the sample with 10% SnF2, and 3408 relates to the sample with 20% SnF2. 3402 yields a broad featureless negative ΔA band or photobleaching (PB) signature at wavelengths >950 nm, but a positive ΔA band or photoinduced absorption (PIA) signature at wavelengths <950 nm. In contrast, the SnF2-added CsSnI3 films (3404, 3406, 3408) show a PB signature with the PB valley at around 950 nm becoming progressively stronger.
FIG. 34C is a pseudo color transient absorption (TA) plot 3400c of wavelength (nanometers or nm) as a function of time (picoseconds or ps) showing the change in absorption (ΔA) as a function of probe wavelength and probe delay time for the 30% SnF2-treated CsSnI3 film according to various embodiments. FIG. 34D is a plot 3400d of change in absorption ΔA (arbitrary units or a.u.) as a function of wavelength (nanometer or nm) showing the transient absorption (TA) shown in FIG. 34B replotted with the transient absorption (TA) of the 30% SnF2-treated sample (denoted by 3410) according to various embodiments for comparison. The PB feature decreases when the SnF2 concentration is increased to 30%. These results show that 20% SnF2 treatment may be close to the optimal conditions for treating the CsSnI3 film. The experiments were conducted with 650 nm pump pulses (1 KHz, 50 fs,  ̃2 μJ/cm2).
FIG. 35A is a plot 3500a of change in absorption ΔA (arbitrary units or a.u.) as a function of time (picoseconds or ps) showing normalized bleaching kinetics at about 950 nm for the SnF2 treated CsSnI3 films according to various embodiments in an optical cryostat under vacuum following excitation at 650 nm (1 KHz, 50 fs,  ̃2 μJ/cm2). 3502 relates to the untreated sample (0% SnF2), 3504 relates to the 5% SnF2 sample, 3506 relates to the 10% SnF2 sample, and 3508 relates to the 20% SnF2 sample. For the SnF2-treated films, the band-edge PB decay lifetime increases with increasing SnF2 addition. Assuming a fixed intrinsic electron-hole recombination rate in CsSnI3, the PB lifetime lengthening indicates that the charge carrier trapping from the band edge to the trap states may be reduced with the SnF2 addition. In the CsSnI3 treated films, the PB decay time closely matches the first order PL lifetime (PL lifetime at low pump fluence). For a p-type semiconductor, the PL lifetime may typically be limited by the photogenerated electron trapping to the mid-gap states. Hence, this indicates that the band-edge PB peak dynamics may be dominated by the state-filling of the electrons. In contrast for the pristine CsSnI3 film, the PB lifetime may be much longer than the PL lifetime (FIGS. 32A, 35A), consistent with the earlier interpretation that it originates from a different source (i.e., the recombination from the mid-gap states).
FIG. 35B is a schematic 3500b illustrating the origins of the various transient absorption (TA) of photobleaching (PB) and photoinduced absorption (PIA) present in the films according to various embodiments.
A PB signature may possibly arise from: (i) near bandgap stimulated emission of the carriers; and/or (ii) state-filling of the band edge states; or (iii) state-filling of the trap states. Mechanisms (i) and (ii) may account for the 950 nm PB valley near the bandgap in the SnF2-added CsSnI3 films—which we term as PB1 in FIGS. 34B, 34D, 35B. On the other hand, the nearly-flat and broad PB band observed for the untreated CsSnI3 films may be consistent with mechanism (iii)—as shown in the schematic in 35B. This may suggest a prevalence of trap states, possibly from Sn vacancies functioning as intrinsic defects. The PB2 band from the trap states (i.e., at wavelengths >1000 nm) in the treated CsSnI3 film becomes less pronounced than the untreated film (FIGS. 34B, 34D)—consistent with the trap reduction. TA measurements thus provide a clear direct evidence for the trap state reduction.
Due to pump fluence dependent transition from trap-assisted monomolecular recombination to free electron-hole bimolecular recombination, the initial time PL intensity (IPL[t=0]) shows a clear transition from linear to quadratic power dependent behavior for the SnF2 treated CsSnI3 films. Here, contributions of two-photon absorption to the quadratic power dependence may not be expected to play a major role as the pump energy (1.9 eV) is much larger than the bandgap of CsSnI3 (1.3 eV).
FIG. 36 are plots 3600a-c of initial photoluminescence intensity (IPL[t=0]) (arbitrary units or a.u.) as a function of pump fluence (micro-Joules per square centimeter or μJ/cm2) showing pump fluence dependence of the initial time photoluminescence (PL) intensity for the pristine (3600a), the 5% SnF2-added (3500b), and the 10% SnF2-added CsSnI3 (3600c) according to various embodiments. The plot for the 20% SnF2-added CsSnI3 has been shown in FIG. 31B. The experiments were conducted with 650 nm laser pulses (1 KHz, 50 fs). The intersection between the linear fit and the quadratic fit yields an estimate of the doped carrier densities.
Using the pump fluence dependent IPL[t=0] approach described earlier, the density of the unintentionally-doped charge carriers for the 5%, 10% and 20% SnF2 added CsSnI3 films may be estimated.
The pump fluences at the transition may be determined to be 3.2±0.6, 1.6±0.3 and 0.6±0.1 μJ/cm2 for the 5%, 10% and 20% SnF2 added CsSnI3 films, respectively. With linear absorption coefficient of 1.45×104/cm at 650 nm, the corresponding unintentionally doped charge carriers densities are estimated to be  ̃1.5×1017/cm3,  ̃7.6×1016/cm3 and  ̃2.8×1016/cm3, respectively. However, for the untreated CsSnI3, the absence of any linear to quadratic transition in the investigated pump fluence range indicates that its doped charge carrier concentration is larger than 5.7×1017/cm3, consistent with Hall measurements.
Akin to their leaded counterparts, these CsSnI3 thin films also exhibit excellent photostability under sustained optical pumping at 1 KHz repetition rate at room temperature. FIG. 37A is a plot 3700a of amplified spontaneous emission (ASE) (arbitrary units or a.u.) as a function of time (hours or hrs) showing time-dependent amplified spontaneous emission intensity of the 5% SnF2-treated CsSnI3 film according to various embodiments with a pump fluence of 70 μJ/cm2 (600 nm, 50 fs, 1 KHz) under excitation for about 20 hours performed at room temperature. High stability is evident even for the lowest SnF2 addition.
The near invariance of the output ASE intensity with a standard deviation of 7% about the mean intensity even for the lowest 5% added films under  ̃20 hours continuous irradiation (i.e.,  ̃10 laser shots in all) may bear testimony to the excellent optical stability of these lead-free perovskite gain media. Such stability may be superior to the state-of-the-art organic semiconducting thin films (50% drop in output power after  ̃107 laser shots) and colloidal QDs (50% drop in output power after  ̃106 laser shots). Lastly, one of the greatest advantage of these low-temperature solution-processable halide perovskite gain media may relate to their facile wavelength tunability using straight-forward mixing of their precursors.
Temperature dependent PL measurements afford us an additional means to recheck the recombination mechanisms of SE and subsequently that of ASE in these SnF2-treated CsSnI3 pervoskites.
FIG. 37B is a plot 3700b of photoluminescence (PL) intensity (arbitrary units or a.u.) as a function of wavelength (nanometers or nm) showing the photoluminescence (PL) spectra from 77 to 300 K for the SnF2 doped CsSnI3 according to various embodiments.
FIG. 37B shows the evolution of the steady state spectra as a function of temperature following 532 nm continuous wave (CW) laser excitation. The PL intensity decreases and the emission peak broadens slightly when the temperature is raised. According to the TRPL measurements, the photo-induced charge carrier dynamics may be well-described with trap-assisted monomolecular recombination and free electron-hole bimolecular recombination. The band edge light emission may originate from the radiative recombination of the free electron-hole plasma. The radiative recombination rate of electron-hole plasma may be known to be inversely proportional to the plasma temperature. With the thermally activated charge carrier trapping and other non-radiative decay channels, the PL intensity may decrease with increasing temperature. The temperature-dependent integrated band edge emission intensities were extracted from FIG. 37B and presented in FIG. 37C.
FIG. 37C is a plot 3700c of photoluminescence (PL) intensity (arbitrary units or a.u.) as a function of temperature (Kelvins or K) showing integrated photoluminescence intensity exhibited by treated and untreated samples according to various embodiments as a function of temperature. For the SnF2-added samples, the solid lines are the fittings with effective thermal induced charge carrier trapping theory. For the untreated CsSnI3, the solid line is a simple linear fit intended as a guide for the eye.
For the SnF2 doped CsSnI3 samples, the intensity data may be well-fitted by an Arrhenius plot with one effective thermal activation process:




  
    
      
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where Eac denotes the activation energy for the effective thermal activation process, A is the Arrhenius constant, kB is the Boltzmann constant, and Io is the initial intensity. From the fit, we obtained the effective activation energies of 26±1, 42±2 and 45±2 meV for the 5%, 10% and 20% SnF2 doped CsSnI3, respectively. Here, this effective thermal activation energy may not be simply attributed to be the exciton binding energy as this is only applicable for the case of decreasing PL intensity with temperature that is dominated by thermally-induced exciton dissociation. In our case, the PL intensity decrease with increasing temperature could also be attributed to: (i) the thermal-induced reduction of the electron-hole plasma recombination rate: (ii) the thermal-induced charge carrier trapping; or (iii) from some other non-radiative process.

For the pristine CsSnI3, the PL intensity linearly decreases with increasing temperature. The temperature dependent PL curve may not be fitted using the Arrhenius equation. However, a linear dependence was obtained instead. Such linear dependence may possibly be caused by the extremely high trap density in the untreated sample.
The free electron-hole plasma recombination rate decreases with increasing temperature. With limited trap states density, the increase in the charge carrier recombination lifetime with increasing temperature becomes apparent. FIGS. 38A-D show the time-resolved photoluminescence (PL) decay transients for the undoped and SnF2 doped CsSnI3 perovskites (integrated over the spectrum) following 650 nm pulses (1 KHz, 50 fs,  ̃1 μJ/cm2) excitation at different temperatures.
FIG. 38A is a plot 3800a of photoluminescence (PL) intensity (arbitrary units or a.u.) as a function of time (nanoseconds or ns) showing the time-resolved photoluminescence (PL) decay transients for untreated CsSnI3 (0% SnF2) according to various embodiments. 3802a represents data relating to the sample at 50K, 3802b represents data relating to the sample at 100K. 3802c represents data relating to the sample at 200K, and 3802d represents data relating to the sample at 300K.
FIG. 38B is a plot 3800b of photoluminescence (PL) intensity (arbitrary units or a.u.) as a function of time (nanoseconds or ns) showing the time-resolved photoluminescence (PL) decay transients for 5% SnF2 added CsSnI3 according to various embodiments. 3804a represents data relating to the sample at 50K, 3804b represents data relating to the sample at 100K, 3804c represents data relating to the sample at 200K, and 3804d represents data relating to the sample at 300K.
FIG. 38C is a plot 3800c of photoluminescence (PL) intensity (arbitrary units or a.u.) as a function of time (nanoseconds or ns) showing the time-resolved photoluminescence (PL) decay transients for 10% SnF2 added CsSnI3 according to various embodiments. 3806a represents data relating to the sample at 50K, 3806b represents data relating to the sample at 100K, 3806c represents data relating to the sample at 200K, and 3806d represents data relating to the sample at 300K.
FIG. 38D is a plot 3800d of photoluminescence (PL) intensity (arbitrary units or a.u) as a function of time (nanoseconds or ns) showing the time-resolved photoluminescence (PL) decay transients for 20% SnF2 added CsSnI3 according to various embodiments. 3808a represents data relating to the sample at 50K, 3808b represents data relating to the sample at 100K. 3808c represents data relating to the sample at 200K, and 3808d represents data relating to the sample at 300K.
With increasing temperatures, the PL recombination lifetimes increases for the 10% and 20% SnF2 doped CsSnI3. The PL recombination lifetimes for the 10% and 20% SnF2 doped CsSnI3 may increase with increasing temperatures due to reduction of trap states by SnF2 treatment. Such phenomena are contrary to that commonly observed in semiconductors with excitonic type luminescence.
The ASE PThr was measured as a function of temperature for all the SnF2 treated samples. FIG. 39 is a plot 3900 of photoluminescence (PL) intensity (arbitrary units or a.u.)/amplified spontaneous emission ncth (arbitrary units or a.u.) as a function of temperature (kelvins or K) showing normalized temperature dependent ASE thresholds (circles), normalized temperature dependent PL intensities at fixed pump fluence (squares) of SnF2 doped CsSnI3 perovskites according to various embodiments. The stars are the products of the ASE thresholds and the relative PL intensities. The ASE characterization is conducted with 650 nm laser pulses (1 KHz, 50 fs).
The results clearly show that PThr increases with increasing temperature for all the treated samples. This kind of threshold fluence increasing may be partly attributed to the reduced free electron-hole recombination rate with temperature.
The atomic and electronic structure of CsSnBrxI3-x (x=0, 1, 2, 3) compounds were calculated employing density-functional-theory (DFT) calculations, using the Perdew-Burke-Ernzerhof (PBE96) exchange-correlation potential, and the projector-augment wave (PAW) method, as implemented in the Vienna ab-initio simulation program (VASP). In these calculations Cs 5s5p6s, Sn 4d5s5p, I 5s5p and Br 4s4p orbitals were treated as valence states, employing the PAW potentials labeled “Cs_sv”, “Sn_d”, “I” and “Br” in the VASP PBE library.
Four compositions were modeled: CsSnBrxI3-x, where x=0, 1, 2, 3. For x=0 and 1, orthorhombic structures were used, and for x=2 and 3, cubic structures were used as input48. For x=1 and 2 the compounds were modeled with a 40-atom supercell, in which the occupation of Br and I on the anion sublattice were chosen randomly, to approximate a disordered structure.
All calculations were fully relaxed with respect to cell internal atomic positions, volume and cell shape. We employed 12*12*12, 6*6*6, 4*8*6 and 8*8*6 k-point meshes for CsSnBr3, CsSnBr2I, CsSnBrI2 and CsSnI3, respectively, and a plane-wave cutoff of 520 eV. After the relaxations, the Δ-sol method was employed to compute the band gaps, based on the changes in energy arising when electrons were added or subtracted from the system. In the implementation of the Δ-sol method, we chose N*=68, as recommended for s-p bonded systems and PBE functionals. When calculating the total energies for systems with surplus and deficient electrons, cell shape, volume and internal atomic positions were held fixed.
FIG. 40 is a plot 4000 of bandgap (electron-volts or eV) as a function of atomic volume (cubic angstroms or Å3) showing theoretical predicted band gaps of CsSnBr3, CsSnBr2I, CsSnBrI2 and CsSnI3 according to various embodiments with the Δ-sol method (4002). The experimental results (4004) were also put here for comparison.
FIG. 41 is a plot 4100 of emission intensity (arbitrary units or a.u.) as a function of wavelength (nanometers or nm) showing wide photoluminescence (PL) and amplified spontaneous emission (ASE) wavelength tunability from CsSnBrrI(3-x) films according to various embodiments fabricated by facile mixing the precursor solutions. The experiments were conducted with 500 nm pump pulses (50 fs, 1 KHz). FIG. 41 shows that the ASE could be tuned at room temperature from 700 nm to 950 nm by varying the bromides and iodides composition to obtain CsSnBr3, CsSnBr2I, CsSnBrI2 and CsSnI3 thin films. The trend of the bandgap variation with composition is qualitatively consistent with theoretical predictions based on the Δ-sol method, as shown in FIG. 40.
Coherent near-infrared (NIR) light sources play a pivotal role in optoelectronics, telecommunications and imaging applications. Conventional NIR semiconductor optical gain media (e.g., InGaAs) are grown lattice-matched under high vacuum conditions which restrict their resonator cavity design and substrate choice. Solution-processed alternatives could unlock advantages of facile on-chip assimilation. However, choices are limited as narrow bandgap materials face inherent challenges from fast non-radiative recombination and magnified Auger losses with decreasing bandgaps.
Solution-processed lead-free halide CsSnI3 perovskite, despite exhibiting very poor photovoltaic performance, may possess exceptional optical gain comparable to the leaded CH3NH3PbI3.
Ultralow threshold ( ̃6 μJ/cm2), large gain (200 cm−1), NIR (0.95 μm) stimulated emission from 20% SnF2-added CsSnI3 samples are demonstrated. Relatively high Q factor NIR lasing ( ̃500) may be achieved using the imperfect natural photonic crystal corrugations in the scales of a butterfly wing. Transient spectroscopy may provide direct evidence that SnF2— addition effectively suppresses the trap states in CsSnI3 and the lasing may originate from free electron-hole bimolecular recombination with a high rate of  ̃10−8 cm3s−1. Room temperature, ultrastable (>20 hours). NIR tunable stimulated emission (700-950 nm) may be achieved with judicious substitution. Importantly, these solution-processable Pb-free perovskites may present a substrate-insensitive infrared wavelength tunable lasing solution for applications in non-conformal, non-planar geometries or flexible substrates.
While the invention has been particularly shown and described with reference to specific embodiments, it should be understood by those skilled in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is thus indicated by the appended claims and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced.

## Claims

1. An emission source comprising:
a gain medium comprising a halide semiconductor material; and
a pump source configured to provide energy to the gain medium comprising the halide semiconductor material so that the gain medium generates a coherent stimulated light to emit a laser beam and the gain medium generates amplified spontaneous emission based on the energy provided,
wherein the halide semiconductor material comprises a lead-free perovskite material,
and wherein the gain medium further comprises an additive to control trap density.

2. The emission source according to claim 1, wherein the pump source is an optical source configured to provide light as energy to the gain medium.

3. The emission source according to claim 1, wherein the pump source is an electrical source configured to provide electrical energy to the gain medium.

4. The emission source according to claim 1, the emission source further comprising:
a resonant cavity, the gain medium arranged within the resonant cavity;
wherein the resonant cavity is defined by a first reflective structure and a second reflective structure, the gain medium arranged between the first reflective structure and the second reflective structure along an optical axis.

5. The emission source according to claim 4, wherein the first reflective structure is arranged to reflect light incident on the first reflective structure towards the second reflective structure along the optical axis and the second reflective structure is arranged to reflect light incident on the second reflective surface towards the first reflective surface along the optical axis.

6. The emission source according to claim 4, wherein the first reflective structure is partially transparent so that light incident in the first reflective structure is partially transmitted through the first reflective structure and partially reflected towards the second reflective structure along the optical axis.

7. The emission source according to claim 1, wherein the lead-free perovskite material comprises a cation of CsSn3+.

8. The emission source according to claim 1, wherein the lead-free perovskite material comprises one or more halide anions selected from a group consisting of F−, I−, Cl− and Br−.

9. The emission source according to claim 1, wherein the emission source is configured to generate light of a wavelength from a range of about 250 nm to about 1 mm.

10. The emission source according to claim 1, wherein the lead-free perovskite material is CsSnI3.

11. The emission source according to claim 1, wherein the gain medium has undergone a post film treatment.

12. The emission source according to claim 1, wherein the additive comprises SnF2.

13. The emission source according to claim 12, wherein the weight concentration of SnF2 is equal to or below 20%.

14. A method of forming an emission source, the method comprising:
providing a gain medium comprising a halide semiconductor material; and
providing a pump source configured to provide energy to the gain medium comprising the halide semiconductor material so that the gain medium generates a coherent stimulated light to emit a laser beam and the gain medium generates amplified spontaneous emission based on the energy provided,
wherein the halide semiconductor material comprises a lead-free perovskite material,
and wherein the gain medium further comprises an additive to control trap density.

15. The method according to claim 14, wherein the lead-free perovskite material comprises a cation of CsSn3+.

16. The method according to claim 14, wherein the lead-free perovskite material comprises one or more halide anions selected from a group consisting of F−, I−, Cl− and Br.

17. The method according to claim 14, wherein the lead-free perovskite material is CsSnI3.

18. The method according to claim 14, wherein the additive comprises SnF2.