Mixed halide perovskite, megalibraries, heterostructures and solid solutions and methods of forming the same
AssigneeNorthwestern University
InventorsChad A. Mirkin, Doonghoon Shin, Minliang Lai
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Abstract
A method of forming a combinatorial mixed halide perovskite library can include depositing an array of halide perovskite particles on a substrate. The method further includes exposing the array of halide perovskites to a laser to from defects in each of or a selected portion of the halide perovskite particles. The exposure conditions are modified across the array to generate a variation of defect concentration in the halide perovskite particles in the array. The defect containing halide perovskites are then exposed to an ion exchange solution and either anion exchanged or cation exchanged to thereby form a mixed halide perovskite particle.
Claims46
A method of forming a combinatorial mixed halide perovskite library, comprising:
- depositing an array of halide perovskite particles on a substrate, wherein each halide perovskite particle is a compound of formula ABX13, wherein A is a cation, B is a metal, and X1 is a first halogen;
- exposing the array of halide perovskite particles to a laser to form defects in at least a portion of the halide perovskite particles, wherein an exposure condition is modified across the array to generate a variation of defect concentration in the halide perovskite particles in the array;
- and
- exposing the array of halide perovskite particles having the defect concentration to an ion exchange solution comprising at least one halogen X2 to thereby exchange a portion of X1 with X2 and form mixed halide perovskite particles, each mixed halide perovskite particle being a compound of formula AB(X1(1-n)X2n)3, wherein 0<n<1), and X2 is a second halogen different from X1.
The method of any one of the preceding claims, wherein the halide perovskite particles have a crystal size of about 100 nm to about 400 nm before laser exposure.
The method of any one of the preceding claims, wherein the exposure condition of the laser is varied such that a gradient of defect concentration is generated across the array of halide perovskite particles.
The method of any one of the preceding claims, wherein ion exchange is performed at a temperature of about 20° C. to about 65° C.
The method of any one of the preceding claims, wherein ion exchange is performed by exposing the array of halide perovskite particles having the defect concentration to a solution comprising a perovskite precursor BX22, cyclohexane, oleic acid, and oleylamine.
The method of any one of the preceding claims, wherein X1 and X2 are independently selected from Cl, Br, F, and I.
The method of any one of the preceding claims, wherein B is one or more of lead, tin, and/or germanium.
The method of any one of the preceding claims, wherein A is one or more of methylammonium, butylammonium, formamidinium, phenethylamine, cesium, and rubidium.
The method of any one of the preceding claims, wherein varying the exposure conditions comprises varying the exposure time.
The method of any one of the preceding claims, wherein varying the exposure conditions comprises varying the laser power.
The method of any one of the preceding claims, wherein the exposure conditions comprise delivering an energy in a range of about 2.5 to about 2000 mJ.
The method of any one of the preceding claims, wherein the laser has a wavelength from about 300 nm to about 700 nm.
A mixed halide perovskite crystal having a lateral heterostructure and being of formula I:
- A′1-xA″xBX3,
- wherein
- A′ is a first cation,
- A″ is a second cation, wherein A′ and A″ are different cations,
- B is a metal,
- X is at least one halogen,
- 0<x<1, and
- the lateral heterostructure comprises an A′ rich phase in a central region of the crystal, surrounded partially by an A″ rich phase.
A solid-solution mixed halide perovskite having the formula A′1-xA″xBX3,
- wherein
- A′1-xA″xBX3,
- wherein
- A′ is a first cation
- A″ is a second cation, wherein A′ and A″ are different cations,
- B is a metal
- X is at least one halogen,
- 0<x<1, and wherein the crystal size is less than 60 nm.
A method of forming mixed halide perovskite crystals having a lateral heterostructure, comprising:
- dissolving at least one first perovskite precursor having the formula A′X′, at least one second perovskite precursor having the formula A″X″ and at least one third perovskite precursor having the formula BX′2, and at least one fourth perovskite precursor having the formula BX″2 in a solvent to form a precursor solution, wherein A′ and A″ are each cations and are different cations, B is a metal, and X and X′ are each a halogen and can each be the same or different;
- depositing the precursor solution onto a substrate;
- and
- evaporating the solvent, wherein the halide perovskite crystals form upon evaporation of the solvent, wherein the crystals form as two stages, the first stage being a A′-X′-rich perovskite phase and the second stage being a A″-X″-rich perovskite phase partially surrounding the A′-X′-rich perovskite phase to thereby form the mixed halide perovskite having a lateral heterostructure and being of formula I
- A′1-xA″xBX3,
- wherein
- A′ is a first cation
- A″ is a second cation, wherein A′ and A″ are different cations,
- B is a metal
- X is at least one halogen,
- 0<x<1.
A method of forming mixed halide perovskite crystal array having a plurality of halide perovskite crystals arranged in a pattern, comprising:
- coating an array of pens with a precursor solution comprising at least one first perovskite precursor having the formula A′X′, at least one second perovskite precursor having the formula A″X″, at least one third perovskite precursor having the formula BX′2 dissolved in a solvent, and at least one fourth perovskite precursor having the formula BX″2 wherein A′ and A″ are each cations and are different cations, B is a metal, and X and X′ are each a halogen and can each be the same or different;
- contacting a substrate with the coated pen array to thereby deposit the precursor solution as a pattern of printed indicia on the substrate, wherein:
- the printed indicia form nanoreactors on the substrate and a mixed halide perovskite crystal nucleates and grows within each nanoreactor in two stages, the first stage being a A′-X′-rich perovskite phase and the second stage being a A″-X″-rich perovskite phase partially surrounding the A′-X′-rich perovskite phase to thereby form the mixed halide perovskite having a lateral heterostructure and being of formula I
- A′1-xA″xBX3,
- wherein
- A′ is a first cation
- A″ is a second cation, wherein A′ and A″ are different cations,
- B is a metal
- X is at least one halogen defined by selection of X′, X″, and X′″,
- 0<x<1.
Dependencies are inferred from the claim text.