# US 12,180,400 B2 · Surface engineered organic-inorganic hybrid perovskite nanocrystals and applications thereof

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- Number: US 12,180,400 B2
- Document ID: US12180400B2
- Status: Granted
- Kind: B2
- Application number: 17/413,271
- Filed: 2019-10-11
- Published: 2022-09-29
- Granted: 2024-12-31
- Earliest claimed: 2018-12-12
- Assignees: The Trustees of Princeton University
- Applicants: The Trustees of Princeton University
- Inventors: Barry P. Rand; Zhengguo Xiao
- Web page: https://patentgrep.com/patent/US12180400B2

## CPC

- C09K 11/025: {non-luminescent particle coatings or suspension media}
- C09K 11/06: containing organic luminescent materials
- C30B 7/14: the crystallising materials being formed by chemical reactions in the solution
- C30B 29/12: Halides
- C30B 29/60: characterised by shape
- H01G 9/2009: {Solid electrolytes}
- H10K 30/10: comprising heterojunctions between organic semiconductors and inorganic semiconductors
- H10K 85/30: Coordination compounds
- B82Y 20/00: Nanooptics, e.g. quantum optics or photonic crystals
- B82Y 40/00: Manufacture or treatment of nanostructures
- C09K 2211/10: Non-macromolecular compounds
- H10K 30/50: Photovoltaic [PV] devices
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C30B: SINGLE-CRYSTAL GROWTH (by using ultra-high pressure, e.g. for the formation of diamonds, B01J3/06); UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL (zone-refining of metals or alloys C22B); PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE (casting of metals, casting of other substances by the same processes or devices B22D; working of plastics B29; modifying the physical structure of metals or alloys C21D, C22F); SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE (for producing semiconductor devices or parts thereof H10); APPARATUS THEREFOR
- H01G: CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE (selection of specified materials as dielectric H01B3/00; capacitors having potential barriers H10D1/62, H10K10/10)
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES

## Abstract

In one aspect, organic-inorganic nanoparticle compositions are described herein comprising engineered surfaces which, in some embodiments, reduce non-radiative recombination mechanisms, thereby providing optoelectronic devices with enhanced efficiencies. In some embodiments, a nanoparticle composition comprises a layer of organic-inorganic perovskite nanocrystals, the organic-inorganic perovskite nanocrystals comprising surfaces associated with growth passivation ligands and trap passivation ligands, wherein the growth passivation ligands are larger than the trap passivation ligands and are of size unable to incorporate into octahedral corner sites of the perovskite crystal structure.

## Claims

### Claim 1

A nanoparticle composition comprising:
a layer of organic-inorganic perovskite nanocrystals, the organic-inorganic perovskite nanocrystals comprising surfaces associated with growth passivation ligands and trap passivation ligands, wherein the growth passivation ligands are larger than the trap passivation ligands and are of size unable to incorporate into octahedral corner sites of the perovskite crystal structure, wherein the layer comprises excess halide, and the organic-inorganic perovskite nanocrystals are of the formula Me1−yAyBX3−zYz, wherein Me is an alkali metal cation, A is an organic cation, B is an element selected from the group consisting of transition metals, Group IVA elements and rare earth elements and X and Y are independently selected from Group VIIA elements, wherein 0<y≤1 and wherein 0≤z<3, and the trap passivation ligands fill uncoordinated surface sites on at least one of B, X and Y.

### Claim 2 (depends on 1)

The nanoparticle composition of claim 1, wherein the organic-inorganic perovskite nanocrystals have an average size less than 20 nm.

### Claim 3 (depends on 1)

The nanoparticle composition of claim 1, wherein the organic-inorganic perovskite nanocrystals have an average size of 1-10 nm.

### Claim 4 (depends on 1)

The nanoparticle composition of claim 1, wherein 0<z<3.

### Claim 5 (depends on 1)

The nanoparticle composition of claim 1, wherein the growth passivation ligands comprise organoammonium ions.

### Claim 6 (depends on 5)

The nanoparticle composition of claim 5, wherein the organoammonium ions comprise one or more substituents selected from the group consisting of alkyl, heteroalkyl, alkenyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, aryl and heteroaryl.

### Claim 7 (depends on 1)

The nanoparticle composition of claim 1, wherein the trap passivation ligands comprise organoammonium ions.

### Claim 8 (depends on 7)

The nanoparticle composition of claim 7, wherein the organoammonium ions comprise one or more substituents selected from the group consisting of alkyl and heteroalkyl.

### Claim 9 (depends on 1)

The nanoparticle composition of claim 1, wherein the trap passivation ligands are selected from the group consisting of formamidinium, hydrazinium, guanidinium, azetidinium, azetamidinium, imidazolium, pyrrolidinium, cesium, rubidium, potassium, and mixtures thereof.

### Claim 10 (depends on 1)

The nanoparticle composition of claim 1, wherein the layer of organic-inorganic perovskite nanocrystals is photoluminescent.

### Claim 11 (depends on 10)

The nanoparticle composition of claim 10, wherein the layer of organic-inorganic perovskite nanocrystals has a quantum yield of at least 16%.

### Claim 12 (depends on 10)

The nanoparticle composition of claim 10, wherein the layer of organic-inorganic perovskite nanocrystals has a quantum yield of at least 18%.

### Claim 13 (depends on 10)

The nanoparticle composition of claim 10, wherein the layer of organic-inorganic perovskite nanocrystals exhibits a radiative recombination rate of at least 4.0×106 s−1.

### Claim 14 (depends on 1)

The nanoparticle composition of claim 1, wherein 0<y<1.

### Claim 15

An optoelectronic device comprising:
a photoactive layer including organic-inorganic perovskite nanocrystals, the organic-inorganic perovskite nanocrystals comprising surfaces associated with growth passivation ligands and trap passivation ligands, wherein the growth passivation ligands are larger than the trap passivation ligands and are of size unable to incorporate into octahedral corner sites of the perovskite crystal structure, wherein the photoactive layer comprises excess halide, and the organic-inorganic perovskite nanocrystals are of the formula Me1−yAyBX3−zYz, wherein Me is an alkali metal cation, A is an organic cation, B is an element selected from the group consisting of transition metals, Group IVA elements and rare earth elements and X and Y are independently selected from Group VIIA elements, wherein 0<y≤1 and wherein 0≤z<3, and the trap passivation ligands fill uncoordinated surface sites on at least one of B, X and Y.

### Claim 16 (depends on 15)

The optoelectronic device of claim 15, wherein the organic inorganic perovskite nanocrystals have an average size less than 20 nm.

### Claim 17 (depends on 15)

The optoelectronic device of claim 15, wherein the trap passivation ligands comprise organoammonium ions.

### Claim 18 (depends on 17)

The optoelectronic device of claim 17, wherein the organoammonium ions comprise one or more substituents selected from the group consisting of alkyl and heteroalkyl.

### Claim 19 (depends on 15)

The optoelectronic device of claim 15, wherein the trap passivation ligands are selected from the group consisting of formamidinium, hydrazinium, guanidinium, azetidinium, azetamidinium, imidazolium, pyrrolidinium, cesium, rubidium, potassium, and mixtures thereof.

### Claim 20 (depends on 15)

The optoelectronic device of claim 15, wherein the photoactive layer is a light emitting layer of a light emitting diode.

### Claim 21 (depends on 20)

The optoelectronic device of claim 20, wherein the light emitting diode has an external quantum efficiency of at least 15 percent.

### Claim 22 (depends on 15)

The optoelectronic device of claim 15, wherein the photoactive layer is a light absorption layer of a photovoltaic device.

### Claim 23 (depends on 21)

The optoelectronic device of claim 21, wherein the light emitting layer has a peak emission from 700-1000 nm.

### Claim 24 (depends on 15)

The optoelectronic device of claim 15, wherein 0<y<1.

### Claim 25

A nanoparticle composition comprising:
a layer of organic-inorganic perovskite nanocrystals, the organic-inorganic perovskite nanocrystals comprising surfaces associated with growth passivation ligands and trap passivation ligands, wherein the growth passivation ligands are larger than the trap passivation ligands and are of size unable to incorporate into octahedral corner sites of the perovskite crystal structure, wherein the organic-inorganic perovskite nanocrystals are of the formula AB1−pMpX3−zYz, wherein A is an organic cation, B and M are elements independently selected from the group consisting of transition metals, Group IVA elements and rare earth elements and X and Y are independently selected from Group VIIA elements, wherein 0<p<1 and wherein 0≤z<3, and wherein the trap passivation ligands are present in stoichiometric excess relative to metal halide of the perovskite nanocrystals.

### Claim 26 (depends on 25)

The nanoparticle composition of claim 25, wherein the organic-inorganic perovskite nanocrystals have an average size less than 20 nm.

### Claim 27 (depends on 25)

The nanoparticle composition of claim 25, wherein the organic-inorganic perovskite nanocrystals have an average size of 1-10 nm.

### Claim 28 (depends on 25)

The nanoparticle composition of claim 25, wherein 0<z<3.

### Claim 29 (depends on 25)

The nanoparticle composition of claim 25, wherein the growth passivation ligands comprise organoammonium ions.

### Claim 30 (depends on 25)

The nanoparticle composition of claim 25, wherein B is lead and M is tin.

### Claim 31

A nanoparticle composition comprising:
a layer of organic-inorganic perovskite nanocrystals, the organic-inorganic perovskite nanocrystals comprising surfaces associated with growth passivation ligands and trap passivation ligands, wherein the growth passivation ligands are larger than the trap passivation ligands and are of size unable to incorporate into octahedral corner sites of the perovskite crystal structure, wherein organic-inorganic perovskite nanocrystals are of the formula Me1−yAyBX3−zYz, wherein Me is an alkali metal cation, A is an organic cation, B is an element selected from the group consisting of transition metals, Group IVA elements and rare earth elements and X and Y are independently selected from Group VIIA elements, wherein 0<y<1 and wherein 0≤z<3, and the trap passivation ligands fill uncoordinated surface sites on at least one of B, X and Y, and wherein the trap passivation ligands are present in stoichiometric excess relative to metal halide of the perovskite nanocrystals.

### Claim 32 (depends on 31)

The nanoparticle composition of claim 31, wherein the growth passivation ligands comprise organoammonium ions.