# US 11,309,138 B2 · Contact passivation for perovskite optoelectronics

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- Number: US 11,309,138 B2
- Document ID: US11309138B2
- Status: Granted
- Kind: B2
- Application number: 15/883,992
- Filed: 2018-01-30
- Published: 2018-08-02
- Granted: 2022-04-19
- Earliest claimed: 2017-01-30
- Assignees: The Governing Council of the University of Toronto
- Applicants: The Governing Council of the University of Toronto
- Inventors: Hairen Tan; Xinzheng Lan; Zhenyu Yang; Sjoerd Hoogland; Edward Sargent
- Web page: https://patentgrep.com/patent/US11309138B2

## CPC

- H10K 71/15: characterised by the solvent used
- H01G 9/0029: {Processes of manufacture}
- H01G 9/2018: {characterised by the ionic charge transport species, e.g. redox shuttles}
- H01G 9/2072: {comprising two or more photoelectrodes sensible to different parts of the solar spectrum, e.g. tandem cells}
- H01G 9/2077: {Sealing arrangements, e.g. to prevent the leakage of the electrolyte}
- H01G 9/2095: {comprising a flexible sustrate}
- H10K 30/82: Transparent electrodes, e.g. indium tin oxide [ITO] electrodes
- H10K 30/88: Passivation; Containers; Encapsulations
- H10K 71/12: using liquid deposition, e.g. spin coating
- H10K 85/50: Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
- H10K 30/151: {the wide bandgap semiconductor comprising titanium oxide, e.g. TiO2}
- H10K 30/50: Photovoltaic [PV] devices
- H10K 30/57: comprising multiple junctions, e.g. tandem PV cells
- H10K 77/111: {Flexible substrates}
- H10K 85/30: Coordination compounds
- Y02E 10/542: Dye sensitized solar cells
- Y02E 10/549: Organic PV cells
- Y02P 70/50: Manufacturing or production processes characterised by the final manufactured product
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES
- 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)
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

Disclosed herein are perovskite based optoelectronic devices made entirely via solution-processing at low temperatures (<150° C.) which provide for simple manufacturing, compatibility with flexible substrates, and perovskite-based tandem devices. These perovskite based optoelectronic devices are produced using an electron transport layer on which the perovskite layer is formed which is passivated using a ligand selected to reduce electron-hole recombination at the interface between the electron transport layer and the perovskite layer.

## Claims

### Claim 1

A perovskite-based optoelectronic device, comprising:
a) an optically transparent electrode;
b) a semiconductor electron transport layer on said optically transparent electrode;
c) a light-absorbing perovskite layer formed on said semiconductor electron transport layer;
d) the electron transport layer having a surface located at an interface or junction between the semiconductor electron transport layer and the light-absorbing perovskite layer at least partially capped with a ligand Z, wherein said ligand Z is selected to passivate surface states at said interface or junction between the semiconductor electron transport layer and the light-absorbing perovskite layer; and
e) a hole transport layer on said light-absorbing perovskite layer, and including an electrode layer located on said hole transport layer.

### Claim 2 (depends on 1)

The perovskite-based optoelectronic device according to claim 1, wherein the ligand Z is any one of a halide, a pseudo halide, a monovalent ammonium cation, and any combination thereof.

### Claim 3 (depends on 2)

The perovskite-based optoelectronic device according to claim 2, wherein the halide is any one of Cl, Br, I, F, and any combination thereof.

### Claim 4 (depends on 2)

The perovskite-based optoelectronic device according to claim 2, wherein the pseudo halide is a polyatomic analogue of halide ions.

### Claim 5 (depends on 4)

The perovskite-based optoelectronic device according to claim 4 wherein the pseudo halide is any one of cyanide (CN), thiocyanate (SCN), cyanate (OCN), and any combination thereof.

### Claim 6 (depends on 2)

The perovskite-based optoelectronic device according to claim 2, wherein the monovalent ammonium cation is any one of positively charged polyatomic ions with the chemical formula of R1R2R3R4N+; where R1, R2, R3, R4 are selected from a group consisting of hydrogen, and compounds derived from linear alkanes, branched alkanes, cycloalkanes, (poly)cycloalkanes, cis- and trans-linear alkenes, cis- and transbranched alkenes, linear alkynes, branched alkynes, (poly)alkynes, aromatic hydrocarbons, (poly)aromatic hydrocarbons, heteroarenes, (poly)heteroarenes, thiophenes, (poly)thiophenes, (poly)anilines, and combination of above mentioned elements.

### Claim 7 (depends on 1)

The perovskite-based optoelectronic device according to claim 1, wherein the semiconductor electron transport layer is any one of doped or undoped TiO2, SnO2, Al2O3, Ga2O3, ZnO, Zn2SnO4, BaSnO3, BaTiO3, Nb2O5, Ta2O5 and ZrO2.

### Claim 8 (depends on 7)

The perovskite-based optoelectronic device according to claim 7, wherein said the semiconductor electron transport layer is planar or mesoporous.

### Claim 9 (depends on 7)

The perovskite-based optoelectronic device according to claim 7, wherein said semiconductor electron transport layer comprises a single layer or multilayers.

### Claim 10 (depends on 1)

The perovskite-based optoelectronic device according to claim 1, wherein said optically transparent electrode is any one of indium doped tin oxide (ITO, In2O3:SnO2), fluorine doped tin oxide (FTO, SnO2:F), aluminum-doped zinc oxide (AZO), gallium-doped zinc oxide (GZO), boron-doped zinc oxide (BZO), indium-doped zinc oxide (IZO).

### Claim 11 (depends on 1)

The perovskite-based optoelectronic device according to claim 1, wherein said optically transparent electrode is a film comprised of any one of silver nanowires, silver nanoparticles, carbon black, carbon nanotube, carbon nanowire, graphene, reduced graphene oxide and ultrathin graphite.

### Claim 12 (depends on 1)

The perovskite-based optoelectronic device according to claim 1, wherein said hole transport layer is any one of an organic hole transport material and an inorganic hole transport material.

### Claim 13 (depends on 12)

The perovskite-based optoelectronic device according to claim 12 wherein said inorganic hole transport material is any one of doped or undoped NiOx, WOx, MoOx, CuSCN, V2O5, MoS2, CuGaO2, PbS and any combination thereof.

### Claim 14 (depends on 12)

The perovskite-based optoelectronic device according to claim 12 wherein said organic hole transport material is any one of doped or undoped Spiro-OMeTAD (N2,N2,N2′,N2′,N7,N7,N7′,N7′-octakis(4-methoxyphenyl)-9,9′-spirobi[9Hfluorene]-2,2′,7,7′-tetramine), PTAA (Poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], P3HT (Poly(3-hexylthiophene-2,5-diyl)), Poly-TPD (Poly(N,N′-bis-4-butylphenyl-N,N′-bisphenyl)benzidine) and PEDOT:PSS (poly(3,4-ethylenedioxythiophene) polystyrene sulfonate).

### Claim 15 (depends on 1)

The perovskite-based optoelectronic device according to claim 1, wherein the perovskite has a general formula of ABX3, where
A is a monovalent cation or ion combination, wherein the monovalent cation is K+, Rb+, Cs+, or any of organic monovalent cations with the general formula of R1R2R3R4N+; where R is selected from a group consisting of hydrogen, and compounds derived from linear alkanes, branched alkanes, cycloalkanes, (poly)cycloalkanes, cis and trans-linear alkenes, cis- and trans-branched alkenes, linear alkynes, branched alkynes, (poly)alkynes, aromatic hydrocarbons, (poly)aromatic hydrocarbons, heteroarenes, (poly)heteroarenes, thiophenes, (poly)thiophenes, (poly)anilines;
B is a divalent metal ion or ion combination, wherein the divalent cation is any of Pb2+, Sn2+, Cu2+, Ge2+, Zn2+, Ni2+, Fe2+, Mn2+, Eu2+, and Co2+; and any combination thereof; and
X is any one of a halide, a pseudo halide, and any combination thereof.

### Claim 16 (depends on 15)

The perovskite-based optoelectronic device according to claim 15 wherein the halide is any one or combination of Cl−, Br−, I− and F.

### Claim 17 (depends on 15)

The perovskite-based optoelectronic device according to claim 15 wherein the pseudo halide is any one or combination of cyanide (CN), thiocyanate (SCN) and cyanate (OCN).

### Claim 18 (depends on 1)

The perovskite-based optoelectronic device according to claim 1, wherein said semiconductor electron transport layer having the surface located at the interface or junction between the electron transport layer and the light-absorbing perovskite layer is fully capped by said ligand Z.

### Claim 19 (depends on 1)

The perovskite-based optoelectronic device according to claim 1, wherein said semiconductor electron transport layer is formed from TiO2 nanocrystals, wherein said ligand is Cl−, and wherein said perovskite is MA0.15FA0.85PbI2.55Br0.45, wherein MA is methylammonium cation and FA is formamidinium cation.

### Claim 20 (depends on 1)

The perovskite-based optoelectronic device according to claim 1, wherein said electron transport layer has a thickness in a range from about 5 nm to about 300 nm, and wherein said hole transport layer has a thickness in a range from about 10 nm to about 300 nm, and wherein said light absorbing perovskite layer a thickness in a range from about 20 nm to about 2000 nm.