# US 12,014,885 B2 · Molecular doping enabled scalable blading of efficient hole transport layer-free perovskite solar cells

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- Number: US 12,014,885 B2
- Document ID: US12014885B2
- Status: Granted
- Kind: B2
- Application number: 16/393,111
- Filed: 2019-04-24
- Published: 2019-10-24
- Granted: 2024-06-18
- Earliest claimed: 2018-04-24
- Assignees: NUtech Ventures
- Applicants: NUtech Ventures
- Inventors: Jinsong Huang; Wuqiang Wu
- Web page: https://patentgrep.com/patent/US12014885B2

## CPC

- H10K 30/20: comprising organic-organic junctions, e.g. donor-acceptor junctions
- H01G 9/2059: {comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution}
- H10K 71/15: characterised by the solvent used
- H10K 71/30: Doping active layers, e.g. electron transporting layers
- H10K 85/50: Organic perovskites; Hybrid organic-inorganic perovskites [HOIP], e.g. CH3NH3PbI3
- H10K 30/50: Photovoltaic [PV] devices
- Y02E 10/542: Dye sensitized solar cells
- Y02E 10/549: Organic PV cells
- 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

## Abstract

A method of forming a photoactive device includes steps of: forming a photoactive layer, the photoactive layer comprising a perovskite material and a dopant; wherein the photoactive device comprises a positive electrode and a negative electrode; wherein said photoactive layer is directly or indirectly in electronic communication with the positive electrode and directly or indirectly in electronic communication with the negative electrode; and wherein the photoactive device is free of a hole transport layer between the photoactive layer and the positive electrode.

## Claims

### Claim 1

A method of forming a photoactive device containing a single photoactive layer, the method comprising steps of:
forming the single photoactive layer, the photoactive layer comprising a perovskite material and a dopant; wherein the step of forming comprises coating a perovskite-dopant solution onto a receiving surface of a substrate; wherein the perovskite-dopant solution comprises at least a perovskite ink and a dopant; wherein the perovskite-dopant solution comprises one or more additives; wherein the photoactive layer comprises crystalline grains characterized by an average physical dimension selected from the range of 1000 nm to 2000 nm; wherein a concentration of the dopant in the photoactive layer is selected from the range of 0.01 wt. % to 0.05 wt. %; wherein the dopant is a p-type dopant;
wherein the one or more additives comprise methylammonium hypophosphite (MHP) having a concentration in the solution selected from the range of 0.01 wt. % to 10 wt. %.;
wherein the step of forming comprises doping the perovskite material with the dopant by solid diffusion;
wherein doping by solid diffusion comprises providing a perovskite material free of the dopant in proximity with a solid dopant material and allowing the solid dopant material to diffuse into the perovskite material;
wherein the photoactive device comprises a positive electrode and a negative electrode;
wherein said photoactive layer is in electronic communication with the positive electrode and in electronic communication with the negative electrode;
wherein the photoactive device is free of a hole transport layer between the photoactive layer and the positive electrode;
wherein the photoactive device comprises an electron transport layer between the photoactive layer and the negative electrode; and
wherein the photoactive device does not contain multiple photoactive layers, and the single photoactive layer is in contact with the electron transport layer.

### Claim 2 (depends on 1)

The method of claim 1, comprising preparing the perovskite-dopant solution by combining at least: the perovskite ink, the dopant, and one or more solvents.

### Claim 3 (depends on 1)

The method of claim 1, the step of coating comprising doctor blading.

### Claim 4 (depends on 1)

The method of claim 1, wherein at least a portion of the photoactive layer is in direct physical contact with the positive electrode.

### Claim 5 (depends on 1)

The method of claim 1, wherein at least one of the substrate and the receiving surface of the substrate is at least a portion of the positive electrode.

### Claim 6 (depends on 1)

The method of claim 1, wherein the dopant comprises 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ).

### Claim 7 (depends on 1)

The method of claim 1, wherein the positive electrode is a transparent electrical conductor.

### Claim 8 (depends on 1)

The method of claim 1, wherein a total concentration of the one or more additives in the perovskite-dopant solution is selected from the range of 0.075 wt. % to 0.8 wt. %.

### Claim 9 (depends on 1)

The method of claim 1, wherein the perovskite material is characterized by a chemical formula comprising at least two chemical species selected from the group consisting of Pb, Sn, Sb, Fe, Ge, Mn, Mo, Ta, Ag, Na, K, Ru, Cs, formamidinium (“FA”), methylammonium (“MA”), ethylammonium, propylammonium, butylammonium, amylammonium, hexylammonium, heptylammonium, octylammonium, oleylammonium, formamidinium, dodecylammonium, phenylethylammonium, benzylammonium, ethylenediammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, hexadecyl trimethyl ammonium, and ethanediammonium, and at least one chemical species selected from the group consisting of I, Br, Cl, F, COO, BF3 and SCN.

### Claim 10 (depends on 1)

The method of claim 1, wherein the photoactive device is a photovoltaic cell.

### Claim 11 (depends on 10)

The method of claim 10, wherein an average photovoltaic efficiency of the photoactive device is greater by a factor of 1.8 to 2.2 times than an average photovoltaic efficiency of an otherwise equivalent photovoltaic cell free of the dopant.

### Claim 12 (depends on 1)

The method of claim 1, wherein the photoactive device is free of an undoped perovskite layer.

### Claim 13 (depends on 1)

The method of claim 1, wherein the positive electrode is in contact with the photoactive layer, the photoactive layer is in contact with the electron transport layer, and the electron transport layer is in contact with the negative electrode.

### Claim 14 (depends on 1)

The method of claim 1, wherein the electron transport layer comprises C60 and/or bathocuproine.

### Claim 15 (depends on 1)

The method of claim 1, wherein a total concentration of the one or more additives in the perovskite-dopant solution is selected from the range of 0.225 wt. % to 1 wt. %.

### Claim 16 (depends on 1)

The method of claim 1, wherein the dopant comprises 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) and wherein the one or more additives comprise methylammonium hypophosphite (MHP).

### Claim 17 (depends on 1)

The method of claim 1, wherein a total concentration of the one or more additives in the perovskite-dopant solution is selected from the range of 0.01 wt. % to 0.35 wt. %.