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# c12) United States Patent 

# Zhu et al. 

# (54) METHODS FOR MAKING PEROVSKITE SOLAR CELLS HAVING IMPROVED HOLE-TRANSPORT LAYERS 

(71) Applicants:Alliance for Sustainable Energy, LLC, Golden, CO (US); Colorado School of Mines, Golden, CO (US) 

(72) Inventors: Kai Zhu, Littleton, CO (US); Zhen Li, Lakewood, CO (US); Alan Sellinger, Golden, CO (US); Jonathan Scott Tinkham, Denver, CO (US) 

(73) Assignee: Alliance for Sustainable Energy, LLC, Golden, CO (US) 

( *) Notice: Subject to any disclaimer, the term ofthis patent is extended or adjusted under 35 U.S.C. 154(b) by O days. 

(21) Appl. No.: 151636,949 

(22) Filed: Jun. 29, 2017 

## (65) Prior Publication Data 

US 201810005762 Al Jan. 4, 2018 

(60) Provisional application No. 621356,328, filed on Jun. 29, 2016. 

(51) Int. Cl. 

<img src='content_image/948175.jpg'>

(52) U.S. Cl. CPC ......... H0lG 9/2004 (2013.01); H0lG 9/2059 (2013.01); H0JL 5110004 (2013.01); (Continued) 

( 58) Field of Classification Search None See application file for complete search history. 

## Related U.S. Application Data 

<img src='content_image/948161.jpg'>

<img src='content_image/948182.jpg'>

# (IO) Patent No.: US 10,332,688 B2 

# Jun.25,2019 (45) Date of Patent: 

## (56) References Cited 

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## FOREIGN PATENT DOCUMENTS 

<img src='content_image/948179.jpg'>

Nam, "Doping Effect of Organosulfonic Acid m Poly(3- hexylthiophene) Films for Organic Field-Effect Transistors", ACS Appl. Mater. Interfaces 2012, 4, 1281-1288 (Year: 2012).* 

Primary Examiner - Devina Pillay (74) Attorney, Agent, or Firm - Michael A. McIntyre 

## (57) ABSTRACT 

An aspect of the present disclosure is a device that includes a first layer that includes a hole-transport material and an acid, where the first layer has a conductivity between 20 µSiem and 500 µSiem. In some embodiments of the present disclosure, the first layer may absorb light having a wave› length between 400 nm and 600 nm. In some embodiments of the present disclosure, the hole-transport material may include at least one of 2,2’,7,7’-tetrakis(N,N-di-p-methoxy› phenylamine )-9 ,9’-spiro bifluorene ( spiro-O Me TAD), a derivative of spiro-OMeTAD, poly(triarylamine), poly(3- hexylthiophene), and/or N,N’-bis(3-methylphenyl)-N,N’-di› phenylbenzidine. 

US010332688B2 

## U.S. PATENT DOCUMENTS 

## OTHER PUBLICATIONS 

## 22 Claims, 35 Drawing Sheets 

(Continued) 

(Continued) 

