Jun.25,2019  (45)  Date of Patent:  (IO)  Patent No.:  US 10,332,688 B2  c12)  United States Patent  Zhu  et al.  (54)  METHODS FOR MAKING PEROVSKITE  SOLAR CELLS HAVING IMPROVED  HOLE-TRANSPORT LAYERS  (56)  References Cited  U.S. PATENT DOCUMENTS  FOREIGN PATENT DOCUMENTS  OTHER PUBLICATIONS  (57)  ABSTRACT  22 Claims, 35 Drawing Sheets  Related U.S. Application Data  (65)  Prior Publication Data  ---~- ....  -- .... __  c  -••-•w/o  acid  •w  iO  C  OJ  -0  ......,  --HPO  3  "  - - -CF,PA  C  !E  5  •••••••••••  H$_{2}$SO,  ’-- ::J  ----- AcOH  0  0  +---.----r--..------.---.--..-----.---.--.----.’_,_--1  0.0  0.2  0.4  0.6  0.8  1.0  Voltage (V)  ( 58)  Field of Classification Search  None  See application file for complete search history.  (52)  U.S. Cl.  CPC .........  H0lG 9/2004  (2013.01);  H0lG 9/2059  (2013.01);  H0JL 5110004  (2013.01);  (Continued)  (51)  Int. Cl.  (60)  Provisional application No. 621356,328, filed on Jun.  29, 2016.  (22)  Filed:  Jun. 29, 2017  (21)  Appl. No.:  151636,949  ( *)  Notice:  Subject to any disclaimer, the term ofthis  patent is extended or adjusted under 35  U.S.C. 154(b) by  O  days.  (73)  Assignee:  Alliance for Sustainable Energy, LLC,  Golden, CO (US)  (71)  Applicants:Alliance for Sustainable Energy, LLC,  Golden, CO (US);  Colorado School of  Mines,  Golden, CO (US)  Primary Examiner  - Devina Pillay  (74)  Attorney, Agent, or Firm  - Michael A. McIntyre  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).*  (Continued)  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.  H0lG 9/20  H0JL 51100  H0JL 51142  (2006.01)  (2006.01)  (2006.01)  US 201810005762 Al  Jan. 4, 2018  2004/0260047 Al* 12/2004 Chen .  C09K 11/06  528/4  2005/0062012 Al*  3/2005 Shinohara ........... HO lL 51/0003  252/62.3 R  (Continued)  EP  EP  WO  1 107 332 A2  1 117 137 A2  WO 2015/159192 Al  6/2001  7/2001  10/2015  (72)  Inventors:  Kai Zhu,  Littleton, CO (US);  Zhen  Li,  Lakewood, CO (US);  Alan Sellinger,  Golden, CO (US);  Jonathan Scott  Tinkham,  Denver, CO (US)  US010332688B2 