skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Room-temperature fabrication of a delafossite CuCrO 2 hole transport layer for perovskite solar cells

Abstract

Delafossite oxides are promising hole transport layer (HTL) candidates for perovskite solar cells, due to their wide band gap, favorable energy band alignment relative to the perovskite absorber and simplicity of processing. Here, we investigate the properties of CuCrO 2 (CCO) delafossite films using an integration of experimental and computational techniques. Phase-pure CCO films are deposited at room temperature by spin-casting suspensions of hydrothermally-synthesized nanoparticles, for use in a glass/ITO/CCO/CH 3NH 3PbI 3/C 60/BCP/Ag device structure. Although density functional theory (DFT) calculations predict an elevated hole effective mass along certain crystallographic directions, the nearly isotropic shape and small size of the CCO nanoparticles preserves transport properties within the films by randomizing particle orientation, preventing these unfavorable directions from dominating the film conductivity. Experimental measurements confirm that the CCO films display appropriate optical and electrical properties for use as an HTL, in good agreement with the DFT calculations. Finally, solar cells made using these films exhibit stabilized power conversion efficiencies exceeding 14%, with only minor hysteresis in the current–voltage characteristics.

Authors:
ORCiD logo [1];  [2];  [3]; ORCiD logo [4];  [2];  [2]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [1]
  1. Duke Univ., Durham, NC (United States)
  2. Univ. of Texas at Dallas, Richardson, TX (United States)
  3. Univ. of Toledo, OH (United States)
  4. Univ. of Texas at Dallas, Richardson, TX (United States); Univ. of Washington, Seattle, WA (United States)
Publication Date:
Research Org.:
Duke Univ., Durham, NC (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
OSTI Identifier:
1593914
Grant/Contract Number:  
[EE0006712; AC02-05CH11231]
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
[ Journal Volume: 6; Journal Issue: 2]; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 14 SOLAR ENERGY

Citation Formats

Dunlap-Shohl, Wiley A., Daunis, Trey B., Wang, Xiaoming, Wang, Jian, Zhang, Boya, Barrera, Diego, Yan, Yanfa, Hsu, Julia W. P., and Mitzi, David B. Room-temperature fabrication of a delafossite CuCrO2 hole transport layer for perovskite solar cells. United States: N. p., 2017. Web. doi:10.1039/C7TA09494A.
Dunlap-Shohl, Wiley A., Daunis, Trey B., Wang, Xiaoming, Wang, Jian, Zhang, Boya, Barrera, Diego, Yan, Yanfa, Hsu, Julia W. P., & Mitzi, David B. Room-temperature fabrication of a delafossite CuCrO2 hole transport layer for perovskite solar cells. United States. doi:10.1039/C7TA09494A.
Dunlap-Shohl, Wiley A., Daunis, Trey B., Wang, Xiaoming, Wang, Jian, Zhang, Boya, Barrera, Diego, Yan, Yanfa, Hsu, Julia W. P., and Mitzi, David B. Mon . "Room-temperature fabrication of a delafossite CuCrO2 hole transport layer for perovskite solar cells". United States. doi:10.1039/C7TA09494A. https://www.osti.gov/servlets/purl/1593914.
@article{osti_1593914,
title = {Room-temperature fabrication of a delafossite CuCrO2 hole transport layer for perovskite solar cells},
author = {Dunlap-Shohl, Wiley A. and Daunis, Trey B. and Wang, Xiaoming and Wang, Jian and Zhang, Boya and Barrera, Diego and Yan, Yanfa and Hsu, Julia W. P. and Mitzi, David B.},
abstractNote = {Delafossite oxides are promising hole transport layer (HTL) candidates for perovskite solar cells, due to their wide band gap, favorable energy band alignment relative to the perovskite absorber and simplicity of processing. Here, we investigate the properties of CuCrO2 (CCO) delafossite films using an integration of experimental and computational techniques. Phase-pure CCO films are deposited at room temperature by spin-casting suspensions of hydrothermally-synthesized nanoparticles, for use in a glass/ITO/CCO/CH3NH3PbI3/C60/BCP/Ag device structure. Although density functional theory (DFT) calculations predict an elevated hole effective mass along certain crystallographic directions, the nearly isotropic shape and small size of the CCO nanoparticles preserves transport properties within the films by randomizing particle orientation, preventing these unfavorable directions from dominating the film conductivity. Experimental measurements confirm that the CCO films display appropriate optical and electrical properties for use as an HTL, in good agreement with the DFT calculations. Finally, solar cells made using these films exhibit stabilized power conversion efficiencies exceeding 14%, with only minor hysteresis in the current–voltage characteristics.},
doi = {10.1039/C7TA09494A},
journal = {Journal of Materials Chemistry. A},
number = [2],
volume = [6],
place = {United States},
year = {2017},
month = {12}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 35 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Fabrication of bipolar CuInO2 with delafossite structure
journal, September 2003


Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Hexagonal polytype of CuCrO2 nanocrystals obtained by hydrothermal method
journal, August 2012


Origin of the Thermal Instability in CH 3 NH 3 PbI 3 Thin Films Deposited on ZnO
journal, June 2015


Enhancing the photovoltaic performance of planar heterojunction perovskite solar cells by doping the perovskite layer with alkali metal ions
journal, January 2016

  • Chang, Jingjing; Lin, Zhenhua; Zhu, Hai
  • Journal of Materials Chemistry A, Vol. 4, Issue 42
  • DOI: 10.1039/C6TA06851K

Interfacial electronic structure at the CH 3 NH 3 PbI 3 /MoO x interface
journal, May 2015

  • Liu, Peng; Liu, Xiaoliang; Lyu, Lu
  • Applied Physics Letters, Vol. 106, Issue 19
  • DOI: 10.1063/1.4921339

Not All That Glitters Is Gold: Metal-Migration-Induced Degradation in Perovskite Solar Cells
journal, May 2016

  • Domanski, Konrad; Correa-Baena, Juan-Pablo; Mine, Nicolas
  • ACS Nano, Vol. 10, Issue 6
  • DOI: 10.1021/acsnano.6b02613

Projector augmented-wave method
journal, December 1994


Optical and electronic properties of delafossite CuBO 2 p -type transparent conducting oxide
journal, September 2013

  • Ruttanapun, Chesta
  • Journal of Applied Physics, Vol. 114, Issue 11
  • DOI: 10.1063/1.4821960

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


Strong Yellow-Green Luminescence in Delafossite-Type CuLaO 2 Doped with Calcium or Strontium
journal, June 2007

  • Katsui, Akinori; Takahashi, Yuhsuke; Matsushita, Hiroaki
  • Japanese Journal of Applied Physics, Vol. 46, Issue No. 23
  • DOI: 10.1143/JJAP.46.L546

Thermal stability of nanocrystalline 3R-CuCrO2
journal, December 2013


High-Efficiency Solution-Processed Planar Perovskite Solar Cells with a Polymer Hole Transport Layer
journal, December 2014

  • Zhao, Dewei; Sexton, Michael; Park, Hye-Yun
  • Advanced Energy Materials, Vol. 5, Issue 6
  • DOI: 10.1002/aenm.201401855

Crystal chemistry and electrical properties of the delafossite structure
journal, February 2006

  • Marquardt, Meagen A.; Ashmore, Nathan A.; Cann, David P.
  • Thin Solid Films, Vol. 496, Issue 1
  • DOI: 10.1016/j.tsf.2005.08.316

Preparation of Trigonal and Hexagonal Cuprous Chromite and Phase Transition Study Based on Single Crystal Structure Data
journal, February 1996

  • Crottaz, O.; Kubel, F.; Schmid, H.
  • Journal of Solid State Chemistry, Vol. 122, Issue 1
  • DOI: 10.1006/jssc.1996.0109

Iodide management in formamidinium-lead-halide–based perovskite layers for efficient solar cells
journal, June 2017


Silver Iodide Formation in Methyl Ammonium Lead Iodide Perovskite Solar Cells with Silver Top Electrodes
journal, July 2015

  • Kato, Yuichi; Ono, Luis K.; Lee, Michael V.
  • Advanced Materials Interfaces, Vol. 2, Issue 13
  • DOI: 10.1002/admi.201500195

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Solution Synthesized p -Type Copper Gallium Oxide Nanoplates as Hole Transport Layer for Organic Photovoltaic Devices
journal, March 2015

  • Wang, Jian; Ibarra, Vanessa; Barrera, Diego
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 6
  • DOI: 10.1021/acs.jpclett.5b00236

Sub-10 nm copper chromium oxide nanocrystals as a solution processed p-type hole transport layer for organic photovoltaics
journal, January 2016

  • Wang, Jian; Lee, Yun-Ju; Hsu, Julia W. P.
  • Journal of Materials Chemistry C, Vol. 4, Issue 16
  • DOI: 10.1039/C6TC00541A

Colloidally prepared La-doped BaSnO 3 electrodes for efficient, photostable perovskite solar cells
journal, March 2017


Ionization potentials of (112) and (11 2 ¯ ) facet surfaces of CuInSe 2 and CuGaSe 2
journal, December 2012


Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
journal, January 1998

  • Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y.
  • Physical Review B, Vol. 57, Issue 3, p. 1505-1509
  • DOI: 10.1103/PhysRevB.57.1505

Highly Reproducible Perovskite Solar Cells with Average Efficiency of 18.3% and Best Efficiency of 19.7% Fabricated via Lewis Base Adduct of Lead(II) Iodide
journal, July 2015

  • Ahn, Namyoung; Son, Dae-Yong; Jang, In-Hyuk
  • Journal of the American Chemical Society, Vol. 137, Issue 27
  • DOI: 10.1021/jacs.5b04930

Solution-processed CuO as an efficient hole-extraction layer for inverted planar heterojunction perovskite solar cells
journal, January 2017


Germanium-Gallium Arsenide Heterojunctions [Letter to the Editor]
journal, July 1960

  • Anderson, R. L.
  • IBM Journal of Research and Development, Vol. 4, Issue 3
  • DOI: 10.1147/rd.43.0283

CuGaO 2 : A Promising Inorganic Hole-Transporting Material for Highly Efficient and Stable Perovskite Solar Cells
journal, December 2016


Structure of poorly crystalline MoS2 — A modeling study
journal, February 1986


Incorporation of rubidium cations into perovskite solar cells improves photovoltaic performance
journal, September 2016


Oxygen intercalation of two polymorphs of CuScO2
journal, August 2004


Chemistry of noble metal oxides. I. Syntheses and properties of ABO2 delafossite compounds
journal, April 1971

  • Shannon, Robert D.; Rogers, Donald Burl; Prewitt, Charles T.
  • Inorganic Chemistry, Vol. 10, Issue 4
  • DOI: 10.1021/ic50098a011

Externally quenched air counter for low‐energy electron emission measurements
journal, January 1981

  • Kirihata, H.; Uda, M.
  • Review of Scientific Instruments, Vol. 52, Issue 1
  • DOI: 10.1063/1.1136448

Electronic band structures and excitonic properties of delafossites: A GW -BSE study
journal, August 2017

  • Wang, Xiaoming; Meng, Weiwei; Yan, Yanfa
  • Journal of Applied Physics, Vol. 122, Issue 8
  • DOI: 10.1063/1.4991913

Effects of Cd Diffusion and Doping in High-Performance Perovskite Solar Cells Using CdS as Electron Transport Layer
journal, July 2016

  • Dunlap-Shohl, Wiley A.; Younts, Robert; Gautam, Bhoj
  • The Journal of Physical Chemistry C, Vol. 120, Issue 30
  • DOI: 10.1021/acs.jpcc.6b05406

Overcoming ultraviolet light instability of sensitized TiO2 with meso-superstructured organometal tri-halide perovskite solar cells
journal, December 2013

  • Leijtens, Tomas; Eperon, Giles E.; Pathak, Sandeep
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms3885

Hydrothermal synthesis of ultrasmall CuCrO2 nanocrystal alternatives to NiO nanoparticles in efficient p-type dye-sensitized solar cells
journal, January 2012

  • Xiong, Dehua; Xu, Zhen; Zeng, Xianwei
  • Journal of Materials Chemistry, Vol. 22, Issue 47
  • DOI: 10.1039/c2jm35101c

Iodine Migration and Degradation of Perovskite Solar Cells Enhanced by Metallic Electrodes
journal, November 2016

  • Besleaga, Cristina; Abramiuc, Laura Elena; Stancu, Viorica
  • The Journal of Physical Chemistry Letters, Vol. 7, Issue 24
  • DOI: 10.1021/acs.jpclett.6b02375

Transport and Defect Mechanisms in Cuprous Delafossites. 2. CuScO 2 and CuYO 2
journal, December 2004

  • Ingram, Brian J.; Harder, Bryan J.; Hrabe, Nikolas W.
  • Chemistry of Materials, Vol. 16, Issue 26
  • DOI: 10.1021/cm048982k

Stacking fault analysis in layered materials
journal, December 2001


Identification and Mitigation of a Critical Interfacial Instability in Perovskite Solar Cells Employing Copper Thiocyanate Hole-Transporter
journal, August 2016

  • Liu, Jiewei; Pathak, Sandeep K.; Sakai, Nobuya
  • Advanced Materials Interfaces, Vol. 3, Issue 22
  • DOI: 10.1002/admi.201600571

Implementation and performance of the frequency-dependent G W method within the PAW framework
journal, July 2006


    Works referencing / citing this record:

    Perovskite Solar Cells Using Surface‐Modified NiO x Nanoparticles as Hole Transport Materials in n‐i‐p Configuration
    journal, May 2019