DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: GeI2 Additive for High Optoelectronic Quality CsPbI3 Quantum Dots and Their Application in Photovoltaic Devices

Abstract

Trioctylphosphine (TOP)-based syntheses of CsPbI3 perovskite quantum dots (QDs) yield unprecedented high photoluminescence quantum yield (PL QY), lower Stokes shifts, and longer carrier lifetimes due to their enhanced crystallinity. This synthetic route relies on a heavily Pb-rich condition or a large Pb:Cs molar ratio in precursor solution to produce QDs with appropriate stoichiometry as well as to guarantee a good colloidal stability. The high Pb condition is achieved by a high concentration of PbI2 prepared in TOP. Here we find such Pb-rich strategies can be avoided by providing additional iodine ions using other metal halide salts. In particular GeI2, which contrary to PbI2, readily dissolves in TOP. CsPbI3 QDs prepared using PbI2/GeI2 combination show near-unity PL QY and improved chemical stability compared to the previous synthetic route. Furthermore, we find no sign of Ge incorporation in the QDs (compositionally or energetically). The ensuing QD solar cells deliver power conversion efficiency of 12.15% and retain 85% of its peak performance after storage over 90 days. The PbI2/GeI2 dual-source iodine synthetic approach presented here represents a more rational and robust route to high-quality CsPbI3 QDs. to guarantee a good colloidal stability. The high Pb condition is achieved by a high concentration ofmore » PbI2 prepared in TOP. Here we find such Pb-rich strategies can be avoided by providing additional iodine ions using other metal halide salts. In particular GeI2, which contrary to PbI2, readily dissolves in TOP. CsPbI3 QDs prepared using PbI2/GeI2 combination show near-unity PL QY and improved chemical stability compared to the previous synthetic route. Furthermore, we find no sign of Ge incorporation in the QDs (compositionally or energetically). The ensuing QD solar cells deliver power conversion efficiency of 12.15% and retain 85% of its peak performance after storage over 90 days. The PbI2/GeI2 dual-source iodine synthetic approach presented here represents a more rational and robust route to high-quality CsPbI3 QDs.« less

Authors:
 [1];  [1];  [1];  [1];  [2]; ORCiD logo [3];  [1];  [4];  [5];  [6];  [7];  [7];  [8];  [8];  [1]
  1. Univ. of Electro-Communications, Tokyo (Japan)
  2. National Renewable Energy Lab. (NREL), Golden, CO (United States); Nankai Univ. (China)
  3. National Renewable Energy Lab. (NREL), Golden, CO (United States)
  4. Kyushu Inst. of Technology, Kitakyushu (Japan)
  5. Ritsumeikan Univ., Shiga (Japan)
  6. Miyazaki Univ. (Japan)
  7. North China Electric Power Univ., Beijing (China)
  8. Eindhoven Univ. of Technology (Netherlands)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE National Renewable Energy Laboratory (NREL), Laboratory Directed Research and Development (LDRD) Program
OSTI Identifier:
1513189
Report Number(s):
NREL/JA-5900-71882
Journal ID: ISSN 0897-4756
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry of Materials
Additional Journal Information:
Journal Volume: 31; Journal Issue: 3; Journal ID: ISSN 0897-4756
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
14 SOLAR ENERGY; 36 MATERIALS SCIENCE; quantum dots; photoluminescence quantum yield; Gel2

Citation Formats

Liu, Feng, Ding, Chao, Zhang, Yaohong, Kamisaka, Taichi, Zhao, Qian, Luther, Joseph M, Toyoda, Taro, Hayase, Shuzi, Minemoto, Takashi, Yoshino, Kenji, Zhang, Bing, Dai, Songyuan, Jiang, Junke, Tao, Shuxia, and Shen, Qing. GeI2 Additive for High Optoelectronic Quality CsPbI3 Quantum Dots and Their Application in Photovoltaic Devices. United States: N. p., 2019. Web. doi:10.1021/acs.chemmater.8b03871.
Liu, Feng, Ding, Chao, Zhang, Yaohong, Kamisaka, Taichi, Zhao, Qian, Luther, Joseph M, Toyoda, Taro, Hayase, Shuzi, Minemoto, Takashi, Yoshino, Kenji, Zhang, Bing, Dai, Songyuan, Jiang, Junke, Tao, Shuxia, & Shen, Qing. GeI2 Additive for High Optoelectronic Quality CsPbI3 Quantum Dots and Their Application in Photovoltaic Devices. United States. https://doi.org/10.1021/acs.chemmater.8b03871
Liu, Feng, Ding, Chao, Zhang, Yaohong, Kamisaka, Taichi, Zhao, Qian, Luther, Joseph M, Toyoda, Taro, Hayase, Shuzi, Minemoto, Takashi, Yoshino, Kenji, Zhang, Bing, Dai, Songyuan, Jiang, Junke, Tao, Shuxia, and Shen, Qing. Mon . "GeI2 Additive for High Optoelectronic Quality CsPbI3 Quantum Dots and Their Application in Photovoltaic Devices". United States. https://doi.org/10.1021/acs.chemmater.8b03871. https://www.osti.gov/servlets/purl/1513189.
@article{osti_1513189,
title = {GeI2 Additive for High Optoelectronic Quality CsPbI3 Quantum Dots and Their Application in Photovoltaic Devices},
author = {Liu, Feng and Ding, Chao and Zhang, Yaohong and Kamisaka, Taichi and Zhao, Qian and Luther, Joseph M and Toyoda, Taro and Hayase, Shuzi and Minemoto, Takashi and Yoshino, Kenji and Zhang, Bing and Dai, Songyuan and Jiang, Junke and Tao, Shuxia and Shen, Qing},
abstractNote = {Trioctylphosphine (TOP)-based syntheses of CsPbI3 perovskite quantum dots (QDs) yield unprecedented high photoluminescence quantum yield (PL QY), lower Stokes shifts, and longer carrier lifetimes due to their enhanced crystallinity. This synthetic route relies on a heavily Pb-rich condition or a large Pb:Cs molar ratio in precursor solution to produce QDs with appropriate stoichiometry as well as to guarantee a good colloidal stability. The high Pb condition is achieved by a high concentration of PbI2 prepared in TOP. Here we find such Pb-rich strategies can be avoided by providing additional iodine ions using other metal halide salts. In particular GeI2, which contrary to PbI2, readily dissolves in TOP. CsPbI3 QDs prepared using PbI2/GeI2 combination show near-unity PL QY and improved chemical stability compared to the previous synthetic route. Furthermore, we find no sign of Ge incorporation in the QDs (compositionally or energetically). The ensuing QD solar cells deliver power conversion efficiency of 12.15% and retain 85% of its peak performance after storage over 90 days. The PbI2/GeI2 dual-source iodine synthetic approach presented here represents a more rational and robust route to high-quality CsPbI3 QDs. to guarantee a good colloidal stability. The high Pb condition is achieved by a high concentration of PbI2 prepared in TOP. Here we find such Pb-rich strategies can be avoided by providing additional iodine ions using other metal halide salts. In particular GeI2, which contrary to PbI2, readily dissolves in TOP. CsPbI3 QDs prepared using PbI2/GeI2 combination show near-unity PL QY and improved chemical stability compared to the previous synthetic route. Furthermore, we find no sign of Ge incorporation in the QDs (compositionally or energetically). The ensuing QD solar cells deliver power conversion efficiency of 12.15% and retain 85% of its peak performance after storage over 90 days. The PbI2/GeI2 dual-source iodine synthetic approach presented here represents a more rational and robust route to high-quality CsPbI3 QDs.},
doi = {10.1021/acs.chemmater.8b03871},
journal = {Chemistry of Materials},
number = 3,
volume = 31,
place = {United States},
year = {2019},
month = {1}
}

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

Citation Metrics:
Cited by: 24 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Interfacial benzenethiol modification facilitates charge transfer and improves stability of cm-sized metal halide perovskite solar cells with up to 20% efficiency
journal, January 2018

  • Lu, Jianfeng; Lin, Xiongfeng; Jiao, Xuechen
  • Energy & Environmental Science, Vol. 11, Issue 7
  • DOI: 10.1039/C8EE00754C

A mixed-cation lead mixed-halide perovskite absorber for tandem solar cells
journal, January 2016


Efficient luminescent solar cells based on tailored mixed-cation perovskites
journal, January 2016


Hierarchical Arrays of Cesium Lead Halide Perovskite Nanocrystals through Electrophoretic Deposition
journal, June 2018

  • Ravi, Vikash Kumar; Scheidt, Rebecca A.; DuBose, Jeffrey
  • Journal of the American Chemical Society, Vol. 140, Issue 28
  • DOI: 10.1021/jacs.8b04803

Polymer-Free Films of Inorganic Halide Perovskite Nanocrystals as UV-to-White Color-Conversion Layers in LEDs
journal, April 2016


Low-threshold amplified spontaneous emission and lasing from colloidal nanocrystals of caesium lead halide perovskites
journal, August 2015

  • Yakunin, Sergii; Protesescu, Loredana; Krieg, Franziska
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms9056

Hole Transport Layer Free Inorganic CsPbIBr 2 Perovskite Solar Cell by Dual Source Thermal Evaporation
journal, February 2016

  • Ma, Qingshan; Huang, Shujuan; Wen, Xiaoming
  • Advanced Energy Materials, Vol. 6, Issue 7
  • DOI: 10.1002/aenm.201502202

µ-Graphene Crosslinked CsPbI 3 Quantum Dots for High Efficiency Solar Cells with Much Improved Stability
journal, May 2018


3D-2D-0D Interface Profiling for Record Efficiency All-Inorganic CsPbBrI 2 Perovskite Solar Cells with Superior Stability
journal, January 2018

  • Zhang, Jingru; Bai, Dongliang; Jin, Zhiwen
  • Advanced Energy Materials, Vol. 8, Issue 15
  • DOI: 10.1002/aenm.201703246

Bandgap-Tunable Cesium Lead Halide Perovskites with High Thermal Stability for Efficient Solar Cells
journal, February 2016

  • Sutton, Rebecca J.; Eperon, Giles E.; Miranda, Laura
  • Advanced Energy Materials, Vol. 6, Issue 8
  • DOI: 10.1002/aenm.201502458

Quantum dot-induced phase stabilization of  -CsPbI3 perovskite for high-efficiency photovoltaics
journal, October 2016


Genesis, challenges and opportunities for colloidal lead halide perovskite nanocrystals
journal, February 2018

  • Akkerman, Quinten A.; Rainò, Gabriele; Kovalenko, Maksym V.
  • Nature Materials, Vol. 17, Issue 5
  • DOI: 10.1038/s41563-018-0018-4

Enhanced stabilization of inorganic cesium lead triiodide (CsPbI3) perovskite quantum dots with tri-octylphosphine
journal, July 2017


Nanocrystals of Cesium Lead Halide Perovskites (CsPbX 3 , X = Cl, Br, and I): Novel Optoelectronic Materials Showing Bright Emission with Wide Color Gamut
journal, February 2015

  • Protesescu, Loredana; Yakunin, Sergii; Bodnarchuk, Maryna I.
  • Nano Letters, Vol. 15, Issue 6
  • DOI: 10.1021/nl5048779

Thermodynamically Stable Orthorhombic γ-CsPbI 3 Thin Films for High-Performance Photovoltaics
journal, August 2018

  • Zhao, Boya; Jin, Shi-Feng; Huang, Sheng
  • Journal of the American Chemical Society, Vol. 140, Issue 37
  • DOI: 10.1021/jacs.8b06050

Polar Solvent Induced Lattice Distortion of Cubic CsPbI 3 Nanocubes and Hierarchical Self-Assembly into Orthorhombic Single-Crystalline Nanowires
journal, August 2018

  • Sun, Jian-Kun; Huang, Sheng; Liu, Xiao-Zhi
  • Journal of the American Chemical Society, Vol. 140, Issue 37
  • DOI: 10.1021/jacs.8b05949

Quantum Dot Light-Emitting Diodes Based on Inorganic Perovskite Cesium Lead Halides (CsPbX 3 )
journal, October 2015


Monodisperse Formamidinium Lead Bromide Nanocrystals with Bright and Stable Green Photoluminescence
journal, October 2016

  • Protesescu, Loredana; Yakunin, Sergii; Bodnarchuk, Maryna I.
  • Journal of the American Chemical Society, Vol. 138, Issue 43
  • DOI: 10.1021/jacs.6b08900

Ligand Mediated Transformation of Cesium Lead Bromide Perovskite Nanocrystals to Lead Depleted Cs 4 PbBr 6 Nanocrystals
journal, April 2017

  • Liu, Zeke; Bekenstein, Yehonadav; Ye, Xingchen
  • Journal of the American Chemical Society, Vol. 139, Issue 15
  • DOI: 10.1021/jacs.7b01409

Mn 2+ -Doped Lead Halide Perovskite Nanocrystals with Dual-Color Emission Controlled by Halide Content
journal, November 2016

  • Liu, Wenyong; Lin, Qianglu; Li, Hongbo
  • Journal of the American Chemical Society, Vol. 138, Issue 45
  • DOI: 10.1021/jacs.6b08085

Colloidal Synthesis of Air-Stable Alloyed CsSn 1– x Pb x I 3 Perovskite Nanocrystals for Use in Solar Cells
journal, November 2017

  • Liu, Feng; Ding, Chao; Zhang, Yaohong
  • Journal of the American Chemical Society, Vol. 139, Issue 46
  • DOI: 10.1021/jacs.7b08628

Synthesis and Optical Properties of Lead-Free Cesium Tin Halide Perovskite Nanocrystals
journal, February 2016

  • Jellicoe, Tom C.; Richter, Johannes M.; Glass, Hugh F. J.
  • Journal of the American Chemical Society, Vol. 138, Issue 9
  • DOI: 10.1021/jacs.5b13470

Ligand-Free, Quantum-Confined Cs 2 SnI 6 Perovskite Nanocrystals
journal, September 2017


Nucleation, Growth, and Structural Transformations of Perovskite Nanocrystals
journal, January 2017


Highly Luminescent Phase-Stable CsPbI 3 Perovskite Quantum Dots Achieving Near 100% Absolute Photoluminescence Quantum Yield
journal, September 2017


Fast Anion-Exchange in Highly Luminescent Nanocrystals of Cesium Lead Halide Perovskites (CsPbX 3 , X = Cl, Br, I)
journal, July 2015


Perovskite Quantum Dot Photovoltaic Materials beyond the Reach of Thin Films: Full-Range Tuning of A-Site Cation Composition
journal, September 2018


Tuning the Optical Properties of Cesium Lead Halide Perovskite Nanocrystals by Anion Exchange Reactions
journal, August 2015

  • Akkerman, Quinten A.; D’Innocenzo, Valerio; Accornero, Sara
  • Journal of the American Chemical Society, Vol. 137, Issue 32
  • DOI: 10.1021/jacs.5b05602

General Strategy for the Growth of CsPbX 3 (X = Cl, Br, I) Perovskite Nanosheets from the Assembly of Nanorods
journal, May 2018


Synthesis of Cesium Lead Halide Perovskite Nanocrystals in a Droplet-Based Microfluidic Platform: Fast Parametric Space Mapping
journal, February 2016


Halide-Rich Synthesized Cesium Lead Bromide Perovskite Nanocrystals for Light-Emitting Diodes with Improved Performance
journal, May 2017


Benzoyl Halides as Alternative Precursors for the Colloidal Synthesis of Lead-Based Halide Perovskite Nanocrystals
journal, January 2018

  • Imran, Muhammad; Caligiuri, Vincenzo; Wang, Mengjiao
  • Journal of the American Chemical Society, Vol. 140, Issue 7
  • DOI: 10.1021/jacs.7b13477

Highly Stable Cesium Lead Halide Perovskite Nanocrystals through in Situ Lead Halide Inorganic Passivation
journal, August 2017


Precise Control of Quantum Confinement in Cesium Lead Halide Perovskite Quantum Dots via Thermodynamic Equilibrium
journal, May 2018


Synthesis and vibrational spectra of some lead(II) halide adducts with O-, S-, and N-donor atom ligands
journal, November 1976

  • Wharf, Ivor; Gramstad, Thor; Makhija, Ramesh
  • Canadian Journal of Chemistry, Vol. 54, Issue 21
  • DOI: 10.1139/v76-493

High Yield of Germanium Nanocrystals Synthesized from Germanium Diiodide in Solution
journal, December 2005

  • Lu, Xianmao; Korgel, Brian A.; Johnston, Keith P.
  • Chemistry of Materials, Vol. 17, Issue 25
  • DOI: 10.1021/cm0515956

Targeted Ligand-Exchange Chemistry on Cesium Lead Halide Perovskite Quantum Dots for High-Efficiency Photovoltaics
journal, July 2018

  • Wheeler, Lance M.; Sanehira, Erin M.; Marshall, Ashley R.
  • Journal of the American Chemical Society, Vol. 140, Issue 33
  • DOI: 10.1021/jacs.8b04984

Highly Dynamic Ligand Binding and Light Absorption Coefficient of Cesium Lead Bromide Perovskite Nanocrystals
journal, January 2016


Ultrasmooth organic–inorganic perovskite thin-film formation and crystallization for efficient planar heterojunction solar cells
journal, January 2015

  • Zhang, Wei; Saliba, Michael; Moore, David T.
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms7142

Organometallic Halide Perovskites: Sharp Optical Absorption Edge and Its Relation to Photovoltaic Performance
journal, March 2014

  • De Wolf, Stefaan; Holovsky, Jakub; Moon, Soo-Jin
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 6
  • DOI: 10.1021/jz500279b

Sharp exponential band tails in highly disordered lead sulfide quantum dot arrays
journal, October 2012


One-Step Preparation of Cesium Lead Halide CsPbX 3 (X = Cl, Br, and I) Perovskite Nanocrystals by Microwave Irradiation
journal, December 2017

  • Liu, Huiwen; Wu, Zhennan; Gao, Hang
  • ACS Applied Materials & Interfaces, Vol. 9, Issue 49
  • DOI: 10.1021/acsami.7b14677

Spectral and Dynamical Properties of Multiexcitons in Semiconductor Nanocrystals
journal, May 2007


Size-Dependent Electron Injection from Excited CdSe Quantum Dots into TiO 2 Nanoparticles
journal, April 2007

  • Robel, István; Kuno, Masaru; Kamat, Prashant V.
  • Journal of the American Chemical Society, Vol. 129, Issue 14
  • DOI: 10.1021/ja070099a

Ultrafast Electron Injection from Photoexcited Perovskite CsPbI 3 QDs into TiO 2 Nanoparticles with Injection Efficiency near 99%
journal, January 2018


Spectral and Dynamical Properties of Single Excitons, Biexcitons, and Trions in Cesium–Lead-Halide Perovskite Quantum Dots
journal, March 2016


Single Cesium Lead Halide Perovskite Nanocrystals at Low Temperature: Fast Single-Photon Emission, Reduced Blinking, and Exciton Fine Structure
journal, January 2016

  • Rainò, Gabriele; Nedelcu, Georgian; Protesescu, Loredana
  • ACS Nano, Vol. 10, Issue 2
  • DOI: 10.1021/acsnano.5b07328

Room Temperature Single-Photon Emission from Individual Perovskite Quantum Dots
journal, September 2015


Exciton Relaxation Dynamics in Photo-Excited CsPbI3 Perovskite Nanocrystals
journal, July 2016

  • Liu, Qinghui; Wang, Yinghui; Sui, Ning
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep29442

Enhanced mobility CsPbI 3 quantum dot arrays for record-efficiency, high-voltage photovoltaic cells
journal, October 2017

  • Sanehira, Erin M.; Marshall, Ashley R.; Christians, Jeffrey A.
  • Science Advances, Vol. 3, Issue 10
  • DOI: 10.1126/sciadv.aao4204

Pseudopotential calculations of electron and hole addition spectra of InAs, InP, and Si quantum dots
journal, July 2000


Observation of solvatochromism in CdSe colloidal quantum dots
journal, April 2001


Electrochromism and Solvatochromism
journal, March 1969


Hybrid organic–inorganic inks flatten the energy landscape in colloidal quantum dot solids
journal, November 2016

  • Liu, Mengxia; Voznyy, Oleksandr; Sabatini, Randy
  • Nature Materials, Vol. 16, Issue 2
  • DOI: 10.1038/nmat4800

Works referencing / citing this record:

Photoexcited carrier dynamics in colloidal quantum dot solar cells: insights into individual quantum dots, quantum dot solid films and devices
journal, January 2020

  • Zhang, Yaohong; Wu, Guohua; Liu, Feng
  • Chemical Society Reviews, Vol. 49, Issue 1
  • DOI: 10.1039/c9cs00560a

One-step solution deposition of CsPbBr 3 based on precursor engineering for efficient all-inorganic perovskite solar cells
journal, January 2019

  • Huang, Dewei; Xie, Pengfei; Pan, Zhenxiao
  • Journal of Materials Chemistry A, Vol. 7, Issue 39
  • DOI: 10.1039/c9ta08465g

Spray‐Coated Colloidal Perovskite Quantum Dot Films for Highly Efficient Solar Cells
journal, September 2019

  • Yuan, Jifeng; Bi, Chenghao; Wang, Shixun
  • Advanced Functional Materials, Vol. 29, Issue 49
  • DOI: 10.1002/adfm.201906615

Perovskite nanocrystals for energy conversion and storage
journal, July 2019

  • Kostopoulou, Athanasia; Brintakis, Konstantinos; Nasikas, Nektarios K.
  • Nanophotonics, Vol. 8, Issue 10
  • DOI: 10.1515/nanoph-2019-0119

Managing Energy Loss in Inorganic Lead Halide Perovskites Solar Cells
journal, September 2019

  • Liu, Chongming; Zeng, Qingsen; Yang, Bai
  • Advanced Materials Interfaces, Vol. 6, Issue 22
  • DOI: 10.1002/admi.201901136