Rb2CuX3 (X = Cl, Br): 1D All-Inorganic Copper Halides with Ultrabright Blue Emission and Up-Conversion Photoluminescence
Abstract
All-inorganic metal halides such as Cs4PbX6 and CsPbX3 (X = Cl, Br, and I) are attracting global attention owing to their promise in optoelectronic applications. However, the presence of the toxic heavy metal lead (Pb) in these materials is a major concern. In this work, a family of nontoxic high-efficiency blue-emitting all-inorganic halides Rb2CuX3 (X = Br and Cl) is reported; the compounds exhibit 1D crystal structures featuring anionic $$^1_∞[CuX_3]$$ 2- ribbons separated by Rb+ cations. The measured record high photoluminescence quantum yield values range from 64% to 100% for Rb2CuBr3 and Rb2CuCl3, respectively. Furthermore, the measured emission linewidths are quite narrow with full width at half maximum values of 54 and 52 nm for Rb2CuBr3 and Rb2CuCl3, respectively. Single crystals of Rb2CuCl3 demonstrate an anti-Stokes photoluminescence signal, shown for the first time for Pb-free metal halides. The discovery of highly efficient narrow blue emitters based on a nontoxic and inexpensive metal copper paves a way for the consideration of low-cost and environmentally friendly copper halides for practical applications.
- Authors:
-
[3];
[1]
- Univ. of Oklahoma, Norman, OK (United States)
- Univ. of California, Santa Barbara, CA (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- OSTI Identifier:
- 1607023
- Alternate Identifier(s):
- OSTI ID: 1574054
- Grant/Contract Number:
- AC05-00OR22725; DMR 1720256; CHE-1726630
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Advanced Optical Materials
- Additional Journal Information:
- Journal Volume: 8; Journal Issue: 2; Journal ID: ISSN 2195-1071
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 1D metal halide; blue-emitting materials; Pb-free halides; up-conversion photoluminescence
Citation Formats
Creason, Tielyr, Yangui, Aymen, Roccanova, Rachel, Strom, Amanda, Du, Mao-Hua, and Saparov, Bayrammurad. Rb2CuX3 (X = Cl, Br): 1D All-Inorganic Copper Halides with Ultrabright Blue Emission and Up-Conversion Photoluminescence. United States: N. p., 2019.
Web. doi:10.1002/adom.201901338.
Creason, Tielyr, Yangui, Aymen, Roccanova, Rachel, Strom, Amanda, Du, Mao-Hua, & Saparov, Bayrammurad. Rb2CuX3 (X = Cl, Br): 1D All-Inorganic Copper Halides with Ultrabright Blue Emission and Up-Conversion Photoluminescence. United States. https://doi.org/10.1002/adom.201901338
Creason, Tielyr, Yangui, Aymen, Roccanova, Rachel, Strom, Amanda, Du, Mao-Hua, and Saparov, Bayrammurad. Wed .
"Rb2CuX3 (X = Cl, Br): 1D All-Inorganic Copper Halides with Ultrabright Blue Emission and Up-Conversion Photoluminescence". United States. https://doi.org/10.1002/adom.201901338. https://www.osti.gov/servlets/purl/1607023.
@article{osti_1607023,
title = {Rb2CuX3 (X = Cl, Br): 1D All-Inorganic Copper Halides with Ultrabright Blue Emission and Up-Conversion Photoluminescence},
author = {Creason, Tielyr and Yangui, Aymen and Roccanova, Rachel and Strom, Amanda and Du, Mao-Hua and Saparov, Bayrammurad},
abstractNote = {All-inorganic metal halides such as Cs4PbX6 and CsPbX3 (X = Cl, Br, and I) are attracting global attention owing to their promise in optoelectronic applications. However, the presence of the toxic heavy metal lead (Pb) in these materials is a major concern. In this work, a family of nontoxic high-efficiency blue-emitting all-inorganic halides Rb2CuX3 (X = Br and Cl) is reported; the compounds exhibit 1D crystal structures featuring anionic $^1_∞[CuX_3]$ 2- ribbons separated by Rb+ cations. The measured record high photoluminescence quantum yield values range from 64% to 100% for Rb2CuBr3 and Rb2CuCl3, respectively. Furthermore, the measured emission linewidths are quite narrow with full width at half maximum values of 54 and 52 nm for Rb2CuBr3 and Rb2CuCl3, respectively. Single crystals of Rb2CuCl3 demonstrate an anti-Stokes photoluminescence signal, shown for the first time for Pb-free metal halides. The discovery of highly efficient narrow blue emitters based on a nontoxic and inexpensive metal copper paves a way for the consideration of low-cost and environmentally friendly copper halides for practical applications.},
doi = {10.1002/adom.201901338},
journal = {Advanced Optical Materials},
number = 2,
volume = 8,
place = {United States},
year = {Wed Nov 13 00:00:00 EST 2019},
month = {Wed Nov 13 00:00:00 EST 2019}
}
Free Publicly Available Full Text
Publisher's Version of Record
Other availability
Search WorldCat to find libraries that may hold this journal
Cited by: 73 works
Citation information provided by
Web of Science
Web of Science
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.
Works referenced in this record:
Rational molecular passivation for high-performance perovskite light-emitting diodes
journal, March 2019
- Xu, Weidong; Hu, Qi; Bai, Sai
- Nature Photonics, Vol. 13, Issue 6
Can Laser Light Cool Semiconductors?
journal, June 2004
- Sheik-Bahae, Mansoor; Epstein, Richard I.
- Physical Review Letters, Vol. 92, Issue 24
Thermally Stable Copper(II)-Doped Cesium Lead Halide Perovskite Quantum Dots with Strong Blue Emission
journal, February 2019
- Bi, Chenghao; Wang, Shixun; Li, Qiang
- The Journal of Physical Chemistry Letters, Vol. 10, Issue 5
Laser cooling of solids to cryogenic temperatures
journal, January 2010
- Seletskiy, Denis V.; Melgaard, Seth D.; Bigotta, Stefano
- Nature Photonics, Vol. 4, Issue 3
Electron–phonon interaction in efficient perovskite blue emitters
journal, May 2018
- Gong, Xiwen; Voznyy, Oleksandr; Jain, Ankit
- Nature Materials, Vol. 17, Issue 6
Bright Luminescence from Nontoxic CsCu 2 X 3 (X = Cl, Br, I)
journal, August 2019
- Roccanova, Rachel; Yangui, Aymen; Seo, Gijun
- ACS Materials Letters, Vol. 1, Issue 4
Laser cooling of a semiconductor by 40 kelvin
journal, January 2013
- Zhang, Jun; Li, Dehui; Chen, Renjie
- Nature, Vol. 493, Issue 7433
Polaron self-localization in white-light emitting hybrid perovskites
journal, January 2017
- Cortecchia, Daniele; Yin, Jun; Bruno, Annalisa
- Journal of Materials Chemistry C, Vol. 5, Issue 11
Phase diagram and high copper ion conductivity of the copper(I) chloride-rubidium chloride system
journal, November 1983
- Kanno, R.; Takeda, Y.; Masuyama, Y.
- Solid State Ionics, Vol. 11, Issue 3
Structural characterization, vibrational, optical properties and DFT investigation of a new luminescent organic–inorganic material: (C6H14N)3Bi2I9
journal, May 2015
- Dammak, Hajer; Yangui, Aymen; Triki, Smail
- Journal of Luminescence, Vol. 161
Disphenoidal Zero-Dimensional Lead, Tin, and Germanium Halides: Highly Emissive Singlet and Triplet Self-Trapped Excitons and X-ray Scintillation
journal, June 2019
- Morad, Viktoriia; Shynkarenko, Yevhen; Yakunin, Sergii
- Journal of the American Chemical Society, Vol. 141, Issue 25
Hybrid Organic–Inorganic Halides (C 5 H 7 N 2 ) 2 MBr 4 (M = Hg, Zn) with High Color Rendering Index and High-Efficiency White-Light Emission
journal, March 2019
- Yangui, Aymen; Roccanova, Rachel; McWhorter, Timothy M.
- Chemistry of Materials, Vol. 31, Issue 8
Spontaneous Self‐Assembly of Cesium Lead Halide Perovskite Nanoplatelets into Cuboid Crystals with High Intensity Blue Emission
journal, May 2019
- Bi, Chenghao; Wang, Shixun; Kershaw, Stephen V.
- Advanced Science
Unraveling luminescence mechanisms in zero-dimensional halide perovskites
journal, January 2018
- Han, Dan; Shi, Hongliang; Ming, Wenmei
- Journal of Materials Chemistry C, Vol. 6, Issue 24
Lead-Free Highly Efficient Blue-Emitting Cs 3 Cu 2 I 5 with 0D Electronic Structure
journal, September 2018
- Jun, Taehwan; Sim, Kihyung; Iimura, Soshi
- Advanced Materials, Vol. 30, Issue 43
Photoluminescence Up-Conversion in CsPbBr 3 Nanocrystals
journal, October 2017
- Morozov, Yurii V.; Zhang, Shubin; Brennan, Michael C.
- ACS Energy Letters, Vol. 2, Issue 10
Six-fold plasmonic enhancement of thermal scavenging via CsPbBr3 anti-Stokes photoluminescence
journal, January 2019
- Roman, Benjamin J.; Sheldon, Matthew T.
- Nanophotonics, Vol. 8, Issue 4
Organic–Inorganic Perovskites: Structural Versatility for Functional Materials Design
journal, March 2016
- Saparov, Bayrammurad; Mitzi, David B.
- Chemical Reviews, Vol. 116, Issue 7
Synthesis, Crystal and Electronic Structures, and Optical Properties of (CH 3 NH 3 ) 2 CdX 4 (X = Cl, Br, I)
journal, November 2017
- Roccanova, Rachel; Ming, Wenmei; Whiteside, Vincent R.
- Inorganic Chemistry, Vol. 56, Issue 22
Low-Dimensional Organometal Halide Perovskites
journal, November 2017
- Lin, Haoran; Zhou, Chenkun; Tian, Yu
- ACS Energy Letters, Vol. 3, Issue 1
Optical refrigeration
journal, December 2007
- Sheik-Bahae, Mansoor; Epstein, Richard I.
- Nature Photonics, Vol. 1, Issue 12
Self-Trapped Excitons in All-Inorganic Halide Perovskites: Fundamentals, Status, and Potential Applications
journal, March 2019
- Li, Shunran; Luo, Jiajun; Liu, Jing
- The Journal of Physical Chemistry Letters, Vol. 10, Issue 8
Laser cooling of organic–inorganic lead halide perovskites
journal, December 2015
- Ha, Son-Tung; Shen, Chao; Zhang, Jun
- Nature Photonics, Vol. 10, Issue 2
Commentary: The Materials Project: A materials genome approach to accelerating materials innovation
journal, July 2013
- Jain, Anubhav; Ong, Shyue Ping; Hautier, Geoffroy
- APL Materials, Vol. 1, Issue 1
Thin-Film Deposition and Characterization of a Sn-Deficient Perovskite Derivative Cs 2 SnI 6
journal, March 2016
- Saparov, Bayrammurad; Sun, Jon-Paul; Meng, Weiwei
- Chemistry of Materials, Vol. 28, Issue 7
Up-converted photoluminescence from perovskite semiconductors: Implications for laser cooling
journal, February 2019
- Yamada, Takumi; Aharen, Tomoko; Kanemitsu, Yoshihiko
- Physical Review Materials, Vol. 3, Issue 2
Efficient and stable emission of warm-white light from lead-free halide double perovskites
journal, November 2018
- Luo, Jiajun; Wang, Xiaoming; Li, Shunran
- Nature, Vol. 563, Issue 7732
Crystal structures and ionic conductivities of ternary derivatives of the silver and copper monohalides—II: ordered phases within the (AgX)x–(MX)1−x and (CuX)x–(MX)1−x (M=K, Rb and Cs; X=Cl, Br and I) systems
journal, September 2004
- Hull, S.; Berastegui, P.
- Journal of Solid State Chemistry, Vol. 177, Issue 9
Low dimensional metal halide perovskites and hybrids
journal, July 2019
- Zhou, Chenkun; Lin, Haoran; He, Qingquan
- Materials Science and Engineering: R: Reports, Vol. 137
Characterisation of n-type γ-CuCl on Si for UV optoelectronic applications
journal, April 2007
- O’Reilly, L.; Mitra, A.; Lucas, F. O.
- Journal of Materials Science: Materials in Electronics, Vol. 18, Issue S1
Rb 4 Ag 2 BiBr 9 : A Lead-Free Visible Light Absorbing Halide Semiconductor with Improved Stability
journal, February 2019
- Sharma, Manila; Yangui, Aymen; Whiteside, Vincent R.
- Inorganic Chemistry, Vol. 58, Issue 7
Broadband Emission in Hybrid Organic–Inorganic Halides of Group 12 Metals
journal, December 2018
- Roccanova, Rachel; Houck, Matthew; Yangui, Aymen
- ACS Omega, Vol. 3, Issue 12
Defect-Mediated CdS Nanobelt Photoluminescence Up-Conversion
journal, July 2017
- Morozov, Yurii V.; Draguta, Sergiu; Zhang, Shubin
- The Journal of Physical Chemistry C, Vol. 121, Issue 30
Interband Optical Transitions in Extremely Anisotropic Semiconductors. I. Bound and Unbound Exciton Absorption
journal, October 1966
- Shinada, Masaki; Sugano, Satoru
- Journal of the Physical Society of Japan, Vol. 21, Issue 10
Structural phase transition causing anomalous photoluminescence behavior in perovskite (C 6 H 11 NH 3 ) 2 [PbI 4 ]
journal, December 2015
- Yangui, A.; Pillet, S.; Mlayah, A.
- The Journal of Chemical Physics, Vol. 143, Issue 22
Color-stable highly luminescent sky-blue perovskite light-emitting diodes
journal, August 2018
- Xing, Jun; Zhao, Yongbiao; Askerka, Mikhail
- Nature Communications, Vol. 9, Issue 1
Electron-hole diffusion lengths > 175 μm in solution-grown CH 3 NH 3 PbI 3 single crystals
journal, January 2015
- Dong, Qingfeng; Fang, Yanjun; Shao, Yuchuan
- Science, Vol. 347, Issue 6225
Blue Emitting Single Crystalline Assembly of Metal Halide Clusters
journal, September 2018
- Zhou, Chenkun; Lin, Haoran; Worku, Michael
- Journal of the American Chemical Society, Vol. 140, Issue 41
Efficient blue light-emitting diodes based on quantum-confined bromide perovskite nanostructures
journal, August 2019
- Liu, Yang; Cui, Jieyuan; Du, Kai
- Nature Photonics, Vol. 13, Issue 11
UV emission on a Si substrate: Optical and structural properties of γ-CuCl on Si grown using liquid phase epitaxy techniques
journal, May 2009
- Cowley, A.; Foy, B.; Danilieuk, D.
- physica status solidi (a), Vol. 206, Issue 5
Optical Investigation of Broadband White-Light Emission in Self-Assembled Organic–Inorganic Perovskite (C 6 H 11 NH 3 ) 2 PbBr 4
journal, October 2015
- Yangui, A.; Garrot, D.; Lauret, J. S.
- The Journal of Physical Chemistry C, Vol. 119, Issue 41
Near-Unity Photoluminescence Quantum Yield in Blue-Emitting Cs 3 Cu 2 Br 5– x I x (0 ≤ x ≤ 5)
journal, February 2019
- Roccanova, Rachel; Yangui, Aymen; Nhalil, Hariharan
- ACS Applied Electronic Materials, Vol. 1, Issue 3
Anti-Stokes Ultraviolet Luminescence and Exciton Detrapping in the Two-Dimensional Perovskite (C 6 H 5 C 2 H 4 NH 3 ) 2 PbCl 4
journal, June 2019
- Cai, Peiqing; Huang, Yanlin; Seo, Hyo Jin
- The Journal of Physical Chemistry Letters, Vol. 10, Issue 14
Highly enhanced UV responsive conductivity and blue emission in transparent CuBr films: implication for emitter and dosimeter applications
journal, January 2017
- Vijayaraghavan, Rajani K.; Chandran, Deepak; Vijayaraghavan, Ratheesh K.
- J. Mater. Chem. C, Vol. 5, Issue 39
Yellowish White-Light Emission Involving Resonant Energy Transfer in a New One-Dimensional Hybrid Material: (C 9 H 10 N 2 )PbCl 4
journal, September 2018
- Barkaoui, H.; Abid, H.; Yangui, A.
- The Journal of Physical Chemistry C, Vol. 122, Issue 42
Disphenoidal Zero-Dimensional Lead, Tin, and Germanium Halides: Highly Emissive Singlet and Triplet Self-Trapped Excitons and X-ray Scintillation
text, January 2019
- Viktoriia, Morad,; Yevhen, Shynkarenko,; Sergii, Yakunin,
- ETH Zurich