Electronic shell structures, self-trapped excitons, and defect-bound excitons in Li2B12H12

Du, Mao-Hua; Shi, Hongliang; Zhang, S. B.

doi:10.1039/c9tc04150h

Title: Electronic shell structures, self-trapped excitons, and defect-bound excitons in Li₂B₁₂H₁₂

Journal Article · 23 October 2019 · Journal of Materials Chemistry C

DOI: https://doi.org/10.1039/c9tc04150h · OSTI ID:1607243

^[1];

^[2]; Zhang, S. B. ^[3]

Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division
Key Laboratory of Micro-Nano Measurement-Manipulation and Physics (Ministry of Education); Department of Physics; Beihang University; Beijing 100191; China
Rensselaer Polytechnic Inst., Troy, NY (United States). Dept. of Electrical, Computer and Systems Engineering

First-principles studies of electronic structures, excitons, and defects in Li₂B₁₂H₁₂ reveal unique photophysical properties of Li₂B₁₂H₁₂ and its potential as a neutron scintillator material. We identify the electronic shell structure in (B₁₂H₁₂)^2-, which gives rise to strong chemical stability of (B₁₂H₁₂)^2- and a large band gap of Li₂B₁₂H₁₂. Based on hybrid functional calculations, we show that excitons in Li₂B₁₂H₁₂ are strongly self-trapped and predict that the exciton excitation and emission are both in the UV range and are not related to the bright blue emission observed in the experiment. The experimentally observed blue emission in Li₂B₁₂H₁₂ is likely due to the emission of excitons bound to hydrogen vacancies. The calculated strong localization and large exciton trapping energy at hydrogen vacancies indicate enhanced radiative recombination, while the calculated large Stokes shift suggests that the self-absorption and the resonance transfer of the excitation energy may be suppressed. These properties should promote efficient defect emission at room temperature. The efficient defect emission, combined with the large thermal neutron capture cross-section by Li and B and the efficient energy transfer between fast neutrons and H, suggests potential applications of Li₂B₁₂H₁₂ as a thermal or fast neutron scintillator. Optical characterization of VH may also be used to monitor H and Li concentrations in Li₂B₁₂H₁₂-based hydrogen storage materials and solid-state electrolytes in Li batteries.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1607243

Journal Information:: Journal of Materials Chemistry C, Journal Name: Journal of Materials Chemistry C Journal Issue: 45 Vol. 7; ISSN JMCCCX; ISSN 2050-7526

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

References (66)

Lead-Free Highly Efficient Blue-Emitting Cs ₃ Cu ₂ I ₅ with 0D Electronic Structure Jun, Taehwan; Sim, Kihyung; Iimura, Soshi Advanced Materials, Vol. 30, Issue 43 https://doi.org/10.1002/adma.201804547	journal	September 2018
Rational Design of Nanosized Light Elements for Hydrogen Storage: Classes, Synthesis, Characterization, and Properties Lai, Qiwen; Wang, Ting; Sun, Yahui Advanced Materials Technologies, Vol. 3, Issue 9 https://doi.org/10.1002/admt.201700298	journal	February 2018
Formation and Diffusion of Metal Impurities in Perovskite Solar Cell Material CH ₃ NH ₃ PbI ₃ : Implications on Solar Cell Degradation and Choice of Electrode Ming, Wenmei; Yang, Dongwen; Li, Tianshu Advanced Science, Vol. 5, Issue 2 https://doi.org/10.1002/advs.201700662	journal	December 2017
Carbon Incorporation and Anion Dynamics as Synergistic Drivers for Ultrafast Diffusion in Superionic LiCB ₁₁ H ₁₂ and NaCB ₁₁ H ₁₂ Dimitrievska, Mirjana; Shea, Patrick; Kweon, Kyoung E. Advanced Energy Materials, Vol. 8, Issue 15 https://doi.org/10.1002/aenm.201703422	journal	February 2018
A Zero-Dimensional Organic Seesaw-Shaped Tin Bromide with Highly Efficient Strongly Stokes-Shifted Deep-Red Emission Zhou, Chenkun; Lin, Haoran; Shi, Hongliang Angewandte Chemie, Vol. 130, Issue 4 https://doi.org/10.1002/ange.201710383	journal	December 2017
Highly Emissive Self-Trapped Excitons in Fully Inorganic Zero-Dimensional Tin Halides Benin, Bogdan M.; Dirin, Dmitry N.; Morad, Viktoriia Angewandte Chemie, Vol. 130, Issue 35 https://doi.org/10.1002/ange.201806452	journal	July 2018
A Zero-Dimensional Organic Seesaw-Shaped Tin Bromide with Highly Efficient Strongly Stokes-Shifted Deep-Red Emission Zhou, Chenkun; Lin, Haoran; Shi, Hongliang Angewandte Chemie International Edition, Vol. 57, Issue 4 https://doi.org/10.1002/anie.201710383	journal	December 2017
Highly Emissive Self-Trapped Excitons in Fully Inorganic Zero-Dimensional Tin Halides Benin, Bogdan M.; Dirin, Dmitry N.; Morad, Viktoriia Angewandte Chemie International Edition, Vol. 57, Issue 35 https://doi.org/10.1002/anie.201806452	journal	July 2018
Formation of Al13I-: Evidence for the Superhalogen Character of Al13. Bergeron, Denis E.; Castleman, A. Welford Jr.; Morisato, Tsuguo ChemInform, Vol. 35, Issue 26 https://doi.org/10.1002/chin.200426023	journal	June 2004
Borane Derivatives: A New Class of Super- and Hyperhalogens Pathak, Biswarup; Samanta , Devleena; Ahuja, Rajeev ChemPhysChem, Vol. 12, Issue 13 https://doi.org/10.1002/cphc.201100320	journal	July 2011
Dual behavior of excess electrons in rutile TiO ₂ Janotti, A.; Franchini, C.; Varley, J. B. physica status solidi (RRL) - Rapid Research Letters, Vol. 7, Issue 3 https://doi.org/10.1002/pssr.201206464	journal	January 2013
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Critical review, with an optimistic outlook, on Boron Neutron Capture Therapy (BNCT) Moss, Raymond L. Applied Radiation and Isotopes, Vol. 88 https://doi.org/10.1016/j.apradiso.2013.11.109	journal	June 2014
Metal boranes: Progress and applications Hansen, Bjarne R. S.; Paskevicius, Mark; Li, Hai-Wen Coordination Chemistry Reviews, Vol. 323 https://doi.org/10.1016/j.ccr.2015.12.003	journal	September 2016
Complex high-temperature phase transitions in Li2B12H12 and Na2B12H12 Verdal, Nina; Her, Jae-Hyuk; Stavila, Vitalie Journal of Solid State Chemistry, Vol. 212 https://doi.org/10.1016/j.jssc.2014.01.006	journal	April 2014
Low dimensional metal halide perovskites and hybrids Zhou, Chenkun; Lin, Haoran; He, Qingquan Materials Science and Engineering: R: Reports, Vol. 137 https://doi.org/10.1016/j.mser.2018.12.001	journal	July 2019
White-Light Emission from Layered Halide Perovskites Smith, Matthew D.; Karunadasa, Hemamala I. Accounts of Chemical Research, Vol. 51, Issue 3 https://doi.org/10.1021/acs.accounts.7b00433	journal	February 2018
Structural, Chemical, and Dynamical Frustration: Origins of Superionic Conductivity in closo -Borate Solid Electrolytes Kweon, Kyoung E.; Varley, Joel B.; Shea, Patrick Chemistry of Materials, Vol. 29, Issue 21 https://doi.org/10.1021/acs.chemmater.7b02902	journal	October 2017
Fast Lithium-Ion Conduction in Atom-Deficient closo -Type Complex Hydride Solid Electrolytes Kim, Sangryun; Toyama, Naoki; Oguchi, Hiroyuki Chemistry of Materials, Vol. 30, Issue 2 https://doi.org/10.1021/acs.chemmater.7b03986	journal	January 2018
Facile Preparation of Light Emitting Organic Metal Halide Crystals with Near-Unity Quantum Efficiency Zhou, Chenkun; Worku, Michael; Neu, Jennifer Chemistry of Materials, Vol. 30, Issue 7 https://doi.org/10.1021/acs.chemmater.8b00129	journal	March 2018
Predicting Band Gaps with Hybrid Density Functionals Garza, Alejandro J.; Scuseria, Gustavo E. The Journal of Physical Chemistry Letters, Vol. 7, Issue 20 https://doi.org/10.1021/acs.jpclett.6b01807	journal	October 2016
Near-Unity Photoluminescence Quantum Yield in Blue-Emitting Cs ₃ Cu ₂ Br _{5– x} I _x (0 ≤ x ≤ 5) Roccanova, Rachel; Yangui, Aymen; Nhalil, Hariharan ACS Applied Electronic Materials, Vol. 1, Issue 3 https://doi.org/10.1021/acsaelm.9b00015	journal	February 2019
A One-Dimensional Organic Lead Chloride Hybrid with Excitation-Dependent Broadband Emissions Wu, Guanhong; Zhou, Chenkun; Ming, Wenmei ACS Energy Letters, Vol. 3, Issue 6 https://doi.org/10.1021/acsenergylett.8b00661	journal	May 2018
Green Emitting Single-Crystalline Bulk Assembly of Metal Halide Clusters with Near-Unity Photoluminescence Quantum Efficiency Zhou, Chenkun; Lin, Haoran; Neu, Jennifer ACS Energy Letters, Vol. 4, Issue 7 https://doi.org/10.1021/acsenergylett.9b00991	journal	June 2019
Broadband Emission in Hybrid Organic–Inorganic Halides of Group 12 Metals Roccanova, Rachel; Houck, Matthew; Yangui, Aymen ACS Omega, Vol. 3, Issue 12 https://doi.org/10.1021/acsomega.8b02883	journal	December 2018
Three-Dimensional Aromaticity in Polyhedral Boranes and Related Molecules King, R. Bruce Chemical Reviews, Vol. 101, Issue 5 https://doi.org/10.1021/cr000442t	journal	May 2001
Applications of Radiolabeled Boron Clusters to the Diagnosis and Treatment of Cancer Hawthorne, M. Frederick; Maderna, Andreas Chemical Reviews, Vol. 99, Issue 12 https://doi.org/10.1021/cr980442h	journal	December 1999
Antiaromaticity in Bare Deltahedral Silicon Clusters Satisfying Wade's and Hirsch's Rules: An Apparent Correlation of Antiaromaticity with High Symmetry King, R. Bruce; Heine, Thomas; Corminboeuf, Clémence Journal of the American Chemical Society, Vol. 126, Issue 2 https://doi.org/10.1021/ja036259+	journal	December 2003
Thermal Stability of Li ₂ B ₁₂ H ₁₂ and its Role in the Decomposition of LiBH ₄ Pitt, Mark P.; Paskevicius, Mark; Brown, David H. Journal of the American Chemical Society, Vol. 135, Issue 18 https://doi.org/10.1021/ja400131b	journal	April 2013
The renaissance of hydrides as energy materials Mohtadi, Rana; Orimo, Shin-ichi Nature Reviews Materials, Vol. 2, Issue 3 https://doi.org/10.1038/natrevmats.2016.91	journal	December 2016
Reducing Dzyaloshinskii-Moriya interaction and field-free spin-orbit torque switching in synthetic antiferromagnets Chen, Ruyi; Cui, Qirui; Liao, Liyang Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-23414-3	journal	May 2021
High-resolution X-ray luminescence extension imaging Ou, Xiangyu; Qin, Xian; Huang, Bolong Nature, Vol. 590, Issue 7846 https://doi.org/10.1038/s41586-021-03251-6	journal	February 2021
Chemical trends of Mn ⁴⁺ emission in solids Du, M. H. J. Mater. Chem. C, Vol. 2, Issue 14 https://doi.org/10.1039/C4TC00031E	journal	January 2014
Bi-functional Li ₂ B ₁₂ H ₁₂ for energy storage and conversion applications: solid-state electrolyte and luminescent down-conversion dye Teprovich, Joseph A.; Colón-Mercado, Héctor; Washington II, Aaron L. Journal of Materials Chemistry A, Vol. 3, Issue 45 https://doi.org/10.1039/C5TA06549F	journal	January 2015
Synthesis, stability and Li-ion mobility of nanoconfined Li ₂ B ₁₂ H ₁₂ Yan, Y.; Rentsch, D.; Battaglia, C. Dalton Transactions, Vol. 46, Issue 37 https://doi.org/10.1039/C7DT02946B	journal	January 2017
Luminescent zero-dimensional organic metal halide hybrids with near-unity quantum efficiency Zhou, Chenkun; Lin, Haoran; Tian, Yu Chemical Science, Vol. 9, Issue 3 https://doi.org/10.1039/C7SC04539E	journal	January 2018
Comment on “Bi-functional Li ₂ B ₁₂ H ₁₂ for energy storage and conversion applications: solid-state electrolyte and luminescent down-conversion dye” by J. A. Teprovich Jr, H. Colón-Mercado, A. L. Washington II, P. A. Ward, S. Greenway, D. M. Missimer, H. Hartman, J. Velten, J. H. Christian and R. Zidan, J. Mater. Chem. A , 2015, 3 , 22853 Paskevicius, M.; Jakobsen, A. S.; Bregnhøj, M. Journal of Materials Chemistry A, Vol. 7, Issue 8 https://doi.org/10.1039/C8TA10735A	journal	January 2019
Unraveling luminescence mechanisms in zero-dimensional halide perovskites Han, Dan; Shi, Hongliang; Ming, Wenmei Journal of Materials Chemistry C, Vol. 6, Issue 24 https://doi.org/10.1039/C8TC01291A	journal	January 2018
Reply to the ‘Comment on “Bi-functional Li ₂ B ₁₂ H ₁₂ for energy storage and conversion applications: solid-state electrolyte and luminescent down-conversion dye”’ by M. Paskevicius, A. S. Jakobsen, M. Bregnhøj, B. R. S. Hansen, K. T. Møller, P. R. Ogilby and T. R. Jensen, J. Mater. Chem. A. , 2019, DOI: 10.1039/c8ta10735a Teprovich, Joseph A.; Zidan, Ragaiy Journal of Materials Chemistry A, Vol. 7, Issue 8 https://doi.org/10.1039/C9TA00407F	journal	January 2019
Zero-dimensional metal oxide Li ₄ TiO ₄ Du, Mao-Hua Journal of Materials Chemistry C, Vol. 7, Issue 19 https://doi.org/10.1039/C9TC00197B	journal	January 2019
First-order phase transition in the Li2B12H12 system Paskevicius, Mark; Pitt, Mark P.; Brown, David H. Physical Chemistry Chemical Physics, Vol. 15, Issue 38 https://doi.org/10.1039/c3cp53090f	journal	January 2013
Hybrid functionals based on a screened Coulomb potential Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias The Journal of Chemical Physics, Vol. 118, Issue 18 https://doi.org/10.1063/1.1564060	journal	May 2003
Potential-energy surfaces for excited states in extended systems Hellman, A.; Razaznejad, B.; Lundqvist, B. I. The Journal of Chemical Physics, Vol. 120, Issue 10 https://doi.org/10.1063/1.1645787	journal	March 2004
Screened hybrid density functionals applied to solids Paier, J.; Marsman, M.; Hummer, K. The Journal of Chemical Physics, Vol. 124, Issue 15 https://doi.org/10.1063/1.2187006	journal	April 2006
Influence of the exchange screening parameter on the performance of screened hybrid functionals Krukau, Aliaksandr V.; Vydrov, Oleg A.; Izmaylov, Artur F. The Journal of Chemical Physics, Vol. 125, Issue 22 https://doi.org/10.1063/1.2404663	journal	December 2006
Rationale for mixing exact exchange with density functional approximations Perdew, John P.; Ernzerhof, Matthias; Burke, Kieron The Journal of Chemical Physics, Vol. 105, Issue 22, p. 9982-9985 https://doi.org/10.1063/1.472933	journal	December 1996
Small hole polarons in rare-earth titanates Bjaalie, L.; Ouellette, D. G.; Moetakef, P. Applied Physics Letters, Vol. 106, Issue 23 https://doi.org/10.1063/1.4922316	journal	June 2015
Neutron scattering lengths and cross sections Sears, Varley F. Neutron News, Vol. 3, Issue 3 https://doi.org/10.1080/10448639208218770	journal	January 1992
Density-functional theory beyond the Hohenberg-Kohn theorem Görling, Andreas Physical Review A, Vol. 59, Issue 5 https://doi.org/10.1103/PhysRevA.59.3359	journal	May 1999
Discrete Electronic Bands in Semiconductors and Insulators: Potential High-Light-Yield Scintillators Shi, Hongliang; Du, Mao-Hua Physical Review Applied, Vol. 3, Issue 5 https://doi.org/10.1103/PhysRevApplied.3.054005	journal	May 2015
Efficient pseudopotentials for plane-wave calculations Troullier, N.; Martins, José Luriaas Physical Review B, Vol. 43, Issue 3 https://doi.org/10.1103/PhysRevB.43.1993	journal	January 1991
Structural and electronic properties of C 60 Troullier, N.; Martins, José Luís Physical Review B, Vol. 46, Issue 3 https://doi.org/10.1103/PhysRevB.46.1754	journal	July 1992
Born-Oppenheimer molecular-dynamics simulations of finite systems: Structure and dynamics of ( H 2 O ) 2 Barnett, Robert N.; Landman, Uzi Physical Review B, Vol. 48, Issue 4 https://doi.org/10.1103/PhysRevB.48.2081	journal	July 1993
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Assessment of correction methods for the band-gap problem and for finite-size effects in supercell defect calculations: Case studies for ZnO and GaAs Lany, Stephan; Zunger, Alex Physical Review B, Vol. 78, Issue 23, Article No. 235104 https://doi.org/10.1103/PhysRevB.78.235104	journal	December 2008
Impurity-bound small polarons in ZnO: Hybrid density functional calculations Du, Mao-Hua; Zhang, S. B. Physical Review B, Vol. 80, Issue 11 https://doi.org/10.1103/PhysRevB.80.115217	journal	September 2009
Energy transport and scintillation of cerium-doped elpasolite Cs 2 LiYCl 6 : Hybrid density functional calculations Biswas, Koushik; Du, Mao-Hua Physical Review B, Vol. 86, Issue 1 https://doi.org/10.1103/PhysRevB.86.014102	journal	July 2012
Vacancies and small polarons in SrTiO 3 Janotti, Anderson; Varley, Joel B.; Choi, Minseok Physical Review B, Vol. 90, Issue 8 https://doi.org/10.1103/PhysRevB.90.085202	journal	August 2014
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Impact of metal n s 2 lone pair on luminescence quantum efficiency in low-dimensional halide perovskites Shi, Hongliang; Han, Dan; Chen, Shiyou Physical Review Materials, Vol. 3, Issue 3 https://doi.org/10.1103/PhysRevMaterials.3.034604	journal	March 2019
The density functional formalism, its applications and prospects Jones, R. O.; Gunnarsson, O. Reviews of Modern Physics, Vol. 61, Issue 3 https://doi.org/10.1103/RevModPhys.61.689	journal	July 1989
The physics of simple metal clusters: experimental aspects and simple models de Heer, Walt A. Reviews of Modern Physics, Vol. 65, Issue 3 https://doi.org/10.1103/RevModPhys.65.611	journal	July 1993
Formation of Al13I-: Evidence for the Superhalogen Character of Al13 Bergeron, D. E. Science, Vol. 304, Issue 5667 https://doi.org/10.1126/science.1093902	journal	April 2004
Al Cluster Superatoms as Halogens in Polyhalides and as Alkaline Earths in Iodide Salts Bergeron, D. E. Science, Vol. 307, Issue 5707 https://doi.org/10.1126/science.1105820	journal	January 2005
Predicting Band Gaps with Hybrid Density Functionals Garza, Alejandro J.; Scuseria, Gustavo E. arXiv https://doi.org/10.48550/arxiv.1608.04796	text	January 2016
An ultrasensitive molybdenum-based double-heterojunction phototransistor Zenodo https://doi.org/10.5281/zenodo.4835973	text	January 2021

Similar Records

Metal Halide Scintillators with Fast and Self‐Absorption‐Free Defect‐Bound Excitonic Radioluminescence for Dynamic X‐Ray Imaging

Journal Article · 2020 · Advanced Functional Materials · OSTI ID:1804223

Zhang, Muyi; Wang, Xiaoming; Yang, Bo; +10 more

Self‐Trapped Hole Migration and Defect‐Mediated Thermal Quenching of Luminescence in α‐ and β‐Ga₂O₃

Journal Article · 2025 · Advanced Functional Materials · OSTI ID:2998938

Hajizadeh, Nima; Frodason, Ymir K.; Petersen, Clemens; +9 more

Scintillation properties and electronic structure of the intrinsic and extrinsic mixed elpasolites Cs₂ Na RBr₃I₃ (R = La, Y)

Journal Article · 2016 · Physical Review Applied · OSTI ID:1244201

Wei, Hua; Du, Mao -Hua; Stand, Luis; +4 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Title: Electronic shell structures, self-trapped excitons, and defect-bound excitons in Li2B12H12

Citation Formats

References (66)

Similar Records

Related Subjects

Title: Electronic shell structures, self-trapped excitons, and defect-bound excitons in Li₂B₁₂H₁₂