Distinguishing electronic contributions of surface and sub-surface transition metal atoms in Ti-based MXenes

Yang, Yizhou; Hantanasirisakul, Kanit; Frey, Nathan C.; Anasori, Babak; Green, Robert J.; Rogge, Paul C.; Waluyo, Iradwikanari; Hunt, Adrian; Shafer, Padraic; Arenholz, Elke; Shenoy, Vivek B.; Gogotsi, Yury; May, Steven J.

doi:10.1088/2053-1583/ab68e7

Title: Distinguishing electronic contributions of surface and sub-surface transition metal atoms in Ti-based MXenes

Journal Article · 04 February 2020 · 2D Materials

DOI: https://doi.org/10.1088/2053-1583/ab68e7 · OSTI ID:1594224

^[1]; Hantanasirisakul, Kanit ^[2];

^[3];

^[4]; Green, Robert J. ^[5]; Rogge, Paul C. ^[2]; Waluyo, Iradwikanari ^[6]; Hunt, Adrian ^[6];

^[7]; Arenholz, Elke ^[8]; Shenoy, Vivek B. ^[3];

^[2];

^[2]

Drexel Univ., Philadelphia, PA (United States); Drexel University
Drexel Univ., Philadelphia, PA (United States)
Univ. of Pennsylvania, Philadelphia, PA (United States)
Drexel Univ., Philadelphia, PA (United States); Indiana Univ.—Purdue Univ. Indianapolis, IN (United States)
Univ. of Saskatchewan, Saskatoon, SK (Canada); Univ. of British Columbia, Vancouver, BC (Canada)
Brookhaven National Lab. (BNL), Upton, NY (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Cornell Univ., Ithaca, NY (United States)

MXenes are a rapidly-expanding family of 2D transition metal carbides and nitrides that have attracted attention due to their excellent performance in applications ranging from energy storage to electromagnetic interference shielding. Numerous other electronic and magnetic properties have been computationally predicted, but not yet realized due to the experimental difficulty in obtaining uniform surface terminations (T_x), necessitating new design approaches for MXenes that are independent of surface groups. In this study, we distinguished the contributions of surface and sub-surface Ti atoms to the electronic structure of four Ti-based MXenes (Ti₂CT_x, Ti₃C₂T_x, Cr₂TiC₂T_x, and Mo₂TiC₂T_x) using soft x-ray absorption spectroscopy, revealing minimal changes in the spectral features between the parent MAX phase and its MXene when no surface Ti atoms are present in the MXene, such as Mo₂TiC₂T_x and Cr₂TiC₂T_x. In contrast, for MXenes with surface Ti atoms, here Ti₃C₂T_x and Ti₂CT_x, the Ti L-edge spectra are significantly modified compared to their parent MAX phase compounds. First principles calculations provide similar trends in the partial density of states derived from surface and interior Ti atoms, corroborating the spectroscopic measurements. Furthermore, these results reveal that electronic states derived from sub-surface M-site layers are largely unperturbed by the surface groups, indicating a relatively short length scale over which the T_x groups alter the nominal electron count associated with Ti atoms and suggesting that desired band features should be hosted by sub-surface M-sites that are electronically more robust than their surface M-site counterparts.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Drexel Univ., Philadelphia, PA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; National Science Foundation; Department of Defense (DoD)

Grant/Contract Number:: SC0018618; SC0012704; AC02-05CH11231

OSTI ID:: 1594224

Journal Information:: 2D Materials, Journal Name: 2D Materials Journal Issue: 2 Vol. 7; ISSN 2053-1583

Publisher:: IOP PublishingCopyright Statement

Country of Publication:: United States

Language:: English

References (69)

Two-Dimensional Nanocrystals Produced by Exfoliation of Ti₃AlC₂ Naguib, Michael; Kurtoglu, Murat; Presser, Volker Advanced Materials, Vol. 23, Issue 37, p. 4248-4253 https://doi.org/10.1002/adma.201102306	journal	August 2011
25th Anniversary Article: MXenes: A New Family of Two-Dimensional Materials Naguib, Michael; Mochalin, Vadym N.; Barsoum, Michel W. Advanced Materials, Vol. 26, Issue 7, p. 992-1005 https://doi.org/10.1002/adma.201304138	journal	December 2013
Pseudocapacitive Electrodes Produced by Oxidant-Free Polymerization of Pyrrole between the Layers of 2D Titanium Carbide (MXene) Boota, Muhammad; Anasori, Babak; Voigt, Cooper Advanced Materials, Vol. 28, Issue 7 https://doi.org/10.1002/adma.201504705	journal	December 2015
Hydrophobic, Flexible, and Lightweight MXene Foams for High-Performance Electromagnetic-Interference Shielding Liu, Ji; Zhang, Hao-Bin; Sun, Renhui Advanced Materials, Vol. 29, Issue 38 https://doi.org/10.1002/adma.201702367	journal	August 2017
Oxide Thin-Film Electronics using All-MXene Electrical Contacts Wang, Zhenwei; Kim, Hyunho; Alshareef, Husam N. Advanced Materials, Vol. 30, Issue 15 https://doi.org/10.1002/adma.201706656	journal	February 2018
Cold Sintered Ceramic Nanocomposites of 2D MXene and Zinc Oxide Guo, Jing; Legum, Benjamin; Anasori, Babak Advanced Materials, Vol. 30, Issue 32 https://doi.org/10.1002/adma.201801846	journal	June 2018
Electronic and Optical Properties of 2D Transition Metal Carbides and Nitrides (MXenes) Hantanasirisakul, Kanit; Gogotsi, Yury Advanced Materials, Vol. 30, Issue 52 https://doi.org/10.1002/adma.201804779	journal	November 2018
Enhanced Terahertz Shielding of MXenes with Nano-Metamaterials Choi, Geunchang; Shahzad, Faisal; Bahk, Young-Mi Advanced Optical Materials, Vol. 6, Issue 5 https://doi.org/10.1002/adom.201701076	journal	January 2018
Crystal structure and formation mechanism of (Cr2/3Ti1/3)3AlC2 MAX phase Liu, Zhimou; Wu, Erdong; Wang, Jiemin Acta Materialia, Vol. 73 https://doi.org/10.1016/j.actamat.2014.04.006	journal	July 2014
X-ray photoelectron spectroscopy of select multi-layered transition metal carbides (MXenes) Halim, Joseph; Cook, Kevin M.; Naguib, Michael Applied Surface Science, Vol. 362 https://doi.org/10.1016/j.apsusc.2015.11.089	journal	January 2016
2D MXenes: Electromagnetic property for microwave absorption and electromagnetic interference shielding Cao, Mao-Sheng; Cai, Yong-Zhu; He, Peng Chemical Engineering Journal, Vol. 359 https://doi.org/10.1016/j.cej.2018.11.051	journal	March 2019
Surface and Heterointerface Engineering of 2D MXenes and Their Nanocomposites: Insights into Electro- and Photocatalysis Peng, Jiahe; Chen, Xingzhu; Ong, Wee-Jun Chem, Vol. 5, Issue 1 https://doi.org/10.1016/j.chempr.2018.08.037	journal	January 2019
Tuning magnetic properties of Cr2M2C3T2 (M = Ti and V) using extensile strain Yang, Jianhui; Luo, Xuepiao; Zhou, Xumeng Computational Materials Science, Vol. 139 https://doi.org/10.1016/j.commatsci.2017.08.016	journal	November 2017
Recent advances in MXenes: From fundamentals to applications Khazaei, Mohammad; Mishra, Avanish; Venkataramanan, Natarajan S. Current Opinion in Solid State and Materials Science, Vol. 23, Issue 3 https://doi.org/10.1016/j.cossms.2019.01.002	journal	June 2019
MXene: a promising transition metal carbide anode for lithium-ion batteries Naguib, Michael; Come, Jérémy; Dyatkin, Boris Electrochemistry Communications, Vol. 16, Issue 1, p. 61-64 https://doi.org/10.1016/j.elecom.2012.01.002	journal	March 2012
Fe 2 C monolayer: An intrinsic ferromagnetic MXene Yue, Yunliang Journal of Magnetism and Magnetic Materials, Vol. 434 https://doi.org/10.1016/j.jmmm.2017.03.058	journal	July 2017
Nitrogen-doped Ti 3 C 2 T x MXene electrodes for high-performance supercapacitors Wen, Yangyang; Rufford, Thomas E.; Chen, Xingzhu Nano Energy, Vol. 38 https://doi.org/10.1016/j.nanoen.2017.06.009	journal	August 2017
On the Chemical Diversity of the MAX Phases Sokol, Maxim; Natu, Varun; Kota, Sankalp Trends in Chemistry, Vol. 1, Issue 2 https://doi.org/10.1016/j.trechm.2019.02.016	journal	May 2019
Oxide Wizard: An EELS Application to Characterize the White Lines of Transition Metal Edges Yedra, Lluís; Xuriguera, Elena; Estrader, Marta Microscopy and Microanalysis, Vol. 20, Issue 3 https://doi.org/10.1017/S1431927614000440	journal	April 2014
Resolving the Structure of Ti ₃ C ₂ T _x MXenes through Multilevel Structural Modeling of the Atomic Pair Distribution Function Wang, Hsiu-Wen; Naguib, Michael; Page, Katharine Chemistry of Materials, Vol. 28, Issue 1 https://doi.org/10.1021/acs.chemmater.5b04250	journal	December 2015
Effects of Synthesis and Processing on Optoelectronic Properties of Titanium Carbonitride MXene Hantanasirisakul, Kanit; Alhabeb, Mohamed; Lipatov, Alexey Chemistry of Materials, Vol. 31, Issue 8 https://doi.org/10.1021/acs.chemmater.9b00401	journal	March 2019
Surface Termination Dependent Work Function and Electronic Properties of Ti ₃ C ₂ T _x MXene Schultz, Thorsten; Frey, Nathan C.; Hantanasirisakul, Kanit Chemistry of Materials, Vol. 31, Issue 17 https://doi.org/10.1021/acs.chemmater.9b00414	journal	December 2018
Rational Design of Two-Dimensional Metallic and Semiconducting Spintronic Materials Based on Ordered Double-Transition-Metal MXenes Dong, Liang; Kumar, Hemant; Anasori, Babak The Journal of Physical Chemistry Letters, Vol. 8, Issue 2 https://doi.org/10.1021/acs.jpclett.6b02751	journal	January 2017
Large-Area Highly Conductive Transparent Two-Dimensional Ti ₂ CT _x Film Yang, Yajie; Umrao, Sima; Lai, Shen The Journal of Physical Chemistry Letters, Vol. 8, Issue 4 https://doi.org/10.1021/acs.jpclett.6b03064	journal	January 2017
Understanding the MXene Pseudocapacitance Zhan, Cheng; Naguib, Michael; Lukatskaya, Maria The Journal of Physical Chemistry Letters, Vol. 9, Issue 6 https://doi.org/10.1021/acs.jpclett.8b00200	journal	February 2018
Large-Gap Quantum Spin Hall State in MXenes: d -Band Topological Order in a Triangular Lattice Si, Chen; Jin, Kyung-Hwan; Zhou, Jian Nano Letters, Vol. 16, Issue 10 https://doi.org/10.1021/acs.nanolett.6b03118	journal	September 2016
Half-Metallic Ferromagnetism and Surface Functionalization-Induced Metal–Insulator Transition in Graphene-like Two-Dimensional Cr ₂ C Crystals Si, Chen; Zhou, Jian; Sun, Zhimei ACS Applied Materials & Interfaces, Vol. 7, Issue 31 https://doi.org/10.1021/acsami.5b05401	journal	August 2015
Ti ₃ C ₂ MXenes with Modified Surface for High-Performance Electromagnetic Absorption and Shielding in the X-Band Han, Meikang; Yin, Xiaowei; Wu, Heng ACS Applied Materials & Interfaces, Vol. 8, Issue 32 https://doi.org/10.1021/acsami.6b06455	journal	August 2016
Two-Dimensional, Ordered, Double Transition Metals Carbides (MXenes) Anasori, Babak; Xie, Yu; Beidaghi, Majid ACS Nano, Vol. 9, Issue 10 https://doi.org/10.1021/acsnano.5b03591	journal	August 2015
High-Throughput Survey of Ordering Configurations in MXene Alloys Across Compositions and Temperatures Tan, Teck Leong; Jin, Hong Mei; Sullivan, Michael B. ACS Nano, Vol. 11, Issue 5 https://doi.org/10.1021/acsnano.6b08227	journal	March 2017
Tuning Noncollinear Spin Structure and Anisotropy in Ferromagnetic Nitride MXenes Frey, Nathan C.; Kumar, Hemant; Anasori, Babak ACS Nano, Vol. 12, Issue 6 https://doi.org/10.1021/acsnano.8b03472	journal	May 2018
Transparent Conductive Two-Dimensional Titanium Carbide Epitaxial Thin Films Halim, Joseph; Lukatskaya, Maria R.; Cook, Kevin M. Chemistry of Materials, Vol. 26, Issue 7 https://doi.org/10.1021/cm500641a	journal	March 2014
In-Situ Analysis of Valence Conversion in Transition Metal Oxides Using Electron Energy-Loss Spectroscopy Wang, Zhong L.; Yin, Jin S.; Mo, Wei Dong The Journal of Physical Chemistry B, Vol. 101, Issue 35 https://doi.org/10.1021/jp971593b	journal	August 1997
Two-Dimensional Transition Metal Carbides Naguib, Michael; Mashtalir, Olha; Carle, Joshua ACS Nano, Vol. 6, Issue 2 https://doi.org/10.1021/nn204153h	journal	January 2012
2D metal carbides and nitrides (MXenes) for energy storage Anasori, Babak; Lukatskaya, Maria R.; Gogotsi, Yury Nature Reviews Materials, Vol. 2, Issue 2 https://doi.org/10.1038/natrevmats.2016.98	journal	January 2017
Two-dimensional Mo1.33C MXene with divacancy ordering prepared from parent 3D laminate with in-plane chemical ordering Tao, Quanzheng; Dahlqvist, Martin; Lu, Jun Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms14949	journal	April 2017
Control of MXenes’ electronic properties through termination and intercalation Hart, James L.; Hantanasirisakul, Kanit; Lang, Andrew C. Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-018-08169-8	journal	January 2019
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
Double transition metal MXene (TixTa4−xC3) 2D materials as anodes for Li-ion batteries Syamsai, Ravuri; Rodriguez, Jassiel R.; Pol, Vilas G. Scientific Reports, Vol. 11, Issue 1 https://doi.org/10.1038/s41598-020-79991-8	journal	January 2021
Control of electronic properties of 2D carbides (MXenes) by manipulating their transition metal layers Anasori, Babak; Shi, Chenyang; Moon, Eun Ju Nanoscale Horizons, Vol. 1, Issue 3 https://doi.org/10.1039/C5NH00125K	journal	January 2016
High and anisotropic carrier mobility in experimentally possible Ti ₂ CO ₂ (MXene) monolayers and nanoribbons Zhang, Xu; Zhao, Xudong; Wu, Dihua Nanoscale, Vol. 7, Issue 38 https://doi.org/10.1039/C5NR04717J	journal	January 2015
Surface group modification and carrier transport properties of layered transition metal carbides (Ti ₂ CT _x , T: –OH, –F and –O) Lai, Shen; Jeon, Jaeho; Jang, Sung Kyu Nanoscale, Vol. 7, Issue 46 https://doi.org/10.1039/C5NR06513E	journal	January 2015
Dependence of elastic and optical properties on surface terminated groups in two-dimensional MXene monolayers: a first-principles study Bai, Yuelei; Zhou, Kun; Srikanth, Narasimalu RSC Advances, Vol. 6, Issue 42 https://doi.org/10.1039/C6RA03090D	journal	January 2016
MXene: a promising photocatalyst for water splitting Guo, Zhonglu; Zhou, Jian; Zhu, Linggang Journal of Materials Chemistry A, Vol. 4, Issue 29 https://doi.org/10.1039/C6TA04414J	journal	January 2016
Probing the impact of magnetic interactions on the lattice dynamics of two-dimensional Ti ₂ X (X = C, N) MXenes Sternik, Małgorzata; Wdowik, Urszula D. Physical Chemistry Chemical Physics, Vol. 20, Issue 11 https://doi.org/10.1039/C7CP08270C	journal	January 2018
Ti ₃ C ₂ MXene: a promising microwave absorbing material Feng, Wanlin; Luo, Heng; Wang, Yu RSC Advances, Vol. 8, Issue 5 https://doi.org/10.1039/C7RA12616F	journal	January 2018
Electronic properties and applications of MXenes: a theoretical review Khazaei, Mohammad; Ranjbar, Ahmad; Arai, Masao Journal of Materials Chemistry C, Vol. 5, Issue 10 https://doi.org/10.1039/C7TC00140A	journal	January 2017
Double transition metal MXenes with wide band gaps and novel magnetic properties Sun, Weiwei; Xie, Yu; Kent, Paul R. C. Nanoscale, Vol. 10, Issue 25 https://doi.org/10.1039/C8NR00513C	journal	January 2018
Prediction of MXene based 2D tunable band gap semiconductors: GW quasiparticle calculations Zhang, Yujuan; Xia, Weiyi; Wu, Yabei Nanoscale, Vol. 11, Issue 9 https://doi.org/10.1039/C9NR01160A	journal	January 2019
Optical properties of functionalized Ti ₃ C ₂ T ₂ (T = F, O, OH) MXene: First-principles calculations Berdiyorov, G. R. AIP Advances, Vol. 6, Issue 5 https://doi.org/10.1063/1.4948799	journal	May 2016
Tunable electronic and magnetic properties of Cr ₂ M′C ₂ T ₂ (M′ = Ti or V; T = O, OH or F) Yang, Jianhui; Zhou, Xumeng; Luo, Xuepiao Applied Physics Letters, Vol. 109, Issue 20 https://doi.org/10.1063/1.4967983	journal	November 2016
Controlling topological electronic structure of multifunctional MXene layer Balcı, Erdem; Akkuş, Ünal Özden; Berber, Savas Applied Physics Letters, Vol. 113, Issue 8 https://doi.org/10.1063/1.5042828	journal	August 2018
Ti 2p X-ray absorption in titanium dioxides (TiO ₂ ): the influence of the cation site environment Crocombette, J. P.; Jollet, F. Journal of Physics: Condensed Matter, Vol. 6, Issue 49 https://doi.org/10.1088/0953-8984/6/49/022	journal	December 1994
Doped Sc ₂ C(OH) ₂ MXene: new type s-pd band inversion topological insulator Balcı, Erdem; Akkuş, Ünal Özden; Berber, Savas Journal of Physics: Condensed Matter, Vol. 30, Issue 15 https://doi.org/10.1088/1361-648X/aab41e	journal	March 2018
White lines and d -electron occupancies for the 3 d and 4 d transition metals Pearson, D. H.; Ahn, C. C.; Fultz, B. Physical Review B, Vol. 47, Issue 14 https://doi.org/10.1103/PhysRevB.47.8471	journal	April 1993
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
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
Atomic-resolution imaging of oxidation states in manganites Varela, M.; Oxley, M. P.; Luo, W. Physical Review B, Vol. 79, Issue 8 https://doi.org/10.1103/PhysRevB.79.085117	journal	February 2009
Hybrid density functional study of structural and electronic properties of functionalized Ti n + 1 X n ( X = C , N) monolayers Xie, Yu; Kent, P. R. C. Physical Review B, Vol. 87, Issue 23 https://doi.org/10.1103/PhysRevB.87.235441	journal	June 2013
Large-gap two-dimensional topological insulator in oxygen functionalized MXene Weng, Hongming; Ranjbar, Ahmad; Liang, Yunye Physical Review B, Vol. 92, Issue 7 https://doi.org/10.1103/PhysRevB.92.075436	journal	August 2015
Topological insulators in the ordered double transition metals M 2 ′ M ″ C 2 MXenes ( M ′ = Mo , W; M ″ = Ti , Zr, Hf) Khazaei, Mohammad; Ranjbar, Ahmad; Arai, Masao Physical Review B, Vol. 94, Issue 12 https://doi.org/10.1103/PhysRevB.94.125152	journal	September 2016
Theoretical prediction of two-dimensional functionalized MXene nitrides as topological insulators Liang, Yunye; Khazaei, Mohammad; Ranjbar, Ahmad Physical Review B, Vol. 96, Issue 19 https://doi.org/10.1103/PhysRevB.96.195414	journal	November 2017
Variable range hopping and thermally activated transport in molybdenum-based MXenes Halim, Joseph; Moon, Eun Ju; Eklund, Per Physical Review B, Vol. 98, Issue 10 https://doi.org/10.1103/PhysRevB.98.104202	journal	September 2018
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
(Cr _2/3 Ti _1/3 ) ₃ AlC ₂ and (Cr _5/8 Ti _3/8 ) ₄ AlC ₃ : New MAX-phase Compounds in Ti-Cr-Al-C System Liu, Zhimou; Zheng, Liya; Sun, Luchao Journal of the American Ceramic Society, Vol. 97, Issue 1 https://doi.org/10.1111/jace.12731	journal	December 2013
2D titanium carbide (MXene) for wireless communication Sarycheva, Asia; Polemi, Alessia; Liu, Yuqiao Science Advances, Vol. 4, Issue 9 https://doi.org/10.1126/sciadv.aau0920	journal	September 2018
Electromagnetic interference shielding with 2D transition metal carbides (MXenes) Shahzad, F.; Alhabeb, M.; Hatter, C. B. Science, Vol. 353, Issue 6304 https://doi.org/10.1126/science.aag2421	journal	September 2016
A Non-Aqueous Asymmetric Cell with a Ti ₂ C-Based Two-Dimensional Negative Electrode Come, J.; Naguib, M.; Rozier, P. Journal of The Electrochemical Society, Vol. 159, Issue 8 https://doi.org/10.1149/2.003208jes	journal	January 2012
Theoretical Prediction of Two-Dimensional Functionalized MXene Nitrides as Topological Insulators Liang, Yunye; Khazaei, Mohammad; Ranjbar, Ahmad arXiv https://doi.org/10.48550/arxiv.1708.09710	text	January 2017

Similar Records

Control of electronic properties of 2D carbides (MXenes) by manipulating their transition metal layers

Journal Article · 2016 · Nanoscale Horizons · OSTI ID:1261289

Anasori, Babak; Shi, Chenyang; Moon, Eun Ju; +7 more

Materials synthesis, neutron powder diffraction, and first-principles calculations of (Mo_xSc_1–x)₂AlC i–MAX phase used as parent material for MXene derivation

Journal Article · 2019 · Physical Review Materials · OSTI ID:1735463

Calder, Stuart; Mockute, A.; Tao, Q.; +3 more

Multimodal Spectroscopic Study of Surface Termination Evolution in Cr₂TiC₂T_x MXene

Journal Article · 2021 · Advanced Materials Interfaces · OSTI ID:1764594

Hart, James L.; Hantanasirisakul, Kanit; Lang, Andrew C.; +6 more

Related Subjects

36 MATERIALS SCIENCE
MXene
electronic structure
titanium
x-ray absorption spectroscopy

Title: Distinguishing electronic contributions of surface and sub-surface transition metal atoms in Ti-based MXenes

Citation Formats

References (69)

Similar Records

Related Subjects