第一性原理计算钛酸铅<em>A</em>位掺杂对其负热膨胀性的影响

引用本文: 王方方, 曹战民, 陈骏, 邢献然. 第一性原理计算钛酸铅A位掺杂对其负热膨胀性的影响[J]. 物理化学学报, 2014, 30(8): 1432-1436. doi: 10.3866/PKU.WHXB201405281 shu

Citation: WANG Fang-Fang, CAO Zhan-Min, CHEN Jun, XING Xian-Ran. Effects of A-Site Substitutions on Negative Thermal Expansion in PbTiO₃ fromFirst-Principles Calculations[J]. Acta Physico-Chimica Sinica, 2014, 30(8): 1432-1436. doi: 10.3866/PKU.WHXB201405281 shu

第一性原理计算钛酸铅A位掺杂对其负热膨胀性的影响

基金项目:
国家自然科学基金（21231001，21031005，21322102）资助项目

摘要:

近年来，实验发现钛酸铅基材料具有负热膨胀性，且其热膨胀程度会受到掺杂元素的影响. 目前所研究的A位掺杂体系中，仅Cd原子掺杂能使钛酸铅负热膨胀性增强. 所以研究A位掺杂钛酸铅，比较Cd原子与其他原子在掺杂钛酸铅时化学键的异同，有助于深刻理解钛酸铅负热膨胀的本质. 本文利用第一性原理，分别优化了Sr、Ba、Cd掺杂钛酸铅的晶格常数，计算了它们的态密度和电荷密度. 结果表明Cd―O键的共价性强于Pb―O键，而Ba―O键和Sr―O键几乎呈离子性，Ba/Sr对Pb的替代削弱了化合物的共价性，降低了自发极化强度. 与实验测量的热膨胀系数对比可以发现，A位原子与氧原子之间的共价性增强，化合物负热膨胀程度升高；若A位原子与氧原子之间的共价性削弱，负热膨胀程度降低. 可见A位原子与氧原子之间的共价性影响了钛酸铅基化合物负热膨胀性.

关键词:

English

Effects of A-Site Substitutions on Negative Thermal Expansion in PbTiO₃ fromFirst-Principles Calculations

1.
1. Department of Physical Chemistry, School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing 100083, P. R. China;
2. Department of Nonferrous Metallurgy, School of Metallurgical and Ecological Engineering, University of Science and Technology Beijing, Beijing 100083, P. R. China
Received Date: 17 March 2014
Available Online: 18 July 2014
Fund Project:
国家自然科学基金（21231001，21031005，21322102）资助项目

Abstract:

Recent experimental results have indicated that the negative thermal expansion is a common phenomenon in PbTiO₃-based materials, and that this expansion is affected by various substitutions. Interestingly, Cd substitution in PbTiO₃ has a unique effect compared with other A-site substitutions, in that it enhances negative thermal expansion. Therefore, studying A-site substitution in PbTiO₃, the role of which still remains unclear, would provide a deeper understanding of the nature of the negative thermal expansion of PbTiO₃-based materials. Herein we report the results of structural calculations, densities of states and the minimumelectron densities of Pb_1-xSr_xTiO₃, Pb_1-xBa_xTiO₃, and Pb_1-xCd_xTiO₃ supercells on the basis of chemical bond first-principles calculations. The results demonstrate that the hybridization between Cd―O orbitals is more pronounced than that between Pb―O orbitals, while the bonding between Ba/Sr and O is almost ionic in nature. Cd substitution was found to have an unusual effect in terms of enhancing the average bulk coefficient of thermal expansion in PbTiO₃. In contrast, Ba and Sr substitutions reduce the coefficient. Thus, the covalency in the bonding between the A- site and O in PbTiO₃- based materials is responsible for the enhanced negative thermal expansion.

Key words:

1. [1]
  
  (1) Xing, X. R.; Deng, J. X.; Chen, J.; Liu, G. R. Rare Met. 2003, 22, 294.
  (1) Xing, X. R.; Deng, J. X.; Chen, J.; Liu, G. R. Rare Met. 2003, 22, 294.
2. [2]
  (2) Chen, J.; Nittala, K.; Forrester, J. S.; Jones, J. L.; Deng, J.; Yu, R.; Xing, X. J. Am. Chem. Soc. 2011, 133 (29), 11114. doi: 10.1021/ja2046292(2) Chen, J.; Nittala, K.; Forrester, J. S.; Jones, J. L.; Deng, J.; Yu, R.; Xing, X. J. Am. Chem. Soc. 2011, 133 (29), 11114. doi: 10.1021/ja2046292
3. [3]
  (3) Chandra, A.; Pandeya, D.; Mathews, M. D.; Tyagi, A. K. J. Mater. Res. 2005, 20, 350. doi: 10.1557/JMR.2005.0062(3) Chandra, A.; Pandeya, D.; Mathews, M. D.; Tyagi, A. K. J. Mater. Res. 2005, 20, 350. doi: 10.1557/JMR.2005.0062
4. [4]
  (4) Evans, J. S. O. Dalton Trans. 1999, 19, 3317.(4) Evans, J. S. O. Dalton Trans. 1999, 19, 3317.
5. [5]
  (5) Mohn, P. Nature 1999, 400, 18. doi: 10.1038/21778(5) Mohn, P. Nature 1999, 400, 18. doi: 10.1038/21778
6. [6]
  (6) Zheng, X. G.; Kubozono, H.; Yamada, H.; Kato, K.; Ishiwata, Y.; Xu, C. N. Nat. Nanotechnol. 2008, 3, 724. doi: 10.1038/nnano.2008.309(6) Zheng, X. G.; Kubozono, H.; Yamada, H.; Kato, K.; Ishiwata, Y.; Xu, C. N. Nat. Nanotechnol. 2008, 3, 724. doi: 10.1038/nnano.2008.309
7. [7]
  (7) Korcök, J. L.; Katz, M. J.; Leznoff, D. B. J. Am. Chem. Soc. 2009, 131, 4866. doi: 10.1021/ja809631r(7) Korcök, J. L.; Katz, M. J.; Leznoff, D. B. J. Am. Chem. Soc. 2009, 131, 4866. doi: 10.1021/ja809631r
8. [8]
  (8) Zwanziger, J. W. Phys. Rev. B 2007, 76, 052102.(8) Zwanziger, J. W. Phys. Rev. B 2007, 76, 052102.
9. [9]
  (9) Greve, B. K.; Martin, K. L.; Lee, P. L.; Chupas, P. J.; Chapman, K. W.;Wilkinson, A. P. J. Am. Chem. Soc. 2010, 132, 15496. doi: 10.1021/ja106711v(9) Greve, B. K.; Martin, K. L.; Lee, P. L.; Chupas, P. J.; Chapman, K. W.;Wilkinson, A. P. J. Am. Chem. Soc. 2010, 132, 15496. doi: 10.1021/ja106711v
10. [10]
  (10) odwin, A. L.; Calleja, M.; Conterio, M. J.; Dove, M. T.; Evans, J. S. O.; Keen, D. A.; Peters, L.; Tucker, M. G. Science 2008, 319, 794. doi: 10.1126/science.1151442(10) odwin, A. L.; Calleja, M.; Conterio, M. J.; Dove, M. T.; Evans, J. S. O.; Keen, D. A.; Peters, L.; Tucker, M. G. Science 2008, 319, 794. doi: 10.1126/science.1151442
11. [11]
  (11) Biernacki, S.; SchefBer, M. Phys. Rev. Lett. 1989, 63, 290. doi: 10.1103/PhysRevLett.63.290(11) Biernacki, S.; SchefBer, M. Phys. Rev. Lett. 1989, 63, 290. doi: 10.1103/PhysRevLett.63.290
12. [12]
  (12) Azuma, M.; Chen, W. T.; Seki, H.; Czapski, M.; Olga, S.; Oka, K.; Mizumaki, M.; Watanuki, T.; Ishimatsu, N.; Kawamura, N.; Ishiwata, S.; Tucker, M. G.; Shimakawa, Y.; Attfield, J. P. Nat. Commun. 2011, 2, 347. doi: 10.1038/ncomms1361(12) Azuma, M.; Chen, W. T.; Seki, H.; Czapski, M.; Olga, S.; Oka, K.; Mizumaki, M.; Watanuki, T.; Ishimatsu, N.; Kawamura, N.; Ishiwata, S.; Tucker, M. G.; Shimakawa, Y.; Attfield, J. P. Nat. Commun. 2011, 2, 347. doi: 10.1038/ncomms1361
13. [13]
  (13) Pryde, A. K. A.; Hammonds, K. D.; Dove, M. T.; Heine, V.; Gale, J. D.; Warren, M. C. Phase Trans. 1997, 61, 141. doi: 10.1080/01411599708223734(13) Pryde, A. K. A.; Hammonds, K. D.; Dove, M. T.; Heine, V.; Gale, J. D.; Warren, M. C. Phase Trans. 1997, 61, 141. doi: 10.1080/01411599708223734
14. [14]
  (14) Chen, J.; Hu, P. H.; Sun, X. Y.; Sun, C.; Xing, X. R. Appl. Phys. Lett. 2007, 91, 171907. doi: 10.1063/1.2794742(14) Chen, J.; Hu, P. H.; Sun, X. Y.; Sun, C.; Xing, X. R. Appl. Phys. Lett. 2007, 91, 171907. doi: 10.1063/1.2794742
15. [15]
  (15) Chen, J.; Xing, X. R.; Sun, C.; Hu, P. H.; Yu, R. B.; Wang, X. W.; Li, L. H. J. Am. Chem. Soc. 2008, 130, 1144. doi: 10.1021/ja7100278(15) Chen, J.; Xing, X. R.; Sun, C.; Hu, P. H.; Yu, R. B.; Wang, X. W.; Li, L. H. J. Am. Chem. Soc. 2008, 130, 1144. doi: 10.1021/ja7100278
16. [16]
  (16) Chen, J.; Xing, X. R.; Yu, R. B.; Liu, G. R. Appl. Phys. Lett. 2005, 87, 231915. doi: 10.1063/1.2140486(16) Chen, J.; Xing, X. R.; Yu, R. B.; Liu, G. R. Appl. Phys. Lett. 2005, 87, 231915. doi: 10.1063/1.2140486
17. [17]
  (17) Wang, F. F.; Xie, Y.; Chen, J.; Fu, H. G.; Xing, X. R. Phys. Chem. Chem. Phys. 2014, 16, 5237. doi: 10.1039/c3cp53197j(17) Wang, F. F.; Xie, Y.; Chen, J.; Fu, H. G.; Xing, X. R. Phys. Chem. Chem. Phys. 2014, 16, 5237. doi: 10.1039/c3cp53197j
18. [18]
  (18) Cheng, H. P.; Chen, G. H.; Qin, R.; Dan, J. K.; Huang, Z. M.; Peng, H.; Chen, T. N., Lei, J. B. Acta Phys. -Chim. Sin. 2014, 30, 281. [程和平,陈光华,覃睿,但加坤,黄智蒙,彭辉,陈图南,雷江波.物理化学学报, 2014, 30, 281.] doi: 10.3866/PKU.WHXB201312171(18) Cheng, H. P.; Chen, G. H.; Qin, R.; Dan, J. K.; Huang, Z. M.; Peng, H.; Chen, T. N., Lei, J. B. Acta Phys. -Chim. Sin. 2014, 30, 281. [程和平,陈光华,覃睿,但加坤,黄智蒙,彭辉,陈图南,雷江波.物理化学学报, 2014, 30, 281.] doi: 10.3866/PKU.WHXB201312171
19. [19]
  (19) Cohen, R. E.; Krakauer, H. Ferroelectrics 1992, 136, 65. doi: 10.1080/00150199208016067(19) Cohen, R. E.; Krakauer, H. Ferroelectrics 1992, 136, 65. doi: 10.1080/00150199208016067
20. [20]
  (20) García, A.; Vanderbilt, D. Phys. Rev. B 1996, 54, 3817. doi: 10.1103/PhysRevB.54.3817(20) García, A.; Vanderbilt, D. Phys. Rev. B 1996, 54, 3817. doi: 10.1103/PhysRevB.54.3817
21. [21]
  (21) Cohen, R. E.; Sághi-Szabó, G. Phys. Rev. Lett. 1998, 80, 4321. doi: 10.1103/PhysRevLett.80.4321(21) Cohen, R. E.; Sághi-Szabó, G. Phys. Rev. Lett. 1998, 80, 4321. doi: 10.1103/PhysRevLett.80.4321
22. [22]
  (22) Cockayne, E.; Burton, B. Phys. Rev. B 2004, 69, 144116. doi: 10.1103/PhysRevB.69.144116(22) Cockayne, E.; Burton, B. Phys. Rev. B 2004, 69, 144116. doi: 10.1103/PhysRevB.69.144116
23. [23]
  (23) Cohen, R. E. Nature 1992, 358, 136. doi: 10.1038/358136a0(23) Cohen, R. E. Nature 1992, 358, 136. doi: 10.1038/358136a0
24. [24]
  (24) Grinberg, I.; Rappe, A. M. Phase Trans. 2007, 80, 351. doi: 10.1080/01411590701228505(24) Grinberg, I.; Rappe, A. M. Phase Trans. 2007, 80, 351. doi: 10.1080/01411590701228505
25. [25]
  (25) Yashima, M.; Omoto, K.; Chen, J.; Kato, H.; Xing, X. R. Chem. Mater. 2011, 23, 3135. doi: 10.1021/cm201184y(25) Yashima, M.; Omoto, K.; Chen, J.; Kato, H.; Xing, X. R. Chem. Mater. 2011, 23, 3135. doi: 10.1021/cm201184y
26. [26]
  (26) Kresse, G.; Joubert, D. Phys. Rev. B 1999, 59, 1758.(26) Kresse, G.; Joubert, D. Phys. Rev. B 1999, 59, 1758.
27. [27]
  (27) Perdew, J. P.; Burke, K.; Ernzerhof, M. Phys. Rev. Lett. 1996, 77, 3865. doi: 10.1103/PhysRevLett.77.3865(27) Perdew, J. P.; Burke, K.; Ernzerhof, M. Phys. Rev. Lett. 1996, 77, 3865. doi: 10.1103/PhysRevLett.77.3865
28. [28]
  (28) Suárez-Sandoval, D. Y.; Davies, P. K. Appl. Phys. Lett. 2003, 82, 3215. doi: 10.1063/1.1573362(28) Suárez-Sandoval, D. Y.; Davies, P. K. Appl. Phys. Lett. 2003, 82, 3215. doi: 10.1063/1.1573362
29. [29]
  (29) Kuroiwa, Y.; Aoyagi, S.; Sawada, A.; Harada, J.; Nishibori, E.; Takata, M.; Sakata, M. Phys. Rev. Lett. 2001, 87, 217601. doi: 10.1103/PhysRevLett.87.217601(29) Kuroiwa, Y.; Aoyagi, S.; Sawada, A.; Harada, J.; Nishibori, E.; Takata, M.; Sakata, M. Phys. Rev. Lett. 2001, 87, 217601. doi: 10.1103/PhysRevLett.87.217601
30. [30]
  (30) Piskunov, S.; Heifets, E.; Eglitis, R. I.; Borstel, G. Comput. Mater. Sci. 2004, 29, 165. doi: 10.1016/j.commatsci.2003.08.036(30) Piskunov, S.; Heifets, E.; Eglitis, R. I.; Borstel, G. Comput. Mater. Sci. 2004, 29, 165. doi: 10.1016/j.commatsci.2003.08.036
31. [31]
  (31) Xing, X. R.; Deng, J. X.; Zhu, Z. Q.; Liu, G. R. J. Alloy. Compd. 2003, 353, 1. doi: 10.1016/S0925-8388(02)01178-7(31) Xing, X. R.; Deng, J. X.; Zhu, Z. Q.; Liu, G. R. J. Alloy. Compd. 2003, 353, 1. doi: 10.1016/S0925-8388(02)01178-7
32. [32]
  (32) Xing, X. R.; Chen, J.; Deng, J. X.; Liu, G. R. J. Alloy. Compd. 2003, 360, 286. doi: 10.1016/S0925-8388(03)00345-1
  (32) Xing, X. R.; Chen, J.; Deng, J. X.; Liu, G. R. J. Alloy. Compd. 2003, 360, 286. doi: 10.1016/S0925-8388(03)00345-1

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

第一性原理计算钛酸铅A位掺杂对其负热膨胀性的影响

English

Effects of A-Site Substitutions on Negative Thermal Expansion in PbTiO₃ fromFirst-Principles Calculations

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第一性原理计算钛酸铅A位掺杂对其负热膨胀性的影响

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