Skip to main content
SpringerLink
Log in

Ultrafast processes in photochromic material YHxOy studied by excited-state density functional theory simulation

光致变色材料YHxOy中超快过程的激发态密度泛函理论研究

  • Articles
  • Published:
Science China Materials Aims and scope Submit manuscript

Abstract

Oxygen-containing rare-earth metal hydride, YHxOy, is a newly found photochromic material showing fast photoresponse. While its preparation method, optical properties and structural features have been studied extensively, the photochromic mechanism in YHxOy remains unknown. Here, using excited-state molecular dynamics simulation based on the recently developed real-time time-dependent density functional theory (RT-TDDFT) method, we study the photochemical reactions in YHxOy. We find that under photoexcitation, dihydrogen defects are formed within 100 fs. The dihydrogen defect behaves as a shallow donor and renders the material strongly n-type doped, which could be responsible for the photochromic effect observed in YHxOy. We also find that oxygen concentration affects the metastability of the dihydrogen species, meaning that the energy barrier for the dihydrogen to dissociate is related to the oxygen concentration. The highest barrier of 0.28 eV is found in our model with O/Y=1:8. If the oxygen concentration is too low, the dihydrogen will quickly dissociate when the excitation is turned off. If the oxygen concentration is too high, the dihydrogen dissociates even when the excitation is still on.

摘要

含氧稀土金属氢化物YHxOy是一种新发现的、具有快速光响应的光致变色材料. 尽管其制备方法、光学性质和结构特征已被广泛研究, 但YHxOy中的光致变色机理仍然未知. 本文采用基于最新开发的含时密度泛函理论的激发态分子动力学模拟研究了 YHxOy中的光化学反应. 结果发现, 光激发下在100 fs内可以形成一种双氢缺陷. 该双氢缺陷为浅施主, 使材料表现出强n型掺杂行为, 这可能是导致YHxOy中光致变色效应的原因. 此外还发现, 氧浓度会影响双氢缺陷的稳定性, 这意味着双氢解离的能垒与氧浓度有关. 在此模型中, 当O/Y=1:8时, 双氢解离的能垒约为0.28 eV. 若氧浓度过低, 在关闭激发时双氢会迅速解离; 若氧浓度过高, 即使在光激发下双氢也会快速解离.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  1. Brown GH. Photochromism. New York: Wiley-Interscience, 1971

    Google Scholar 

  2. Irie M, Fukaminato T, Matsuda K, et al. Photochromism of diarylethene molecules and crystals: memories, switches, and actuators. Chem Rev, 2014, 114: 12174–12277

    CAS  Google Scholar 

  3. Irie M. Photochromism: memories and switches—Introduction. Chem Rev, 2000, 100: 1683–1684

    CAS  Google Scholar 

  4. Zhang J, Zou Q, Tian H. Photochromic materials: more than meets the eye. Adv Mater, 2013, 25: 378–399

    CAS  Google Scholar 

  5. Pardo R, Zayat M, Levy D. Photochromic organic-inorganic hybrid materials. Chem Soc Rev, 2011, 40: 672–687

    CAS  Google Scholar 

  6. Leydecker T, Herder M, Pavlica E, et al. Flexible non-volatile optical memory thin-film transistor device with over 256 distinct levels based on an organic bicomponent blend. Nat Nanotech, 2016, 11: 769–775

    CAS  Google Scholar 

  7. Gemayel ME, Börjesson K, Herder M, et al. Optically switchable transistors by simple incorporation of photochromic systems into small-molecule semiconducting matrices. Nat Commun, 2015, 6: 6330

    Google Scholar 

  8. Cacciarini M, Skov AB, Jevric M, et al. Towards solar energy storage in the photochromic dihydroazulene-vinylheptafulvene system. Chem Eur J, 2015, 21: 7454–7461

    CAS  Google Scholar 

  9. Wang Y, Runnerstrom EL, Milliron DJ. Switchable materials for smart windows. Annu Rev Chem Biomol Eng, 2016, 7: 283–304

    Google Scholar 

  10. Bouas-Laurent H, Dürr H. Organic photochromism (IUPAC technical report). Pure Appl Chem, 2001, 73: 639–665

    CAS  Google Scholar 

  11. Mukhopadhyay A, Maka VK, Savitha G, et al. Photochromic 2D metal-organic framework nanosheets (MONs): design, synthesis, and functional MON-ormosil composite. Chem, 2018, 4: 1059–1079

    CAS  Google Scholar 

  12. Park J, Jiang Q, Feng D, et al. Controlled generation of singlet oxygen in living cells with tunable ratios of the photochromic switch in metal-organic frameworks. Angew Chem Int Ed, 2016, 55: 7188–7193

    CAS  Google Scholar 

  13. Su J, Fukaminato T, Placial JP, et al. Giant amplification of photoswitching by a few photons in fluorescent photochromic organic nanoparticles. Angew Chem Int Ed, 2016, 55: 3662–3666

    CAS  Google Scholar 

  14. Peters GM, Tovar JD. Pendant photochromic conjugated polymers incorporating a highly functionalizable thieno[3,4-b]thiophene switching motif. J Am Chem Soc, 2019, 141: 3146–3152

    CAS  Google Scholar 

  15. Li W, Zhuang Y, Zheng P, et al. Tailoring trap depth and emission wavelength in Y3Al5−xGaxO12:Ce3+,V3+ phosphor-in-glass films for optical information storage. ACS Appl Mater Interfaces, 2018, 10: 27150–27159

    CAS  Google Scholar 

  16. Norrbo I, Curutchet A, Kuusisto A, et al. Solar UV index and UV dose determination with photochromic hackmanites: from the assessment of the fundamental properties to the device. Mater Horiz, 2018, 5: 569–576

    CAS  Google Scholar 

  17. Wu J, Tao C, Li Y, et al. Methylviologen-templated layered bimetal phosphate: a multifunctional X-ray-induced photochromic material. Chem Sci, 2014, 5: 4237–4241

    CAS  Google Scholar 

  18. Chen S, Akai T, Kadono K, et al. A silver-containing halogen-free inorganic photochromic glass. Chem Commun, 2001, 20: 2090–2091

    Google Scholar 

  19. Ren Y, Yang Z, Wang Y, et al. Reversible multiplexing for optical information recording, erasing, and reading-out in photochromic BaMgSiO4:Bi3+ luminescence ceramics. Sci China Mater, 2020, 63: 582–592

    CAS  Google Scholar 

  20. Faughnan BW, Crandall RS, Heyman PM. Electrochromism in WO3 amorphous films. RCA Rev, 1975, 36: 177–197

    CAS  Google Scholar 

  21. He T, Yao J. Photochromism of molybdenum oxide. J Photochem Photobiol C-Photochem Rev, 2003, 4: 125–143

    CAS  Google Scholar 

  22. He T, Yao JN. Photochromism in transition-metal oxides. Res Chem Intermed, 2004, 30: 459–488

    CAS  Google Scholar 

  23. Miniotas A, Hjörvarsson B, Douysset L, et al. Gigantic resistivity and band gap changes in GdOyHx thin films. Appl Phys Lett, 2000, 76: 2056–2058

    CAS  Google Scholar 

  24. Nafezarefi F, Schreuders H, Dam B, et al. Photochromism of rareearth metal-oxy-hydrides. Appl Phys Lett, 2017, 111: 103903

    Google Scholar 

  25. Cornelius S, Colombi G, Nafezarefi F, et al. Oxyhydride nature of rare-earth-based photochromic thin films. J Phys Chem Lett, 2019, 10: 1342–1348

    CAS  Google Scholar 

  26. Huiberts JN, Griessen R, Rector JH, et al. Yttrium and lanthanum hydride films with switchable optical properties. Nature, 1996, 380: 231–234

    CAS  Google Scholar 

  27. Ohmura A, Machida A, Watanuki T, et al. Photochromism in yttrium hydride. Appl Phys Lett, 2007, 91: 151904

    Google Scholar 

  28. Ohmura A, Machida A, Watanuki T, et al. Infrared spectroscopic study of the band-gap closure in YH3 at high pressure. Phys Rev B, 2006, 73: 104105

    Google Scholar 

  29. Mongstad T, Platzer-Björkman C, Maehlen JP, et al. A new thin film photochromic material: oxygen-containing yttrium hydride. Sol Energy Mater Sol Cells, 2011, 95: 3596–3599

    CAS  Google Scholar 

  30. Chandran CV, Schreuders H, Dam B, et al. Solid-state NMR studies of the photochromic effects of thin films of oxygen-containing yttrium hydride. J Phys Chem C, 2014, 118: 22935–22942

    CAS  Google Scholar 

  31. Montero J, Martinsen FA, García-Tecedor M, et al. Photochromic mechanism in oxygen-containing yttrium hydride thin films: an optical perspective. Phys Rev B, 2017, 95: 201301

    Google Scholar 

  32. Plokker MP, Eijt SWH, Naziris F, et al. Electronic structure and vacancy formation in photochromic yttrium oxy-hydride thin films studied by positron annihilation. Sol Energy Mater Sol Cells, 2018, 177: 97–105

    CAS  Google Scholar 

  33. Pishtshev A, Karazhanov SZ. Role of oxygen in materials properties of yttrium trihydride. Solid State Commun, 2014, 194: 39–42

    CAS  Google Scholar 

  34. Maehlen JP, Mongstad TT, You CC, et al. Lattice contraction in photochromic yttrium hydride. J Alloys Compd, 2013, 580: S119–S121

    CAS  Google Scholar 

  35. You CC, Mongstad T, Maehlen JP, et al. Engineering of the band gap and optical properties of thin films of yttrium hydride. Appl Phys Lett, 2014, 105: 031910

    Google Scholar 

  36. Kresse G, Furthmüller J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys Rev B, 1996, 54: 11169–11186

    CAS  Google Scholar 

  37. Perdew JP, Burke K, Ernzerhof M. Generalized gradient approximation made simple. Phys Rev Lett, 1996, 77: 3865–3868

    CAS  Google Scholar 

  38. Monkhorst HJ, Pack JD. Special points for brillouin-zone integrations. Phys Rev B, 1976, 13: 5188–5192

    Google Scholar 

  39. Kresse G, Hafner J. Ab initio molecular dynamics for liquid metals. Phys Rev B, 1993, 47: 558–561

    CAS  Google Scholar 

  40. Henkelman G, Uberuaga BP, Jónsson H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J Chem Phys, 2000, 113: 9901–9904

    CAS  Google Scholar 

  41. Soler JM, Artacho E, Gale JD, et al. The SIESTA method for ab initio order-N materials simulation. J Phys-Condens Matter, 2002, 14: 2745–2779

    CAS  Google Scholar 

  42. Meng S, Kaxiras E. Real-time, local basis-set implementation of time-dependent density functional theory for excited state dynamics simulations. J Chem Phys, 2008, 129: 054110

    Google Scholar 

  43. Sugino O, Miyamoto Y. Density-functional approach to electron dynamics: stable simulation under a self-consistent field. Phys Rev B, 1999, 59: 2579–2586

    CAS  Google Scholar 

Download references

Acknowledgements

Chai J and Sun Y-Y acknowledge the support by the National Natural Science Foundation of China (11774365).

Author information

Author notes

  1. Theses authors contributed equally to this work.

Authors and Affiliations

  1. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai, 201899, China

    Jun Chai  (柴骏), Zewei Shao  (邵泽伟), Chen Ming  (明辰), Xun Cao  (曹逊), Ping Jin  (金平实) & Yi-Yang Sun  (孙宜阳)

  2. University of Chinese Academy of Sciences, Beijing, 100049, China

    Jun Chai  (柴骏) & Zewei Shao  (邵泽伟)

  3. Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California, 94720, USA

    Han Wang  (王涵)

  4. Department of Electrical and Computer Engineering, University of North Carolina at Charlotte, Charlotte, North Carolina, 28223, USA

    Wanseok Oh, Tang Ye  (叶唐) & Yong Zhang  (张勇)

  5. Department of Physics, Applied Physics, and Astronomy, Rensselaer Polytechnic Institute, Troy, New York, 12180, USA

    Shengbai Zhang  (张绳百)

Authors
  1. Jun Chai  (柴骏)
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Zewei Shao  (邵泽伟)
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Han Wang  (王涵)
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Chen Ming  (明辰)
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Wanseok Oh
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Tang Ye  (叶唐)
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Yong Zhang  (张勇)
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. Xun Cao  (曹逊)
    View author publications

    You can also search for this author in PubMed Google Scholar

  9. Ping Jin  (金平实)
    View author publications

    You can also search for this author in PubMed Google Scholar

  10. Shengbai Zhang  (张绳百)
    View author publications

    You can also search for this author in PubMed Google Scholar

  11. Yi-Yang Sun  (孙宜阳)
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

Sun YY and Cao X initiated and coordinated the research. Chai J, Wang H, Ming C, Zhang S and Sun YY conducted the computational studies and data analysis. Shao Z, Jin P and Cao X prepared the samples. Shao Z, Jin P, Cao X, Oh W, Ye T and Zhang Y conducted experimental measurements on the samples. All authors participated in the discussion of the results. Chai J, Shao Z, Wang H, Cao X and Sun YY wrote the paper.

Corresponding authors

Correspondence to Xun Cao  (曹逊) or Yi-Yang Sun  (孙宜阳).

Additional information

Conflict of interest

The authors declare that they have no conflict of interest.

Jun Chai received his BSc degree from the School of Materials Science and Engineering, Shanghai University in 2017. Now he is a PhD candidate in Prof. Yi-Yang Sun’s group at the State Key Laboratory of High-Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences. His current research focuses on the physical and chemical mechanisms of defects in energy materials using the first-principles calculations.

Zewei Shao received his BSc degree in material science and engineering from the University of Science and Technology of China in 2016. Now he is a PhD candidate in Prof. Xun Cao’s group at the State Key Laboratory of High-Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences. His current research focuses on the design of functional oxide films and their applications for smart windows.

Han Wang received his PhD degree from Rensselaer Polytechnic Institute (RPI) in 2017. Currently he is working as a postdoctoral fellow at Lawrence Berkeley National Laboratory (LBNL), USA. His current research interest is the study of non-adiabatic dynamics of molecular and solid systems and the simulation of ground and excited state X-ray absorption spectra.

Xun Cao is a Professor at the State Key Laboratory of High-Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences (SICCAS). He obtained his PhD degree from SICCAS in 2010. He joined the University of California in 2015 as a visiting research fellow. At present, the he works as a Professor and Deputy Head of the Research Group of Smart Materials in SICCAS. His research interests include functional films and chromogenic materials.

Yi-Yang Sun received his PhD degree from National University of Singapore (NUS) in 2004. He has worked as postdoc at NUS, National Renewable Energy Laboratory, and Rensselaer Polytechnic Institute (RPI). In 2010, he was appointed research assistant professor and later research scientist at RPI. In 2017, he assumed a professor position at Shanghai Institute of Ceramics, Chinese Academy of Sciences. His research focuses on the study of energy-related materials using the first-principles computations.

Supporting Information for

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Chai, J., Shao, Z., Wang, H. et al. Ultrafast processes in photochromic material YHxOy studied by excited-state density functional theory simulation. Sci. China Mater. 63, 1579–1587 (2020). https://doi.org/10.1007/s40843-020-1343-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s40843-020-1343-x

Keywords

Search

Navigation