Abstract

The alumina-based compound, \${{12CaO.7Al}}_{2}{{O}}_{3}\$ , is a ceramic material with a unique cage-like lattice. Such a structure has enabled scientists to extract various new characteristics from this compound, most of which were unknown until quite recently. This compound has the ability to incorporate different anionic species and even electrons to the empty space inside its cages, thereby changing from an insulator into a conductive oxide. The cage walls can also incorporate different rare earth phosphor elements producing an oxide-based phosphor. All these characteristics are obtained without a significant change in the structure of the lattice. It is, therefore, reasonable to expect that this compound will receive attention as a potential material for display applications. This review article presents recent investigations into the application of 12CaO.7Al \$_{2}\$ O \$_{3}\$ ceramic in various display devices, the challenges, opportunities and possible areas of future investigation into the development of this naturally abundant and environmental friendly material in the field of display.

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  29. X. L. Liu, Y. X. Liu, D. T. Yan, H. C. Zhu, C. G. Liu, C. S. Xu, "Luminescence and energy transfer characteristics of Ce $^{3+}$ - and Tb $^{3+}$ -codoped nanoporous 12CaO.7Al $_{2}$ O $_{3}$ phosphors," J. Nanosci. Nanotechnol. 11, 9953-9957 (2011).
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  39. H. Yanagi, "Low threshold voltage and carrier injection properties of inverted organic light-emitting diodes with [Ca $_{24}$ Al $_{28}$ O $_{64}$ ] $^{4+}$ (4e $^{-})$ cathode and Cu2- $x$ Se anode," J. Phys. Chem. C 113, 18379-18384 (2009).
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2014 (2)

H. Zhu, "Long lasting blue phosphorescence and photostimulated luminescence in 12CaO $\_$ 7Al $_{2}$ O $_{3}$ : Eu thin films grown by pulsed laser deposition," Opt. Mater. 36, 1771-1775 (2014).

Y. X. Liu, "Effects of encaged anions on the optical and EPR spectroscopies of RE doped C12A7," J. Lumin. 152, 28-32 (2014).

2013 (1)

X. Liu, "A multiphase strategy for realizing green cathodoluminescence in 12CaO.7Al $_{2}$ O $_{3}$ -CaCeAl $_{3}$ O $_{7}$ :Ce $^{3+}$ ,Tb $^{3+}$ conductive phosphor," Dalton Trans. 42, 16311-16317 (2013).

2012 (4)

S. W. Kim, H. Hosono, "Synthesis and properties of 12CaO $\cdot$ 7Al $_{2}$ O $_{3}$ electride: Review of single crystal and thin film growth," Philosophical Mag. 92, 2596-2628 (2012).

J. A. McLeod, "Spectroscopic characterization of a multiband complex oxide: Insulating and conducting cement 12CaO $\cdot$ 7Al $_{2}$ O $_{3}$ ," Phys. Rev. B: Condens. Matter 85, (2012) Art no 045204.

X. Liu, Y. Liu, D. Yan, H. Zhu, C. Liu, "Single-phased white-emitting 12CaO.7Al2O3:Ce $^{3+}$ , Dy $^{3+}$ phosphors with suitable electrical conductivity for field emission displays Cite this," J. Mater. Chem. 22, 16839-16843 (2012).

H. Yanagi, T. Kuroda, K. Kim, Y. Toda, T. Kamiya, H. Hosono, "Electron injection barriers between air-stable electride with low work function, C12A7:e $^{-}$ , and pentacene, C60 and copper phthalocyanine," J. Mater. Chem. 22, 4278-4281 (2012).

2011 (4)

S. Watanabe, "Secondary electron emission and glow discharge properties of 12CaO.7Al $_{2}$ O $_{3}$ electride for fluorescent lamp applications," Sci. Technol. Adv. Mater. 12, (2011) Art no 034410.

H. Zhu, Y. Liu, D. Yan, X. Yan, C. Liu, C. Xu, "White luminescence of Dy3 $+$ ions doped 12CaO.7Al $_{2}$ O $_{3}$ nanopowders under UV light excitation," J. Nanosci. Nanotechnol. 11, 9958-9963 (2011).

X. L. Liu, Y. X. Liu, D. T. Yan, H. C. Zhu, C. G. Liu, C. S. Xu, "Luminescence and energy transfer characteristics of Ce $^{3+}$ - and Tb $^{3+}$ -codoped nanoporous 12CaO.7Al $_{2}$ O $_{3}$ phosphors," J. Nanosci. Nanotechnol. 11, 9953-9957 (2011).

Y. Toda, Y. Kubota, M. Hirano, H. Hirayama, H. Hosono, "Surface of room-temperature-stable electride [Ca $_{24}$ Al $_{28}$ O $_{64}$ ] $^{4+}$ (e $^{-}$ ) $_{4}$ : Preparation and its characterization by atomic-resolution scanning tunneling microscopy," ACS Nano 5, 1907-1914 (2011).

2010 (3)

E. Tõldsepp, "Synthesis and luminescence properties of Ce $^{3+}$ doped nanoporous 12CaO $\_$ 7Al $_{2}$ O $_{3}$ powders and ceramics," Opt. Mater. 32, 784-788 (2010).

H. Liu, V. Avrutin, N. Izyumskaya, Ü. Özgür, H. Morkoç, "Transparent conducting oxides for electrode applications in light emitting and absorbing devices," Superlattice. Microst. 48, 458-484 (2010).

M. Miyakawa, H. Hiramatsu, T. Kamiya, M. Hirano, H. Hosono, "Fabrication and electron transport properties of epitaxial films of electron-doped12CaO $\_$ 7Al $_{2}$ O $_{3}$ and 12SrO $_{7}$ Al $_{2}$ O $_{3}$ ," J. Solid State Chem. 183, 385-391 (2010).

2009 (3)

M. Miyakawa, "Thermal conductivity and seebeck coefficient of 12CaO.7Al2O3 electride with a cage structure," J. Ceram. Soc. Jpn. 117, 395-401 (2009).

H. Yanagi, "Low threshold voltage and carrier injection properties of inverted organic light-emitting diodes with [Ca $_{24}$ Al $_{28}$ O $_{64}$ ] $^{4+}$ (4e $^{-})$ cathode and Cu2- $x$ Se anode," J. Phys. Chem. C 113, 18379-18384 (2009).

S. Park, Y. Kim, J. Han, "All solution-processed high-resolution bottom-contact transparent metal-oxide thin film transistors," J. Phys. D: Appl. Phys. 42, (2009) Art no 125102.

2008 (3)

R. Kiyanagi, J. W. Richardson, Jr.N. Sakamoto, M. Yoshimura, "Free oxygen ions and cage deformation in the nanoporous material 12CaO $\cdot$ 7Al $_{2}$ O $_{3}$ : A temperature-dependent neutron powder diffraction study," Solid State Ionics 179, 2365-2371 (2008).

D. Wang, Y. X. Liu, Y. C. Liu, C. S. Xu, C. L. Shao, X. H. Li, "Preparation and visible emission of Er-doped 12CaO.7Al2O3 powder," J. Nanosci. Nanotechnol. 8, 1458-1463 (2008).

D. Wang, Y. Liu, C. Xu, Y. Liu, G. Wang, X. Li, "Local microstructure and photoluminescence of Er-doped 12CaO.7Al $_{2}$ O $_{3}$ powder," J. Rare Earth 26, 433-438 (2008).

2007 (6)

H. Hosono, "Recent progress in transparent oxide semiconductors: Materials and device application," Thin Solid Films 515, 6000-6014 (2007).

K. Hayashi, "Nanoporous crystal 12CaO $\cdot$ 7Al $_{2}$ O $_{3}$ : A playground for studies of ultraviolet optical absorption of negative ions," J. Phys. Chem. B 111, 1946-1956 (2007).

S. Kim, S. Matsuishi, M. Miyakawa, K. Hayashi, M. Hirano, H. Hosono, "Fabrication of room temperature-stable 12CaO $\_$ 7Al2O3 electride: A review," J. Mater. Sci: Mater. Electron. 18, S5-S14 (2007).

S. W. Kim, "Metallic state in a lime-alumina compound with nanoporous structure," Nano Lett. 7, (2007).

M. Miyakawa, M. Hirano, T. Kamiya, H. Hosono, "High electron doping to a wide band gap semiconductor 12CaO.7Al $_{2}$ O $_{3}$ thin film," Appl. Phys. Lett. 90, (2007) Art no 182105.

K. Kim, "Photoelectron spectroscopic study of C12A7:e $^{-}$ and Alq $_{3}$ interface: The formation of a low electron-injection barrier," J. Phys. Chem. C 111, 8403-8406 (2007).

2006 (2)

S. W. Kim, Y. Toda, K. Hayashi, M. Hirano, H. Hosono, "Synthesis of a room temperature stable 12CaO.7Al $_{2}$ O $_{3}$ electride from the melt and its application as an electron field emitter," Chem. Mater. 18, 1938-1944 (2006).

P. V. Sushko, A. L. Shluger, K. Hayashi, M. Hirano, H. Hosono, "Mechanisms of oxygen ion diffusion in a nanoporous complex oxide 12CaO $\cdot$ 7Al $_{2}$ O $_{3}$ ," Phys. Rev. B 73, (2006) Art no 014101.

2005 (2)

T. Kamiya, "Field-induced current modulation in nanoporous semiconductor, electron-doped 12CaO.7Al $_{2}$ O $_{3}$ ," Chem. Mater. 17, 6311-6316 (2005).

P. V. Sushko, A. L. Shluger, K. Hayashi, M. Hirano, H. Hosono, "Localisation assisted by the lattice relaxation and the optical absorption of extra-framework electrons in 12CaO.Al $_{2}$ O $_{3}$ ," Mater. Sci. Eng. C 25, 722-726 (2005).

2004 (2)

Y. Toda, "Field emission in subnanometer-sized cages in [Ca $_{24}$ Al $_{28}$ O $_{64}$ ] $^{4+}$ (4e $^{-}$ )," Adv. Mater. 16, 685-689 (2004).

S. Cherian, C. Donley, D. Mathine, L. LaRussa, W. Xia, N. Armstrong, "Effects of field dependent mobility and contact barriers on liquid crystalline phthalocyanine organic transistors," J. Appl. Phys. 96, 5638-5643 (2004).

2003 (5)

R. L. Hoffman, B. J. Norris, J. F. Wager, "ZnO-based transparent thin-film transistors," Appl. Phys. Lett. 82, 733-735 (2003).

K. Nomura, H. Ohta, K. Ueda, T. Kamiya, M. Hirano, H. Hosono, "Thin-film transistor fabricated in single-crystalline transparent oxide semiconductor," Science 300, 1269-1272 (2003).

H. S. Bae, M. H. Yoon, J. H. Kim, S. Im, "Photodetecting properties of ZnO-based thin-film transistors," Appl. Phys. Lett. 83, 5313-5315 (2003).

Y. Toda, M. Miyakawa, K. Hayashi, T. Kamiya, M. Hirano, H. Hosono, "Thin film fabrication of nano-porous 12CaO.7Al2O3 crystal and its conversion into transparent conductive films by light illumination," Thin Solid Films 445, 309-312 (2003).

S. Matsuishi, "High-density electron anions in a nanoporous Single Crystal: $[{{Ca}}_{24}{{Al}}_{28}{{O}}_{64}]4\cdot (4e^{-})$ ," Science 301, 626-629 (2003).

2002 (1)

U. Kaufmann, "Single chip white LEDs," Phys. Sstat. Sol. (a) 192, 246-253 (2002).

2001 (1)

M. Shiraishi, M. Ata, "Work function of carbon nanotubes," Carbon 39, 1913-1917 (2001).

2000 (1)

O. Gröning, O. M. Küttel, C. Emmenegger, P. Gröning, L. Schlapbach, "Field emission properties of carbon nanotubes," J. Vac. Sci. Technol. B 18, 665 (2000).

ACS Nano (1)

Y. Toda, Y. Kubota, M. Hirano, H. Hirayama, H. Hosono, "Surface of room-temperature-stable electride [Ca $_{24}$ Al $_{28}$ O $_{64}$ ] $^{4+}$ (e $^{-}$ ) $_{4}$ : Preparation and its characterization by atomic-resolution scanning tunneling microscopy," ACS Nano 5, 1907-1914 (2011).

Adv. Mater. (1)

Y. Toda, "Field emission in subnanometer-sized cages in [Ca $_{24}$ Al $_{28}$ O $_{64}$ ] $^{4+}$ (4e $^{-}$ )," Adv. Mater. 16, 685-689 (2004).

Appl. Phys. Lett. (3)

M. Miyakawa, M. Hirano, T. Kamiya, H. Hosono, "High electron doping to a wide band gap semiconductor 12CaO.7Al $_{2}$ O $_{3}$ thin film," Appl. Phys. Lett. 90, (2007) Art no 182105.

H. S. Bae, M. H. Yoon, J. H. Kim, S. Im, "Photodetecting properties of ZnO-based thin-film transistors," Appl. Phys. Lett. 83, 5313-5315 (2003).

R. L. Hoffman, B. J. Norris, J. F. Wager, "ZnO-based transparent thin-film transistors," Appl. Phys. Lett. 82, 733-735 (2003).

Carbon (1)

M. Shiraishi, M. Ata, "Work function of carbon nanotubes," Carbon 39, 1913-1917 (2001).

Chem. Mater. (2)

T. Kamiya, "Field-induced current modulation in nanoporous semiconductor, electron-doped 12CaO.7Al $_{2}$ O $_{3}$ ," Chem. Mater. 17, 6311-6316 (2005).

S. W. Kim, Y. Toda, K. Hayashi, M. Hirano, H. Hosono, "Synthesis of a room temperature stable 12CaO.7Al $_{2}$ O $_{3}$ electride from the melt and its application as an electron field emitter," Chem. Mater. 18, 1938-1944 (2006).

Dalton Trans. (1)

X. Liu, "A multiphase strategy for realizing green cathodoluminescence in 12CaO.7Al $_{2}$ O $_{3}$ -CaCeAl $_{3}$ O $_{7}$ :Ce $^{3+}$ ,Tb $^{3+}$ conductive phosphor," Dalton Trans. 42, 16311-16317 (2013).

J. Lumin. (1)

Y. X. Liu, "Effects of encaged anions on the optical and EPR spectroscopies of RE doped C12A7," J. Lumin. 152, 28-32 (2014).

J. Appl. Phys. (1)

S. Cherian, C. Donley, D. Mathine, L. LaRussa, W. Xia, N. Armstrong, "Effects of field dependent mobility and contact barriers on liquid crystalline phthalocyanine organic transistors," J. Appl. Phys. 96, 5638-5643 (2004).

J. Ceram. Soc. Jpn. (1)

M. Miyakawa, "Thermal conductivity and seebeck coefficient of 12CaO.7Al2O3 electride with a cage structure," J. Ceram. Soc. Jpn. 117, 395-401 (2009).

J. Mater. Chem. (1)

X. Liu, Y. Liu, D. Yan, H. Zhu, C. Liu, "Single-phased white-emitting 12CaO.7Al2O3:Ce $^{3+}$ , Dy $^{3+}$ phosphors with suitable electrical conductivity for field emission displays Cite this," J. Mater. Chem. 22, 16839-16843 (2012).

J. Mater. Chem. (1)

H. Yanagi, T. Kuroda, K. Kim, Y. Toda, T. Kamiya, H. Hosono, "Electron injection barriers between air-stable electride with low work function, C12A7:e $^{-}$ , and pentacene, C60 and copper phthalocyanine," J. Mater. Chem. 22, 4278-4281 (2012).

J. Mater. Sci: Mater. Electron. (1)

S. Kim, S. Matsuishi, M. Miyakawa, K. Hayashi, M. Hirano, H. Hosono, "Fabrication of room temperature-stable 12CaO $\_$ 7Al2O3 electride: A review," J. Mater. Sci: Mater. Electron. 18, S5-S14 (2007).

J. Nanosci. Nanotechnol. (1)

H. Zhu, Y. Liu, D. Yan, X. Yan, C. Liu, C. Xu, "White luminescence of Dy3 $+$ ions doped 12CaO.7Al $_{2}$ O $_{3}$ nanopowders under UV light excitation," J. Nanosci. Nanotechnol. 11, 9958-9963 (2011).

J. Nanosci. Nanotechnol. (2)

D. Wang, Y. X. Liu, Y. C. Liu, C. S. Xu, C. L. Shao, X. H. Li, "Preparation and visible emission of Er-doped 12CaO.7Al2O3 powder," J. Nanosci. Nanotechnol. 8, 1458-1463 (2008).

X. L. Liu, Y. X. Liu, D. T. Yan, H. C. Zhu, C. G. Liu, C. S. Xu, "Luminescence and energy transfer characteristics of Ce $^{3+}$ - and Tb $^{3+}$ -codoped nanoporous 12CaO.7Al $_{2}$ O $_{3}$ phosphors," J. Nanosci. Nanotechnol. 11, 9953-9957 (2011).

J. Phys. Chem. C (1)

H. Yanagi, "Low threshold voltage and carrier injection properties of inverted organic light-emitting diodes with [Ca $_{24}$ Al $_{28}$ O $_{64}$ ] $^{4+}$ (4e $^{-})$ cathode and Cu2- $x$ Se anode," J. Phys. Chem. C 113, 18379-18384 (2009).

J. Phys. Chem. B (1)

K. Hayashi, "Nanoporous crystal 12CaO $\cdot$ 7Al $_{2}$ O $_{3}$ : A playground for studies of ultraviolet optical absorption of negative ions," J. Phys. Chem. B 111, 1946-1956 (2007).

J. Phys. Chem. C (1)

K. Kim, "Photoelectron spectroscopic study of C12A7:e $^{-}$ and Alq $_{3}$ interface: The formation of a low electron-injection barrier," J. Phys. Chem. C 111, 8403-8406 (2007).

J. Phys. D: Appl. Phys. (1)

S. Park, Y. Kim, J. Han, "All solution-processed high-resolution bottom-contact transparent metal-oxide thin film transistors," J. Phys. D: Appl. Phys. 42, (2009) Art no 125102.

J. Rare Earth (1)

D. Wang, Y. Liu, C. Xu, Y. Liu, G. Wang, X. Li, "Local microstructure and photoluminescence of Er-doped 12CaO.7Al $_{2}$ O $_{3}$ powder," J. Rare Earth 26, 433-438 (2008).

J. Solid State Chem. (1)

M. Miyakawa, H. Hiramatsu, T. Kamiya, M. Hirano, H. Hosono, "Fabrication and electron transport properties of epitaxial films of electron-doped12CaO $\_$ 7Al $_{2}$ O $_{3}$ and 12SrO $_{7}$ Al $_{2}$ O $_{3}$ ," J. Solid State Chem. 183, 385-391 (2010).

J. Vac. Sci. Technol. B (1)

O. Gröning, O. M. Küttel, C. Emmenegger, P. Gröning, L. Schlapbach, "Field emission properties of carbon nanotubes," J. Vac. Sci. Technol. B 18, 665 (2000).

Mater. Sci. Eng. C (1)

P. V. Sushko, A. L. Shluger, K. Hayashi, M. Hirano, H. Hosono, "Localisation assisted by the lattice relaxation and the optical absorption of extra-framework electrons in 12CaO.Al $_{2}$ O $_{3}$ ," Mater. Sci. Eng. C 25, 722-726 (2005).

Nano Lett. (1)

S. W. Kim, "Metallic state in a lime-alumina compound with nanoporous structure," Nano Lett. 7, (2007).

Opt. Mater. (2)

H. Zhu, "Long lasting blue phosphorescence and photostimulated luminescence in 12CaO $\_$ 7Al $_{2}$ O $_{3}$ : Eu thin films grown by pulsed laser deposition," Opt. Mater. 36, 1771-1775 (2014).

E. Tõldsepp, "Synthesis and luminescence properties of Ce $^{3+}$ doped nanoporous 12CaO $\_$ 7Al $_{2}$ O $_{3}$ powders and ceramics," Opt. Mater. 32, 784-788 (2010).

Philosophical Mag. (1)

S. W. Kim, H. Hosono, "Synthesis and properties of 12CaO $\cdot$ 7Al $_{2}$ O $_{3}$ electride: Review of single crystal and thin film growth," Philosophical Mag. 92, 2596-2628 (2012).

Phys. Rev. B (1)

P. V. Sushko, A. L. Shluger, K. Hayashi, M. Hirano, H. Hosono, "Mechanisms of oxygen ion diffusion in a nanoporous complex oxide 12CaO $\cdot$ 7Al $_{2}$ O $_{3}$ ," Phys. Rev. B 73, (2006) Art no 014101.

Phys. Rev. B: Condens. Matter (1)

J. A. McLeod, "Spectroscopic characterization of a multiband complex oxide: Insulating and conducting cement 12CaO $\cdot$ 7Al $_{2}$ O $_{3}$ ," Phys. Rev. B: Condens. Matter 85, (2012) Art no 045204.

Phys. Sstat. Sol. (a) (1)

U. Kaufmann, "Single chip white LEDs," Phys. Sstat. Sol. (a) 192, 246-253 (2002).

Sci. Technol. Adv. Mater. (1)

S. Watanabe, "Secondary electron emission and glow discharge properties of 12CaO.7Al $_{2}$ O $_{3}$ electride for fluorescent lamp applications," Sci. Technol. Adv. Mater. 12, (2011) Art no 034410.

Science (2)

S. Matsuishi, "High-density electron anions in a nanoporous Single Crystal: $[{{Ca}}_{24}{{Al}}_{28}{{O}}_{64}]4\cdot (4e^{-})$ ," Science 301, 626-629 (2003).

K. Nomura, H. Ohta, K. Ueda, T. Kamiya, M. Hirano, H. Hosono, "Thin-film transistor fabricated in single-crystalline transparent oxide semiconductor," Science 300, 1269-1272 (2003).

Solid State Ionics (1)

R. Kiyanagi, J. W. Richardson, Jr.N. Sakamoto, M. Yoshimura, "Free oxygen ions and cage deformation in the nanoporous material 12CaO $\cdot$ 7Al $_{2}$ O $_{3}$ : A temperature-dependent neutron powder diffraction study," Solid State Ionics 179, 2365-2371 (2008).

Superlattice. Microst. (1)

H. Liu, V. Avrutin, N. Izyumskaya, Ü. Özgür, H. Morkoç, "Transparent conducting oxides for electrode applications in light emitting and absorbing devices," Superlattice. Microst. 48, 458-484 (2010).

Thin Solid Films (1)

H. Hosono, "Recent progress in transparent oxide semiconductors: Materials and device application," Thin Solid Films 515, 6000-6014 (2007).

Thin Solid Films (1)

Y. Toda, M. Miyakawa, K. Hayashi, T. Kamiya, M. Hirano, H. Hosono, "Thin film fabrication of nano-porous 12CaO.7Al2O3 crystal and its conversion into transparent conductive films by light illumination," Thin Solid Films 445, 309-312 (2003).

Other (2)

M. T. Cole, M. Nakamoto, W. I. Milne, Handbook of Digital Imaging (Wiley, 2015).

D. Han, "Fabrication and characteristics of ZnO-based thin film transistors," 9th ICSICT (2008) pp. 982-984.

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