Synthesis and Characterization of CaAl2O4: Dy3+ and CaAl2O4: Sm3+ Phosphor Powders

Year 2022, Volume: 9 Issue: 1, 360 - 370, 31.01.2022

Erkul Karacaoğlu

https://doi.org/10.31202/ecjse.1002508

Abstract

Calcium aluminate, CaAl2O4 is efficient and well known host material for inorganic phosphors. Although this host structure is mostly doped with Eu2+, different types of rare earth ions have also been studied. In this study, attention was drawn to CaAl2O4 type phosphors doped with Dy3+ and Sm3+ at different concentrations. Ca1-xAl2O4: Dy3+x (x= 0.008, 0.012, 0.02, 0.03) and Ca1-yAl2O4: Sm3+y (y= 0.008, 0.012, 0.02, 0.03) phosphors were synthesized as powder samples through the solid-state reaction method. After heat treatments, monoclinic CaAl2O4 structure was confirmed for all rare earth doped samples by the XRD analysis. PL characteristics of samples depend on activator ion. The PL emission spectra of Dy3+ doped powder samples show two strong bands at 484 nm and 577 nm which are attributed to a typical 4F9/2 → 6H15/2 and 4F9/2 → 6H13/2 transitions of Dy3+ ions. Sm3+ activated phosphors have the emission peaks at 565 nm, 604 nm, 649 nm, and 712 nm which are assigned to Sm3+ transitions: 4G5/2 → 6H5/2, 4G5/2 → 6H7/2, 4G5/2 → 6H9/2, 4G5/2 → 6H11/2, respectively. The Commission International De IEclairage (CIE) 1976 chromaticity coordinates were evaluated from the emission spectra in two different rare earth ion doped phosphors, the values (uꞌ = 0.21805, vꞌ = 0.52537) and (uꞌ = 0.36078, vꞌ = 0.54567) were colors of yellow-orange and brick red, respectively. Consequently, synthesized Ca1-xAl2O4: Dy3+x (x= 0.008) and Ca1-xAl2O4: Sm3+y (y= 0.008) phosphors emitting in different color regions can be useful for LED’s and display applications.

Keywords

CaAl2O4, Dy3+, Sm3+, solid state reaction method, LED phosphors

Supporting Institution

TUBITAK–2214-A International Doctoral Research Fellowship Programme

Project Number

1059B141700014

Thanks

Erkul Karacaoglu acknowledges TUBITAK–2214-A International Doctoral Research Fellowship Programme for supporting a portion of this research to be conducted at the Georgia Institute of Technology.

CaAl2O4: Dy+3 ve CaAl2O4: Sm+3 Işıldar Tozlarının Üretimi ve Karakterizasyonu

Abstract

Kalsiyum alüminat, CaAl2O4, inorganik fosforlarda oldukça işlevsel ve iyi bilinen bir konut malzemedir. Bu konut yapıdaki fosforlar çoğunlukla Eu2+ ile katkılanmakla birlikte farklı tipte nadir toprak iyonları da çalışılmıştır. Bu çalışmada CaAl2O4 tipindeki konut yapı, Dy3+ ve Sm3+ ile farklı konsantrasyonlarda katkılanmıştır. Ca1-xAl2O4: Dy+3x (x= 0.008, 0.012, 0.02, 0.03) ve Ca1-yAl2O4: Sm+3y (y= 0.008, 0.012, 0.02, 0.03) fosforları toz numuneler halinde katı-hal tepkimesi yöntemiyle sentezlenmişlerdir. Isıl işlemlerden sonra XRD analizi yapılarak nadir toprak iyonları katkılı fosfor tozları monoklinik CaAl2O4 yapısında indislenmiştir. Fotolüminesans özellikler katkı iyonuna bağlı olarak belirlenmiştir. Dy+3 katkılı fosforlara ait 484 nm ve 577 nm iki belirgin pik, 4F9/2 → 6H15/2 ve 4F9/2 → 6H13/2: Dy+3 geçişlerine aittir. Sm3+ katkılı fosforlarda ise 565 nm, 604 nm, 649 nm, and 712 nm’deki pikler 4G5/2 → 6H5/2, 4G5/2 → 6H7/2, 4G5/2 → 6H9/2, 4G5/2 → 6H11/2: Sm+3 geçişleri ile ilgilidir. Commission International De IEclairage (CIE) 1976 renklilik diyagramından faydalanılarak fosfor tozlarına ait ışıma dalga boylarına bağlı olarak belirlenen (uꞌ = 0.21805, vꞌ = 0.52537) ve (uꞌ = 0.36078, vꞌ = 0.54567) koordinatlarına göre sırasıyla Dy+3 iyonları sarı-turuncu bölgede, Sm+3 iyonları ise kiremit kırmızısı renk bölgelerinde ışımaların oluştuğunu göstermiştir. Sonuç olarak iki farklı alternatif nadir toprak iyonu ile katkılanan CaAl2O4 fosforlarının LED’lerde ve görüntü oluşturma uygulamalarında değerlendirilmeleri mümkündür.

Keywords

CaAl2O4, Dy+3, Sm+3, katı hal tepkimesi yöntemi, LED fosforları

Project Number

1059B141700014

References

• [1]. Karacaoglu, E., Ozturk, E., Uyaner, M., Losego, M.D., “Atomic layer deposition (ALD) of nanoscale coatings on SrAl2O4-based phosphor powders to prevent aqueous degradation”, Journal of American Ceramic Society, 2020, 103: 3706–3715.
• [2]. Kaya, S.Y., Karacaoglu, E., Karasu, B., “Effect of Al/Sr ratio on the luminescence properties of SrAl2O4: Eu2+, Dy3+ phosphors”, Ceramics International, 2012, 38(5): 3701-3706.
• [3]. Kim, D., “Recent Developments in Lanthanide-Doped Alkaline Earth Aluminate Phosphors with Enhanced and Long-Persistent Luminescence”. Nanomaterials, 2021, 11: 723.
• [4]. Kim, D., Kim, H.E., Kim, C.H., “Development of a Blue Emitting Calcium-Aluminate Phosphor”, PLoS ONE, 2016, 11(9): e0162920.
• [5]. Mills, A., “Phosphors development for LED lighting, III-Vs Review”, 2005, 18(3): 32-34.
• [6]. Xia, Z., Xu, Z., Chen, M., Liu, Q., “Recent developments in the new inorganic solid state LED phosphors”, Dalton Trans., 2016, 45: 11214-11232.
• [7]. Singh, M.N., Singh, L.R., Barua, A.G., “Effects of doping concentration on thermoluminescence parameters of CaAl2O4:Re3+ (Re3+ = Dy3+, Sm3+, Tm3+) prepared by combustion method”, Radiation Physics and Chemistry, 2021, 188: 109631.
• [8]. Chen, Z., Xu, H., Cao, C., Chen, X., Zhang, M., Jian, M., Li, Y., Xie, A. “Synthesis, Luminescent Properties and White LED Fabrication of Sm3+ Doped Lu2WMoO9”, Coatings 2021, 11: 403.
• [9]. Wako, A.H., Dejene, B.F., Swart, H.C., “Properties of blue emitting CaAl2O4:Eu2+, Nd3+ phosphor by optimizing the amount of flux and fuel”, Physica B: Condensed Matter, 2014, 439: 160-164.
• [10]. Pan, X., Zhang, D., Wu, Y., Yu, H., “Synthesis and characterization of calcium aluminate compounds from gehlenite by high-temperature solid-state reaction”, Ceramics International, 2018, 44(12): 13544-13550.
• [11]. Sharma, V., Das, A., Kumar, V., Kumar, V., Verma, K., Swart, H.C., “Combustion synthesis and characterization of blue long lasting phosphor CaAl2O4: Eu2+, Dy3+ and its novel application in latent fingerprint and lip mark detection”, Physica B: Condensed Matter, Volume 535, 2018, Pages 149-156.
• [12]. Vitola, V., Millers, D., Bite, I., Smits, K., Spustaka, A., “Recent progress in understanding the persistent luminescence in SrAl2O4: Eu, Dy” Materials Science and Technology, 2019, 35(14): 1661-1677.
• [13]. Yang, Y., Pan, H., Guan, L., Wang, D., Zhao, J., Yang, J., Yang, Z., Li, X., “Electronic structure and luminescent properties of Sr3Al2O6:Sm3+ orange phosphor prepared by hydrothermal method”, Journal of Materials Research and Technology, 2020, 9(3): 3847-3855.
• [14]. Kaur, P., Khanna, A., “Structural, thermal and light emission properties of Eu, Sm, Dy, Er and Mn doped CaAl2O4 and SrAl2O4”, Ceramics International, 2021, 47(10): 14655-14664.
• [15]. Ziyauddin, M., Tigga, S., Brahme, N., Bisen, D.P., “Photoluminescence and thermoluminescence studies of CaAl2O4:Dy3+ phosphor”, Luminescence, 2015, 31(1): 76-80.
• [16]. Shashikala, B.S., Premkumar, H.B., Darshan, G.P., Nagabhushana, H., Sharmaf, S.C., Prashanthag, S.C., Nagaswarupag, H.P., “Synthesis and Photoluminescence Studies of an Orange Red Color Emitting novel CaAl2O4: Sm3+ nanophosphor for LED Applications”, Materials Today: Proceedings 4, 2017, 11820–11826.