Effect of annealing atmosphere on the structure and    spectral properties of GdScO<sub>3</sub> and Yb:GdScO<sub>3</sub> crystals

Li Jia-Hong; Sun Gui-Hua; Zhang Qing-Li; Wang Xiao-Fei; Zhang De-Ming; Liu Wen-Peng; Gao Jin-Yun; Zheng Li-Li; Han Song; Chen Zhao; Yin Shao-Tang

doi:10.7498/aps.71.20220196

Abstract

GdScO₃ and Yb:GdScO₃ single crystals are grown by the chzochralski method in nitrogen atmosphere, and they are characterized by X-ray diffraction(XRD), Raman spectra and transmission spectra . Their lattice parameters, atomic coordinates and temperature factors are determined by Rietveld refinement. It is found that the cell volume of GdScO₃ and Yb:GdScO₃ annealed in air atmosphere increase, but after these sample are annealed in H₂ atmosphere their cell volumes decrease. Based on these results, we demonstrate that the crystal grown in nitrogen atmosphere has interstitial oxygen atoms, and the number of interstitial oxygen atoms in the sample annealed in air atmosphere increases, but that annealed in H₂ atmosphere decreases. The Raman peaks of 155 cm^–1, 298 cm^–1, 351 cm^–1 of GdScO₃ are weakened or even disappear when Yb³⁺ ions are doped into it. The Raman spectra of the Yb:GdScO₃ unannealed and annealed in H₂ and air atmosphere are nearly consistent with each other, which indicates that Raman spectrum is insensitive to the defects such as oxygen interstitial caused by annealing. It is suggested that the optical loss of GdScO₃ in the visible wavelength originates mainly from the defect energy level absorption of oxygen interstitial, and transmissivity of Yb:GdScO₃ increases when it is annealed in hydrogen atmosphere, which results from the fact that ytterbium ion can reduce some interstitial oxygen atoms. When GdScO₃ and Yb:GdScO₃ are annealed in air or hydrogen atmosphere, the optical absorption loss of GdScO₃ and Yb:GdScO₃ in a wavelength range of 1000–3000 nm increase due to the trap level produced near the conduction or valence band. The effect on structure and spectral properties of Yb:GdScO₃ and GdScO₃ are explored preliminarily, which is useful for further studying and optimizing laser performance of rare earth doped GdScO₃ crystal.

Keywords:

Authors and contacts

1.
The Key Laboratory of Photonic Devices and Materials, Anhui Province, Anhui Institute of Optics and Fine Mechanics, Hefei institutes of Physical Science, Chinese Academy of Sciences, Hefei 230031, China
2.
University of Science and Technology of China, Hefei 230026, China
3.
Advanced Laser Technology Laboratory of Anhui Province, Hefei 230031, China

Corresponding author: Sun Gui-Hua, ghsun@aiofm.ac.cn ; Zhang Qing-Li, zql@aiofm.ac.cn ;

Funds: Project supported by the National Natural Science Foundation of China (Grant Nos. 51502292, 51802307) and the Open Project of Advanced Laser Technology Laboratory of Anhui Province, China (Grant No. NO.AHL 20220 ZR04).

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References

[1]	Chaix-Pluchery O, Kreisel J 2011 Phase Transitions 84 542 Google Scholar
[2]	Sheng J M, Kan X C, Ge H, Yuan P Q, Zhang L, Zhao N, Song Z M, Yao Y Y, Tang J N, Wang S M, Tian M L, Tong X, Wu L S 2020 Chin. Phys. B 29 66 Google Scholar
[3]	Jia J H, Ke Y J, Zhang X X, Wang J F, Su L, Wu Y D, Xia Z C 2019 J. Alloys Compd. 803 992 Google Scholar
[4]	Rong S S, Faheem M B, Li Y B 2021 J. Electron. Sci. Technol. 19 119 Google Scholar
[5]	Aamir M, Bibi I, Ata S, Jilani K, Majid F, Kamal S, Alwadai N, Raza M A S, Bashir M, Iqbal S, Aadil M, Iqbal M 2021 Ceram. Int. 47 16696 Google Scholar
[6]	Lin S H, Lin Z Q, Chen C W 2021 Ceram. Int 47 16828 Google Scholar
[7]	Rumyantsev S, Stillman W, Shur M, Heeg T, Schlom D G, Koveshnikov S, Kambhampati R, Tokranov V, Oktyabrsky S 2012 Int. J. High Speed Electron. Syst. 20 105 Google Scholar
[8]	Mizzi C A, Koirala P, Marks L D 2018 Phys. Rev. Mater. 2 025001 Google Scholar
[9]	Schäfer A, Besmehn A, Luysberg M, Winden A, Stoica T, Schnee M, Zander W, Niu G, Schroeder T, Mantl S, Hardtdegen H, Mikulics M, Schubert J 2014 Semicond. Sci. Technol. 29 075005 Google Scholar
[10]	Schäfer A, Rahmanizadeh K, Bihlmayer G, Luysberg M, Wendt F, Besmehn A, Fox A, Schnee M, Niu G, Schroeder T, Mantl S, Hardtdegen H, Mikulics M, Schubert J 2015 J. Alloys Compd. 651 514 Google Scholar
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[12]	Mansley Z R, Mizzi C A, Koirala P, Wen J, Marks L D 2020 Phys. Rev. Mater. 4 045003 Google Scholar
[13]	Paull R J, Mansley Z R, Ly T, Marks L D, Poeppelmeier K R 2018 Inorg. Chem. 57 4104 Google Scholar
[14]	Seidel S, Schmid A, Miersch C, Schubert J, Heitmann J 2021 Appl. Phys. Lett. 118 052902 Google Scholar
[15]	Briones J, Guinto M C, Pelicano C M 2021 Mater. Lett. 298 130040 Google Scholar
[16]	Liu Y 2021 IOP Conference Series:Earth and Environmental Science 781 022069 Google Scholar
[17]	Hidde J, Guguschev C, Ganschow S, Klimm D 2018 J. Alloys Compd. 738 415 Google Scholar
[18]	Wu Y D, Chen H, Hua J Y, Qin Y L, Ma X H, Wei Y Y, Zi Z F 2019 Ceram. Int. 45 13094 Google Scholar
[19]	Peng F, Liu W, Zhang Q, Luo J, Sun D, Sun G, Zhang D, Wang X 2018 J. Lumin. 201 176 Google Scholar
[20]	Li Q, Dong J, Wang Q, Xue Y, Tang H, Xu X, Xu J 2020 Opt. Mater. 109 110298 Google Scholar
[21]	Li Q, Dong J, Wang Q, Zhao H, Xue Y, Tang H, Xu X, Xu J 2021 J. Lumin. 230 117681 Google Scholar
[22]	Hou W, Zhao H, Qin Z, Liu J, Wang D, Xue Y, Wang Q, Xie G, Xu X, Xu J 2020 Opt. Mater. Express 10 2730 Google Scholar
[23]	Wang D, Hou W, Li N, Xue Y, Wang Q, Xu X, Li D, Zhao H, Xu J 2019 Opt. Mater. Express 9 4218 Google Scholar
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[26]	Gupta S K, Grover V, Shukla R, Srinivasu K, Natarajan V, Tyagi A K 2016 Chem. Eng. J. 283 114 Google Scholar
[27]	Arsenev P A, Bienert K E, Sviridova R K 1972 Phys. Status Solidi A 9 K103 Google Scholar
[28]	Rietveld H 1967 Acta Crystallogr. 22 151 Google Scholar
[29]	Rietveld H 1969 J. Appl. Crystallogr 2 65 Google Scholar
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[32]	Grover V, Shukla R, Jain D, Deshpande S K, Arya A, Pillai C G S, Tyagi A K 2012 Chem. Mater. 24 2186 Google Scholar
[33]	Chaix-Pluchery O, Kreisel J 2009 J. Phys. Condens. Matter 21 175901 Google Scholar
[34]	Weber M C, Guennou M, Zhao H J, Íñiguez J, Vilarinho R, Almeida A, Moreira J A, Kreisel J 2016 Phys. Rev. B 94 214103 Google Scholar
[35]	Iliev M N, Abrashev M V, Laverdière J, Jandl S, Gospodinov M M, Wang Y Q, Sun Y Y 2006 Phys. Rev. B 73 064302 Google Scholar
[36]	Alsowayigh M M, Timco G A, Borilovic I, Alanazi A, Vitorica-Yrezabal I J, Whitehead G F S, McNaughter P D, Tuna F, O'Brien P, Winpenny R E P, Lewis D J, Collison D 2020 Inorg. Chem. 59 15796 Google Scholar
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[38]	Ruffo A, Mozzati M C, Albini B, Galinetto P, Bini M 2020 J. Mater. Sci.: Mater. Electron. 31 18263 Google Scholar
[39]	Nikl M, Nitsch K, Hybler J, Chval J, Reiche P 1996 Phys. Status Solidi B 196 7 Google Scholar
[40]	李涛, 赵广军, 何晓明, 徐军, 潘守夔 2002 人工晶体学报 31 456 Li T, Zhao G J, He X M, Xu J, Pan S K 2002 J. Artif. Cryst. 31 456

Cited By

图 1 GdScO₃晶体XRD数据Rietveld精修结果(cal, obs, bckgr和diff表示计算值、实验值、背底以及实验值和计算值之间的误差)

Figure 1. Rietveld refinement results of the GdScO₃ crystal obtained from the XRD data. (cal, obs, bckgr, and diff mean calculated data, observed data, background, and the difference between observed data and calculated data).

DownLoad: Full-Size Img PowerPoint

图 2 不同气氛退火GdScO₃晶体XRD精修结果与GdScO₃标准卡片(ICSD#65513)　(a) Yb:GdScO₃未退火; (b) Yb:GdScO₃空气气氛退火; (c) Yb:GdScO₃ H₂气氛退火; (d) GdScO₃空气气氛退火; (e) GdScO₃ H₂气氛退火; (f) GdScO₃(ICSD#65513)

Figure 2. Rietveld refinement results of the GdScO₃ crystal obtained from the XRD data annealed in different atmospheres and (ICSD#65513): (a) Yb:GdScO₃ unannealed; (b) Yb:GdScO₃ annealed in air atmosphere; (c) Yb:GdScO₃ annealed in H₂; (d) GdScO₃ annealed in air atmosphere; (e) GdScO₃ annealed in H₂; (f) GdScO₃(ICSD#65513).

DownLoad: Full-Size Img PowerPoint

图 3 不同退火气氛下Yb:GdScO₃和GdScO₃晶体的拉曼光谱　(a) Yb:GdScO₃ 未退火; (b) Yb:GdScO₃ 空气气氛退火; (c) Yb:GdScO₃ H₂气氛退火; (d) GdScO₃ 空气气氛退火; (e) GdScO₃ H₂气氛退火

Figure 3. Raman spectra of Yb:GdScO₃ and GdScO₃ crystals annealed in different atmospheres: (a) Yb:GdScO₃ unannealed; ( b) Yb:GdScO₃ annealed in air atmosphere; (c) Yb:GdScO₃ annealed in H₂; (d) GdScO₃ annealed in air atmosphere; (e) GdScO₃ annealed in H_2.

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图 4 不同退火气氛条件下GdScO₃晶体在250—3000 nm范围内的透射光谱　(a) GdScO₃ H₂气氛退火(样品厚度d = 1.60 mm); (b) GdScO₃ 未退火(样品厚度d = 1.63 mm); (c) GdScO₃ 空气气氛退火(样品厚度d=1.62 mm)

Figure 4. Transmittance spectra of the GdScO₃ crystal before and after annealed in the range of 250–3000 nm: (a) GdScO₃ annealed in H₂; (b) GdScO₃ unannealed; (c) GdScO₃ annealedin air atmosphere.

DownLoad: Full-Size Img PowerPoint

图 5 不同气氛条件下Yb:GdScO₃晶体在250—3000 nm范围内的透射光谱　(a) Yb:GdScO₃ H₂气氛退火(样品厚度d = 1.65 mm); (b) Yb:GdScO₃ 未退火(样品厚度d = 1.60 mm); (c) Yb:GdScO₃ 空气气氛退火(样品厚度d = 1.66 mm)

Figure 5. Transmittance spectra of the Yb:GdScO₃ crystal before and after annealed in the range of 250—3000 nm: (a) Yb:GdScO₃ annealed in H₂; (b) Yb:GdScO₃ unannealed; (c) Yb:GdScO₃ annealed in air atmosphere.

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表 1 GdScO₃晶体XRD数据精修结构参数

Table 1. Refined structural parameters of GdScO₃ crystal obtained from XRD data.

Atom	Multiplicity Wyckoff letter	x	y	z	Occupancy	U_iso	R factor
Atom	Multiplicity Wyckoff letter	x	y	z	Occupancy	U_iso	R_p	R_wp
GdScO₃ annealed in H₂
O1	4c	0.451078	0.250000	0.112375	1.0144	0.01800
Sc1	4b	0.000000	0.000000	0.500000	0.9994	0.02418	4.12%	5.19%
O2	8d	0.193300	0.557177	0.182774	0.9985	0.04452
Gd1	4c	0.440567	0.750000	0.482340	0.9268	0.01880
GdScO₃ annealed in air atmosphere
O1	4c	0.468803	0.250000	0.108393	0.0298	0.01489
Sc1	4b	0.000000	0.000000	0.500000	0.9984	0.01157	4.56%	5.83%
O2	8d	0.205347	0.561459	0.188795	1.0616	0.01910
Gd1	4c	0.440566	0.750000	0.486551	1.0022	0.01328
Yb:GdScO₃ annealed in H₂
O1	4c	0.459576	0.250000	0.103701	1.1295	0.00793
Sc1	4b	0.000000	0.000000	0.500000	1.0062	0.01648	4.45%	5.66%
O2	8d	0.199195	0.559033	0.183212	1.0482	0.01898
Gd1	4c	0.439748	0.750000	0.485806	0.9781	0.01645
Yb1	4c	0.451014	0.750000	0.404342	0.0189	0.07962
Yb:GdScO₃ annealed in air atmosphere
O1	4c	0.462904	0.250000	0.092804	1.0952	0.01311
Sc1	4b	0.000000	0.000000	0.500000	1.0241	0.02387	4.67%	5.99%
O2	8d	0.184743	0.552496	0.189058	1.0101	0.03297
Gd1	4c	0.438027	0.750000	0.483159	0.9807	0.02051
Yb1	4c	0.443478	0.750000	0.413392	0.0192	0.04427
Yb:GdScO₃ unannealed
O1	4c	0.465020	0.250000	0.338290	1.3635	0.01824
Sc1	4b	0.000000	0.000000	0.500000	0.9707	0.01780	5.20%	7.13%
O2	8d	0.177886	0.573337	0.202298	1.0466	0.03207
Gd1	4c	0.437167	0.750000	0.482011	0.9540	0.01456
Yb 1	4c	0.459029	0.750000	0.370978	0.0181	0.09000

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表 2 不同气氛退火GdScO₃和Yb: GdScO₃的晶胞参数、晶胞体积和计算密度

Table 2. Refined lattice parameters, unit cell volumes and calculated densities of GdScO₃ and Yb:GdScO₃ annealed in different atmospheres.

GdScO₃	a/Å	b/Å	c/Å	V/Å³	ρ/(g·cm^–3)
GdScO₃ annealed in H₂	5.750224	7.936361	5.485410	250.331367	6.6380
GdScO₃ annealed in air	5.750860	7.936271	5.485696	250.369268	6.6399
Yb:GdScO₃ annealed in H₂	5.747629	7.931895	5.481167	249.884155	6.6584
Yb:GdScO₃ annealed in air	5.754268	7.942210	5.488072	250.843313	6.6328
Yb:GdScO₃ unannealed	5.748397	7.936244	5.482695	250.124281	6.6519

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map

[1]	Chaix-Pluchery O, Kreisel J 2011 Phase Transitions 84 542 Google Scholar
[2]	Sheng J M, Kan X C, Ge H, Yuan P Q, Zhang L, Zhao N, Song Z M, Yao Y Y, Tang J N, Wang S M, Tian M L, Tong X, Wu L S 2020 Chin. Phys. B 29 66 Google Scholar
[3]	Jia J H, Ke Y J, Zhang X X, Wang J F, Su L, Wu Y D, Xia Z C 2019 J. Alloys Compd. 803 992 Google Scholar
[4]	Rong S S, Faheem M B, Li Y B 2021 J. Electron. Sci. Technol. 19 119 Google Scholar
[5]	Aamir M, Bibi I, Ata S, Jilani K, Majid F, Kamal S, Alwadai N, Raza M A S, Bashir M, Iqbal S, Aadil M, Iqbal M 2021 Ceram. Int. 47 16696 Google Scholar
[6]	Lin S H, Lin Z Q, Chen C W 2021 Ceram. Int 47 16828 Google Scholar
[7]	Rumyantsev S, Stillman W, Shur M, Heeg T, Schlom D G, Koveshnikov S, Kambhampati R, Tokranov V, Oktyabrsky S 2012 Int. J. High Speed Electron. Syst. 20 105 Google Scholar
[8]	Mizzi C A, Koirala P, Marks L D 2018 Phys. Rev. Mater. 2 025001 Google Scholar
[9]	Schäfer A, Besmehn A, Luysberg M, Winden A, Stoica T, Schnee M, Zander W, Niu G, Schroeder T, Mantl S, Hardtdegen H, Mikulics M, Schubert J 2014 Semicond. Sci. Technol. 29 075005 Google Scholar
[10]	Schäfer A, Rahmanizadeh K, Bihlmayer G, Luysberg M, Wendt F, Besmehn A, Fox A, Schnee M, Niu G, Schroeder T, Mantl S, Hardtdegen H, Mikulics M, Schubert J 2015 J. Alloys Compd. 651 514 Google Scholar
[11]	Uecker R, Velickov B, Klimm D, Bertram R, Bernhagen M, Rabe M, Albrecht M, Fornari R, Schlom D G 2008 J. Cryst. Growth 310 2649 Google Scholar
[12]	Mansley Z R, Mizzi C A, Koirala P, Wen J, Marks L D 2020 Phys. Rev. Mater. 4 045003 Google Scholar
[13]	Paull R J, Mansley Z R, Ly T, Marks L D, Poeppelmeier K R 2018 Inorg. Chem. 57 4104 Google Scholar
[14]	Seidel S, Schmid A, Miersch C, Schubert J, Heitmann J 2021 Appl. Phys. Lett. 118 052902 Google Scholar
[15]	Briones J, Guinto M C, Pelicano C M 2021 Mater. Lett. 298 130040 Google Scholar
[16]	Liu Y 2021 IOP Conference Series:Earth and Environmental Science 781 022069 Google Scholar
[17]	Hidde J, Guguschev C, Ganschow S, Klimm D 2018 J. Alloys Compd. 738 415 Google Scholar
[18]	Wu Y D, Chen H, Hua J Y, Qin Y L, Ma X H, Wei Y Y, Zi Z F 2019 Ceram. Int. 45 13094 Google Scholar
[19]	Peng F, Liu W, Zhang Q, Luo J, Sun D, Sun G, Zhang D, Wang X 2018 J. Lumin. 201 176 Google Scholar
[20]	Li Q, Dong J, Wang Q, Xue Y, Tang H, Xu X, Xu J 2020 Opt. Mater. 109 110298 Google Scholar
[21]	Li Q, Dong J, Wang Q, Zhao H, Xue Y, Tang H, Xu X, Xu J 2021 J. Lumin. 230 117681 Google Scholar
[22]	Hou W, Zhao H, Qin Z, Liu J, Wang D, Xue Y, Wang Q, Xie G, Xu X, Xu J 2020 Opt. Mater. Express 10 2730 Google Scholar
[23]	Wang D, Hou W, Li N, Xue Y, Wang Q, Xu X, Li D, Zhao H, Xu J 2019 Opt. Mater. Express 9 4218 Google Scholar
[24]	Peng F, Liu W, Luo J, Sun D, Chen Y, Zhang H, Ding S, Zhang Q 2018 Crystengcomm 20 6291 Google Scholar
[25]	Yamaji A, Kochurikhin V, Fujimoto Y, Futami Y, Yanagida T, Yokota Y, Kurosawa S, Yoshikawa A 2012 Phys. Status SolidiC 9 2267 Google Scholar
[26]	Gupta S K, Grover V, Shukla R, Srinivasu K, Natarajan V, Tyagi A K 2016 Chem. Eng. J. 283 114 Google Scholar
[27]	Arsenev P A, Bienert K E, Sviridova R K 1972 Phys. Status Solidi A 9 K103 Google Scholar
[28]	Rietveld H 1967 Acta Crystallogr. 22 151 Google Scholar
[29]	Rietveld H 1969 J. Appl. Crystallogr 2 65 Google Scholar
[30]	张克从, 张乐潓 1997 晶体生长科学与技术(上) (北京: 科学出版社) 第472页 Zhang K C, Zhang L H 1997 Crystal Growth Science and Technology (Vol. 1) (Beijing: Science Press) p472 (in Chinese)
[31]	Chopelas A 2011 Phys. Chem. Miner. 38 709 Google Scholar
[32]	Grover V, Shukla R, Jain D, Deshpande S K, Arya A, Pillai C G S, Tyagi A K 2012 Chem. Mater. 24 2186 Google Scholar
[33]	Chaix-Pluchery O, Kreisel J 2009 J. Phys. Condens. Matter 21 175901 Google Scholar
[34]	Weber M C, Guennou M, Zhao H J, Íñiguez J, Vilarinho R, Almeida A, Moreira J A, Kreisel J 2016 Phys. Rev. B 94 214103 Google Scholar
[35]	Iliev M N, Abrashev M V, Laverdière J, Jandl S, Gospodinov M M, Wang Y Q, Sun Y Y 2006 Phys. Rev. B 73 064302 Google Scholar
[36]	Alsowayigh M M, Timco G A, Borilovic I, Alanazi A, Vitorica-Yrezabal I J, Whitehead G F S, McNaughter P D, Tuna F, O'Brien P, Winpenny R E P, Lewis D J, Collison D 2020 Inorg. Chem. 59 15796 Google Scholar
[37]	Singh M K, Jang H M, Gupta H C, Katiyar R S 2008 J. Raman Spectrosc. 39 842 Google Scholar
[38]	Ruffo A, Mozzati M C, Albini B, Galinetto P, Bini M 2020 J. Mater. Sci.: Mater. Electron. 31 18263 Google Scholar
[39]	Nikl M, Nitsch K, Hybler J, Chval J, Reiche P 1996 Phys. Status Solidi B 196 7 Google Scholar
[40]	李涛, 赵广军, 何晓明, 徐军, 潘守夔 2002 人工晶体学报 31 456 Li T, Zhao G J, He X M, Xu J, Pan S K 2002 J. Artif. Cryst. 31 456

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Vol. 71, Issue 16 - 2022-08-20

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Effect of annealing atmosphere on the structure and spectral properties of GdScO₃ and Yb:GdScO₃ crystals

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Corresponding author: Sun Gui-Hua, ghsun@aiofm.ac.cn ; Zhang Qing-Li, zql@aiofm.ac.cn ;

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Effect of annealing atmosphere on the structure and spectral properties of GdScO3 and Yb:GdScO3 crystals

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Corresponding author: Sun Gui-Hua, ghsun@aiofm.ac.cn ; Zhang Qing-Li, zql@aiofm.ac.cn ;

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Effect of annealing atmosphere on the structure and spectral properties of GdScO₃ and Yb:GdScO₃ crystals