Theoretical Studies on the Structural Stability and Doping Effects of RE2SiO5 (RE=Sc, Y, La)

doi:10.16553/j.cnki.issn1000-985x.2025.0255

Abstract

Abstract: Rare earth silicates RE₂SiO₅ （RE=rare earth） with significant applications as laser host， scintillator， thermal barrier coatings， and quantum memory devices， generally exhibit two distinct structural phases： X1-type （lower temperature， space group P2₁/c） and X2-type （higher temperature， space group C2/c）. Each structure contains two unique sites hosting the rare earth ions， characterized by different coordination numbers （CNs）. Theoretical calculations with the electronic structure and molecular dynamics software package CP2K were performed to better understand the structural stabilities of these compounds and the preferential site occupations of doping rare earth ions. The Gaussian basis set and the Perdew-Burke-Ernzerhof for solids （PBEsol） functional were employed due to their high computation speed and their reliable structural optimization results for solid materials. According to the results from theoretical calculations， it is found that the dispersion correction plays a vital role in correctly predicting the relative structural stability of the RE₂SiO₅ phases. Furthermore， the doping behaviors of rare earth ions with varying sizes in Y₂SiO₅ are systematically investigated. Our findings reveal that in both phases， Y1 site （CN=9 for X1-type， and CN=7 for X2-type） is preferentially occupied by larger ions like La³⁺， while smaller ions such as Sc³⁺ demonstrate greater stability at Y2 site （CN=7 for X1-type， and CN=6 for X2-type）. These results provide valuable insights into the structural properties and doping mechanisms of this class of crystals.

Key words: rare earth silicate; first-principle; structural phase transition; structural stability; doping; phosphor; scintillator materialCLC number：TB34

CLC Number:

O743.4

JIANG Qianyue, LI Rukang. Theoretical Studies on the Structural Stability and Doping Effects of RE₂SiO₅ (RE=Sc, Y, La)[J]. Journal of Synthetic Crystals, 2026, 55(4): 566-573.

Figures/Tables 6

References 48

[1]	TOROPOV N A， BONDAR I A. Silicates of the rare earth elements ［J］. Russ Chem Bull， 1961， 10（4）： 502-8.
[2]	WARSHAW I， ROY R. Polymorphism of the rare earth sesquioxides1［J］. The Journal of Physical Chemistry， 1961， 65（11）： 2048-2051.
[3]	HARRIS L A， FINCH C B. Crystallographic data for Er₂SiO₅ and Y₂SiO₅ ［J］. American Mineralogist， 1965， 50（9）： 1493-1495.
[4]	TIAN Z L， ZHENG L Y， WANG J M， et al. Theoretical and experimental determination of the major thermo-mechanical properties of RE₂SiO₅ （RE=Tb， Dy， Ho， Er， Tm， Yb， Lu， and Y） for environmental and thermal barrier coating applications［J］. Journal of the European Ceramic Society， 2016， 36（1）： 189-202.
[5]	JACQUEMET M， JACQUEMET C， JANEL N， et al. Efficient laser action of Yb∶LSO and Yb∶YSO oxyorthosilicates crystals under high-power diode-pumping［J］. Applied Physics B， 2005， 80（2）： 171-176.
[6]	THIBAULT F， PELENC D， DRUON F， et al. Efficient diode-pumped Yb³⁺∶Y₂SiO₅ and Yb³⁺∶Lu₂SiO₅ high-power femtosecond laser operation［J］. Optics Letters， 2006， 31（10）： 1555-1557.
[7]	KANG F W， ZHANG Y， PENG M Y. Controlling the energy transfer via multi luminescent centers to achieve white light/tunable emissions in a single-phased X2-type Y₂SiO₅∶Eu³⁺， Bi³⁺ phosphor for ultraviolet converted LEDs［J］. Inorganic Chemistry， 2015， 54（4）： 1462-1473.
[8]	COOKE D W， MCCLELLAN K J， BENNETT B L， et al. Crystal growth and optical characterization of cerium-doped Lu_1.8Y_0.2SiO₅ ［J］. Journal of Applied Physics， 2000， 88（12）： 7360-7362.
[9]	VAN EIJK C W E. Development of inorganic scintillators［J］. Nuclear Instruments and Methods in Physics Research Section A： Accelerators， Spectrometers， Detectors and Associated Equipment， 1997， 392（1/2/3）： 285-290.
[10]	MELCHER C L， ERIKSSON L A， AYKAC M， et al. Current and future use of LSO∶Ce scintillators in pet［M］//Radiation Detectors for Medical Applications. Springer Netherlands， 2006： 243-257.
[11]	HAM B S， HEMMER P R， SHAHRIAR M S. Efficient electromagnetically induced transparency in a rare-earth doped crystal［J］. Optics Communications， 1997， 144（4/5/6）： 227-230.
[12]	ZHONG M J， HEDGES M P， AHLEFELDT R L， et al. Optically addressable nuclear spins in a solid with a six-hour coherence time［J］. Nature， 2015， 517（7533）： 177-180.
[13]	TURUKHIN A V， SUDARSHANAM V S， SHAHRIAR M S， et al. Observation of ultraslow and stored light pulses in a solid［J］. Physical Review Letters， 2002， 88（2）： 023602.
[14]	FELSCHE J. The crystal chemistry of the rare-earth silicates［M］//Rare Earths. Berlin， Heidelberg： Springer， 1973： 99-197.
[15]	CANNAS C， MUSINU A， PICCALUGA G， et al. Advances in the structure and microstructure determination of yttrium silicates using the Rietveld method［J］. Journal of Solid State Chemistry， 2005， 178（5）： 1526-1532.
[16]	ZHANG X， ZHANG C Y， WANG X F， et al. Investigation on doping behavior of Ho ions in Lu₂SiO₅ lattice by XRD Rietveld refinement and first-principles calculations［J］. Journal of Solid State Chemistry， 2024， 331： 124505.
[17]	MIRZAI A， AHADI A， MELIN S， et al. First-principle investigation of doping effects on mechanical and thermodynamic properties of Y₂SiO₅ ［J］. Mechanics of Materials， 2021， 154： 103739.
[18]	WEN J， DUAN C K， NING L X， et al. Spectroscopic distinctions between two types of Ce³⁺ ions in X2-Y₂SiO₅： a theoretical investigation［J］. The Journal of Physical Chemistry A， 2014， 118（27）： 4988-4994.
[19]	LIN J， SU Q， WANG S B， et al. Influence of crystal structure on the luminescence properties of bismuth（III）， europium（III） and dysprosium（III） in Y₂SiO₅ ［J］. Journal of Materials Chemistry， 1996， 6（2）： 265-269.
[20]	CHING W Y， OUYANG L Z， XU Y N. Electronic and optical properties of Y₂SiO₅ and Y₂Si₂O₇ with comparisons to α-SiO₂ and Y₂O₃ ［J］. Physical Review B， 2003， 67（24）： 245108.
[21]	LUO Y X， WANG J M， WANG J Y， et al. Theoretical predictions on elastic stiffness and intrinsic thermal conductivities of yttrium silicates［J］. Journal of the American Ceramic Society， 2014， 97（3）： 945-951.
[22]	JIA Y C， MIGLIO A， GONZE X， et al. Ab-initio study of oxygen vacancy stability in bulk and cerium-doped lutetium oxyorthosilicate［J］. Journal of Luminescence， 2018， 204： 499-505.
[23]	SU F， XU G T， YAO Z H， et al. First-principles calculations of Y-Si-O nanoclusters and effect of Si on microstructure and mechanical properties of 12Cr ODS steel in vacuum sintering system［J］. Metals， 2022， 12（1）： 155.
[24]	JIANG F R， CHENG L F， WEI H J， et al. Hot corrosion behavior of Lu₂SiO₅ and La₂SiO₅ in a molten Na₂SO₄ environment： a first-principles corrosion resistance investigation［J］. Ceramics International， 2019， 45（12）： 15532-15537.
[25]	WANG L F， FAN L C， WANG T， et al. Investigation of phase evolution and Gd occupation in （Lu_1- _x Gd _x ）₂SiO₅ lattice by Rietveld refinement and DFT simulation［J］. Journal of Solid State Chemistry， 2021， 300： 122252.
[26]	ZHU J J， GU M， JIA L C， et al. Structural properties of Lu₂SiO₅ doped with rare-earth elements［J］. Materials Letters， 2019， 256： 126410.
[27]	MIRZAI A， AHADI A. First-principles study of luminescence and electronic properties of Ce-doped Y₂SiO₅ ［J］. The Journal of Chemical Physics， 2023， 159（16）： 164301.
[28]	ZHU J J， GU M， LIU X L， et al. Phase transition and elastic and optical properties of Lu₂SiO₅ ［J］. Optical Materials， 2013， 35（9）： 1659-1663.
[29]	CSONKA G I， PERDEW J P， RUZSINSZKY A， et al. Assessing the performance of recent density functionals for bulk solids［J］. Physical Review B， 2009， 79（15）： 155107.
[30]	LABAT F， BRÉMOND E， CORTONA P， et al. Assessing modern GGA functionals for solids［J］. Journal of Molecular Modeling， 2013， 19（7）： 2791-2796.
[31]	TERENTJEV A V， CONSTANTIN L A， PITARKE J M. Dispersion-corrected PBEsol exchange-correlation functional［J］. Physical Review B， 2018， 98（21）： 214108.
[32]	AYYASAMY M V， BALACHANDRAN P V. Correlation between d-orbital bandwidth and local coordination environment in RE₂SiO₅ compounds with implications in minimizing the coefficient of thermal expansion anisotropy （RE=Sc， Y， La）［J］. AIP Advances， 2022， 12（4）： 045012.
[33]	KÜHNE T D， IANNUZZI M， DEL BEN M， et al. CP2K： an electronic structure and molecular dynamics software package-quickstep： efficient and accurate electronic structure calculations［J］. The Journal of Chemical Physics， 2020， 152（19）： 194103.
[34]	PERDEW J P， RUZSINSZKY A， CSONKA G I， et al. Restoring the density-gradient expansion for exchange in solids and surfaces［J］. Physical Review Letters， 2008， 100（13）： 136406.
[35]	GRIMME S， ANTONY J， EHRLICH S， et al. A consistent and accurate ab initio parametrization of density functional dispersion correction （DFT-D） for the 94 elements H-Pu［J］. The Journal of Chemical Physics， 2010， 132（15）： 154104.
[36]	GRIMME S， EHRLICH S， GOERIGK L. Effect of the damping function in dispersion corrected density functional theory［J］. Journal of Computational Chemistry， 2011， 32（7）： 1456-1465.
[37]	MOMMA K， IZUMI F. VESTA： a three-dimensional visualization system for electronic and structural analysis［J］. Journal of Applied Crystallography， 2008， 41（3）： 653-658.
[38]	LU T， CHEN F W. Multiwfn： a multifunctional wavefunction analyzer［J］. Journal of Computational Chemistry， 2012， 33（5）： 580-592.
[39]	LU T. A comprehensive electron wavefunction analysis toolbox for chemists， Multiwfn［J］. The Journal of Chemical Physics， 2024， 161（8）： 082503.
[40]	WANG J G， TIAN S J， LI G B， et al. Preparation and X-ray characterization of low-temperature phases of R₂SiO₅ （R=rare earth elements）［J］. Materials Research Bulletin， 2001， 36（10）： 1855-1861.
[41]	DENAULT K A， BRGOCH J， KLOSS S D， et al. Average and local structure， Debye temperature， and structural rigidity in some oxide compounds related to phosphor hosts［J］. ACS Applied Materials & Interfaces， 2015， 7（13）： 7264-7272.
[42]	RODEWALD U C， ZHENG L， HEYING B， et al. Rare earth site preference in the doped laser host material Sc₂SiO₅： a single-crystal X-Ray study［J］. Zeitschrift für Naturforschung B， 2012， 67： 113.
[43]	FUKUDA K， IWATA T， CHAMPION E. Crystal structure of lanthanum oxyorthosilicate， La₂SiO₅ ［J］. Powder Diffraction， 2006， 21（4）： 300-303.
[44]	ALIZADEH Y， WELLS J P R， REID M F， et al. Laser site-selective spectroscopy of Nd³⁺-doped Y₂SiO₅ ［J］. Journal of Luminescence， 2021， 234： 117959.
[45]	DENOYER A， LÉVESQUE Y， JANDL S， et al. Cooperative emission study in ytterbium-doped Y₂SiO₅ ［J］. Journal of Luminescence， 2008， 128（9）： 1389-1393.
[46]	MANSUY C， LEROUX F， MAHIOU R， et al. Preferential site substitution in sol-gel derived Eu³⁺ doped Lu₂SiO₅： a combined study by X-ray absorption and luminescence spectroscopies［J］. Journal of Materials Chemistry， 2005， 15（38）： 4129-4135.
[47]	PAULING L. The nature of the chemical bond［M］. New York： Cornell University Press， 1960.
[48]	SHANNON R D. Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides［J］. Acta Crystallographica Section A， 1976， 32（5）： 751-767.

Structure	Method	a/Å	b/Å	c/Å	β/（°）	V/Å³
X1-type	Exp. ^［40］	9.014	6.928	6.643	106.68	397.38
	Cal.	9.045	6.863	6.676	106.32	397.72
	Cal. （DFT-D3）	8.978	6.832	6.642	106.35	390.88
X2-type	Exp. ^［41］	14.406	6.728	10.421	122.19	854.75
	Cal.	14.426	6.734	10.383	122.13	854.21
	Cal. （DFT-D3）	14.381	6.682	10.319	122.21	839.03

Structure	Method	a/Å	b/Å	c/Å	β/（°）	V/Å³
X1-type	Exp. ^［40］	9.014	6.928	6.643	106.68	397.38
	Cal.	9.045	6.863	6.676	106.32	397.72
	Cal. （DFT-D3）	8.978	6.832	6.642	106.35	390.88
X2-type	Exp. ^［41］	14.406	6.728	10.421	122.19	854.75
	Cal.	14.426	6.734	10.383	122.13	854.21
	Cal. （DFT-D3）	14.381	6.682	10.319	122.21	839.03

Method	Space group	Sc₂SiO₅	Y₂SiO₅	La₂SiO₅
Only PBEsol	X1	0	0	0
Only PBEsol	X2	-57.14	-51.70	+223.13
PBEsol+D3（BJ）	X1	0	0	0
PBEsol+D3（BJ）	X2	+32.65	+57.14	+306.67

Method	Space group	Sc₂SiO₅	Y₂SiO₅	La₂SiO₅
Only PBEsol	X1	0	0	0
Only PBEsol	X2	-57.14	-51.70	+223.13
PBEsol+D3（BJ）	X1	0	0	0
PBEsol+D3（BJ）	X2	+32.65	+57.14	+306.67

Structure	Compound	Doped site	a/Å	b/Å	c/Å	β/（°）	V/Å³	Total energy （Hartree）
X1-type	La-doped	Y1	9.343	6.990	6.861	109.20	423.15	-617.673 19
	La-doped	Y2	8.874	7.620	6.692	108.66	428.72	-617.623 42
	Sc-doped	Y1	8.777	6.542	6.450	97.67	367.08	-677.461 93
	Sc-doped	Y2	8.803	6.701	6.438	106.15	364.78	-677.469 44
	Undoped	—	8.978	6.832	6.642	106.35	390.88	-644.210 96
X2-type	La-doped	Y1	14.589	6.765	10.753	122.28	897.13	-1 235.292 93
	La-doped	Y2	14.485	6.891	10.567	121.67	898.46	-1 235.186 85
	Sc-doped	Y1	14.100	6.549	9.934	121.69	780.58	-1 354.845 03
	Sc-doped	Y2	14.002	6.511	10.042	122.23	774.48	-1 354.978 20
	Undoped	—	14.381	6.682	10.319	122.21	839.03	-1 288.404 53

Theoretical Studies on the Structural Stability and Doping Effects of RE₂SiO₅ (RE=Sc, Y, La)

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Structure	Y site	La-doping	Sc-doping
X1-Y₂SiO₅	Y1	0	0
X1-Y₂SiO₅	Y2	+338.58	-51.09
X2-Y₂SiO₅	Y1	0	0
X2-Y₂SiO₅	Y2	+364.02	-452.97

Structure	RE³⁺	Y1 site	Y2 site
X1-type	Y	0.779	0.696
	La	0.881	0.797
	Sc	0.630^*	0.630^*
X2-type	Y	0.696	0.652
	La	0.797	0.748
	Sc	0.630^*	0.540

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