Synthesis, Crystal Structure, and Electrical Conductivity of Pd-intercalated NbSe2

doi:10.15541/jim20190125

Abstract

Abstract:

New intercalated compounds Pd_xNbSe₂ (x=0-0.17) were synthesized via solid-state reaction. They possess the parent structure of 2H-NbSe₂ and crystalize in the hexagonal space group of P6₃/mmc. The intercalated Pd occupies the octahedral position in the van der Waals gaps of 2H-NbSe₂. Unit cell parameter c increases linearly with the Pd content, while a is nearly unchanged. The lattice parameter of Pd_0.17NbSe₂ (a=b=0.34611(2) nm, c= 1.27004(11) nm) is identified by single crystal X-ray diffraction. The intercalated Pd stabilizes the crystal structure of NbSe₂ by connecting the adjacent Nb-Se layers with [PdSe₆] octahedra and leads to the enhanced thermostability in air. Temperature dependence of electric resistivity reveals that the residual resistivity ratio of Pd_xNbSe₂ monotonically decreases with addition of the intercalated Pd content. The decreased superconducting critical temperature of Pd_xNbSe₂ indicates the suppression effect of Pd intercalation on the superconductivity in the host NbSe₂.

Key words: Pd_xNbSe₂, transition metal dichalcogenide, crystal structure, superconducting

CLC Number:

O782

HUANG Chong,ZHAO Wei,WANG Dong,BU Kejun,WANG Sishun,HUANG Fuqiang. Synthesis, Crystal Structure, and Electrical Conductivity of Pd-intercalated NbSe₂[J]. Journal of Inorganic Materials, 2020, 35(4): 505-510.

Figures/Tables 11

References 24

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Chemical formula	Pd_0.17NbSe₂
M_r/(g∙mol^-1)	269.03
Crystal system	Hexagonal, P6₃/mmc
a, c/nm	0.34611(2), 1.27004(11)
V/nm³	0.13176(2)
Z	2
Radiation type	Mo Kα, λ=0.071073 nm
Crystal color	Black
ρ_c/(g∙cm^-3)	6.781
µ/mm^-1	32.93
Crystal size/mm³	0.01×0.01×0.003
Diffractometer	Bruker D8 QUEST
T_min, T_max	0.494, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	1480, 121, 103
R_int	0.053
(sinθ/λ)_max/nm^-1	7.55
R₁, wR₂, S^a	0.019, 0.035, 1.14
No. of reflections	121
No. of parameters	9

Chemical formula	Pd_0.17NbSe₂
M_r/(g∙mol^-1)	269.03
Crystal system	Hexagonal, P6₃/mmc
a, c/nm	0.34611(2), 1.27004(11)
V/nm³	0.13176(2)
Z	2
Radiation type	Mo Kα, λ=0.071073 nm
Crystal color	Black
ρ_c/(g∙cm^-3)	6.781
µ/mm^-1	32.93
Crystal size/mm³	0.01×0.01×0.003
Diffractometer	Bruker D8 QUEST
T_min, T_max	0.494, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	1480, 121, 103
R_int	0.053
(sinθ/λ)_max/nm^-1	7.55
R₁, wR₂, S^a	0.019, 0.035, 1.14
No. of reflections	121
No. of parameters	9

Atom	Wyck. Site	x	y	z	U_iso* or U_eq/nm²	Occ.
Nb	2b	0	1	1/4	0.000075(2)	1
Se	4f	1/3	2/3	0.38104(5)	0.0000736(17)	1
Pd	2a	0	1	1/2	0.000059(11)	0.171(3)

Atom	Wyck. Site	x	y	z	U_iso* or U_eq/nm²	Occ.
Nb	2b	0	1	1/4	0.000075(2)	1
Se	4f	1/3	2/3	0.38104(5)	0.0000736(17)	1
Pd	2a	0	1	1/2	0.000059(11)	0.171(3)

	U₁₁/nm²	U₂₂/nm²	U₃₃/nm²	U₁₂/nm²
Nb	0.000074(3)	0.000074(3)	0.000075(4)	0.0000372(13)
S	0.000064(2)	0.000064(2)	0.000094(3)	0.0000318(10)
Pd	0.000062(13)	0.000062(13)	0.000052(19)	0.000031(7)

Synthesis, Crystal Structure, and Electrical Conductivity of Pd-intercalated NbSe₂

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Figures/Tables 11

References 24

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Bond	Distance/nm	Bond	Distance/nm
Nb1—Se2ⁱ	0.26006(4)	Se2—Pd3^viii	0.25051(4)
Nb1—Se2ⁱⁱ	0.26006(4)	Se2—Nb1^viii	0.26006(4)
Nb1—Se2ⁱⁱⁱ	0.26006(4)	Se2—Nb1^vii	0.26006(4)
Nb1—Se2^iv	0.26006(4)	Pd3—Se2^ix	0.25051(4)
Nb1—Se2	0.26006(4)	Pd3—Se2^iv	0.25051(4)
Nb1—Se2^v	0.26006(4)	Pd3—Se2^x	0.25051(4)
Nb1—Pd3^vi	0.31751(3)	Pd3—Se2ⁱ	0.25051(4)
Nb1—Pd3	0.31751(3)	Pd3—Se2^xi	0.25051(4)
Se2—Pd3^vii	0.25051(4)	Pd3—Nb1^xi	0.31751(3)
Se2—Pd3	0.25051(4)
Bond	Angle/(°)	Bond	Angle/(°)
Se2ⁱ—Nb1—Se2ⁱⁱ	134.813 (8)	Pd3^viii—Se2—Nb1	133.822 (3)
Se2ⁱ—Nb1—Se2ⁱⁱⁱ	79.58 (2)	Nb1^viii—Se2—Nb1	83.434 (16)
Se2ⁱⁱ—Nb1—Se2ⁱⁱⁱ	83.434 (16)	Pd3^vii—Se2—Nb1^vii	76.881 (6)
Se2ⁱ—Nb1—Se2^iv	83.434 (16)	Pd3—Se2—Nb1^vii	133.822 (3)
Se2ⁱⁱ—Nb1—Se2^iv	79.58 (2)	Pd3^viii—Se2—Nb1^vii	133.822 (3)
Se2ⁱⁱⁱ—Nb1—Se2^iv	134.813 (7)	Nb1^viii—Se2—Nb1^vii	83.434 (16)
Se2ⁱ—Nb1—Se2	83.433 (16)	Nb1—Se2—Nb1^vii	83.434 (16)
Se2ⁱⁱ—Nb1—Se2	134.812 (7)	Se2—Pd3—Se2^ix	92.612 (17)
Se2ⁱⁱⁱ—Nb1—Se2	134.812 (8)	Se2—Pd3—Se2^iv	87.388 (17)
Se2^iv—Nb1—Se2	83.433 (16)	Se2^ix—Pd3—Se2^iv	180.0
Se2ⁱ—Nb1—Se2^v	134.812 (8)	Se2—Pd3—Se2^x	92.612 (17)
Se2ⁱⁱ—Nb1—Se2^v	83.434 (16)	Se2^ix—Pd3—Se2^x	87.388 (17)
Se2ⁱⁱⁱ—Nb1—Se2^v	83.434 (16)	Se2^iv—Pd3—Se2^x	92.612 (17)
Bond	Angle/(°)	Bond	Angle/(°)
Se2^iv—Nb1—Se2^v	134.812 (8)	Se2—Pd3—Se2ⁱ	87.388 (17)
Se2—Nb1—Se2^v	79.58 (2)	Se2^ix—Pd3—Se2ⁱ	92.612 (17)
Se2ⁱ—Nb1—Pd3^vi	129.790 (11)	Se2^iv—Pd3—Se2ⁱ	87.388 (17)
Se2ⁱⁱ—Nb1—Pd3^vi	50.210 (11)	Se2^x—Pd3—Se2ⁱ	180.0
Se2ⁱⁱⁱ—Nb1—Pd3^vi	50.210 (11)	Se2—Pd3—Se2^xi	180.0
Se2^iv—Nb1—Pd3^vi	129.790 (11)	Se2^ix—Pd3—Se2^xi	87.388 (17)
Se2—Nb1—Pd3^vi	129.790 (11)	Se2^iv—Pd3—Se2^xi	92.612 (17)
Se2^v—Nb1—Pd3^vi	50.210 (11)	Se2^x—Pd3—Se2^xi	87.388 (17)
Se2ⁱ—Nb1—Pd3	50.210 (11)	Se2ⁱ—Pd3—Se2^xi	92.612 (17)
Se2ⁱⁱ—Nb1—Pd3	129.790 (11)	Se2—Pd3—Nb1	52.909 (12)
Se2ⁱⁱⁱ—Nb1—Pd3	129.790 (11)	Se2^ix—Pd3—Nb1	127.092 (12)
Se2^iv—Nb1—Pd3	50.210 (11)	Se2^iv—Pd3—Nb1	52.908 (12)
Se2—Nb1—Pd3	50.210 (11)	Se2^x—Pd3—Nb1	127.092 (12)
Se2^v—Nb1—Pd3	129.790 (11)	Se2ⁱ—Pd3—Nb1	52.908 (12)
Pd3^vi—Nb1—Pd3	180.0	Se2^xi—Pd3—Nb1	127.091 (12)
Pd3^vii—Se2—Pd3	87.388 (17)	Se2—Pd3—Nb1^xi	127.091 (12)
Pd3^vii—Se2—Pd3^viii	87.388 (17)	Se2^ix—Pd3—Nb1^xi	52.908 (12)
Pd3—Se2—Pd3^viii	87.388 (17)	Se2^iv—Pd3—Nb1^xi	127.092 (12)
Pd3^vii—Se2—Nb1^viii	133.822 (2)	Se2^x—Pd3—Nb1^xi	52.908 (12)
Pd3—Se2—Nb1^viii	133.822 (3)	Se2ⁱ—Pd3—Nb1^xi	127.092 (12)
Pd3^viii—Se2—Nb1^viii	76.881 (6)	Se2^xi—Pd3—Nb1^xi	52.909 (12)
Pd3^vii—Se2—Nb1	133.822 (2)	Nb1—Pd3—Nb1^xi	180.0
Pd3—Se2—Nb1	76.881 (6)

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