Lingyong Zeng, Huawei Zhou, Hong Du, Ruidan Zhong, Ruixin Guo, Shu Guo, Wanzhen Su, Kuan Li, Chao Zhang, Peifeng Yu, Huixia Luo
Lingyong Zeng, Huawei Zhou, Hong Du, Ruidan Zhong, Ruixin Guo, Shu Guo, Wanzhen Su, Kuan Li, Chao Zhang, Peifeng Yu, Huixia Luo
Lingyong Zeng, Huawei Zhou, Hong Du, Ruidan Zhong, Ruixin Guo, Shu Guo, Wanzhen Su, Kuan Li, Chao Zhang, Peifeng Yu, Huixia Luo
Lingyong Zenga, #, Huawei Zhou a, #, Hong Dub, Ruidan Zhongb, Ruixin Guoc,d, Shu
Guoc,d, Wanzhen Sua, Kuan Lia, Chao Zhanga, Peifeng Yua, Huixia Luoa*
a
School of Materials Science and Engineering, State Key Laboratory of
Optoelectronic Materials and Technologies, Key Lab of Polymer Composite &
Functional Materials, Guangzhou Key Laboratory of Flexible Electronic Materials
and Wearable Devices, Sun Yat-Sen University, No. 135, Xingang Xi Road,
Guangzhou, 510275, P. R. China.
b
Tsung-Dao Lee institute , Shanghai Jiao Tong University, Shanghai, 200240, P. R.
China.
c
Shenzhen Institute for Quantum Science and Engineering, Southern University of
Science and Technology, Shenzhen 518055, China.
d
International Quantum Academy, Shenzhen 518048, China.
#
These authors contributed equally to this work.
Corresponding author’ email address: [email protected]; complete details
*
Experimental
The polycrystalline samples V3-xCoxSi (0 ≤ x ≤ 0.30) were synthesized through an
arc-melting method. Stoichiometric mixtures of V (99.5%, Aladdin), Co (99.5%, Alfa
Aesar), and Si (99.99%, Macklin) powders were well-ground together, pressed into a
cylinder and placed into a water-cooled melting furnace. They were arc melted in an
argon atmosphere and rapidly cooled. The samples were subsequently annealed at 1000
o
C under a vacuum. The weight loss during the melting process is almost negligible.
Powder x-ray diffraction (PXRD) collected the phase composition and lattice
structure information from powdered samples at room temperature. We analyze the
PXRD data with the Rietveld refinement model of the Fullprof suite software.
Microstructural characterization of the samples was conducted by scanning electron
microscope (SEM, EVO MA10) with energy dispersive spectroscopy (EDS).
Temperature-dependent resistivity (four-point probe), zero-field-cooling (ZFC)
magnetic susceptibility, and heat capacity were determined through the physical
property measurement system (PPMS, DynaCool, Quantum Design, Inc).
alloys with space group Pm-3n. (b) PXRD pattern of V3-xCoxSi alloys. (c) Cobalt-doped content
Element ratio V Si Co
Sample
0.25).
temperature range of 8-18 K. (b) cobalt content dependent on the RRR and ∆Tc values. (c)
Magnetic characterization of V3-xCoxSi (0 ≤ x ≤ 0.30) alloys with ZFC model. (d) the
∗
μ0 H𝑐1 (0)(1-(T/Tc )2 ). Due to demagnetization, the estimated value μ0Hc1(0) should be
∗
modified using the formula μ0Hc1(0) = μ0 H𝑐1 (0) /(1-N), where the demagnetization
factor N of V2.975Co0.025Si and V3Si is 0.31 and 0.43, respectively. The N value has been
used to correct the magnetic susceptibility data. The modified lower critical field
μ0Hc1(0) of V2.975Co0.025Si and V3Si is 120.0 mT and 138.0 mT, respectively. All the
superconducting parameters are summarized in Table 3. It can be seen that with the
increase of cobalt content, the μ0Hc1(0) also gradually decreases.
Table 2. The geometric parameters of the susceptibility test sample.
Geometric
2b 2a 2c Theoretical Actual
parameters
(mm) (mm) (mm) N value N value
Samples
the M(H) curves at different temperatures. The bottom left corner inset shows the M-Mfit as a
model for V3Si, V2.975Co0.025Si, and V2.96Co0.04Si are 34.89 T, 34.29 T, and 32.90 T,
respectively. Additionally, we fit the Pauli limiting field (μ0HP) of V3-xCoxSi (0 ≤ x ≤
0.30) alloys by the formula μ0HP = 1.85*Tc, the values are present in Table 3. The
experimentally estimated μ0Hc2(0) values for all samples are very close to the Pauli
limiting field. Furthermore, we can also obtain the μ0Hc2(0) value of 30.57 T, 30.03 T,
and 28.92 T for V3-xCoxSi (x = 0, 0.025, 0.04) alloys fitted with GL formula:
1−(𝑇/𝑇 )2
μ0 Hc2 (T) = μ0 Hc2 (0) ∗ 1+(𝑇/𝑇𝑐)2 . As displayed in Fig. 5, the distribution of spots
𝑐
obeys the function nicely. For comparison, we also calculated the μ0Hc2(0) value of V3-
xCoxSi (0.08 ≤ x ≤ 0.30) samples. There are two superconducting transitions in the
V2.7Co0.3Si sample, possibly due to inhomogeneity. It can be seen that with the increase
of cobalt content, the μ0Hc2(0) also gradually decreases, except for the V2.7Co0.3Si alloy.
Fig. 5 The upper critical fields of V3-xCoxSi (0 ≤ x ≤ 0.30) samples. The top right inset shows
compound.
As a comparison, we also performed the heat capacity measurement on the sample
with high cobalt content. Fig. 6(c) displays the Cp/T(T) curves of V2.8Co0.2Si down to
2 K at 0 T and 5 T fields. However, two specific heat jumps can be observed in Fig.
6(c), one of which has a minor anomaly in heat capacity data. The clear anomaly jump
is around 12.3 K at 0 T field, which is consistent with the Tc in Table 1. Meanwhile, the
normal-state specific heat data also fitted with the following formula: Cp/T = γ + βT2,
giving γ = 17.61 mJ/mol/K2 and β = 0.06 mJ/mol/k4. Fig. 6(b) shows the Cel/T(T) curves
at a temperature between 2 - 20 K under 0 T. Using the standard equal-area entropy
construction method, and we can determine ∆Cel/γTc = 1.22, which is slightly smaller
than the BCS weak coupling limit (1.43), revealing its superconducting nature. Based
on the above parameters, the ΘD and λep are calculated to be 506 K and 0.72, respectively.
The inset in Fig. 6(c) displays the Cp/T(T2) data at low temperatures. Comparing the
heat capacity data under the applied magnetic field of 0 T and 5 T, the external magnetic
field will suppress the Tc, corresponding to the specific heat peak of the
superconducting transition moving to a lower temperature. However, the minor
anomaly in Cp/T(T2) curves around 8.5 K did not change under an external magnetic
field of 5 T, which can rule out superconductivity and magnetic transitions. Interestingly,
this minor anomaly of 8.5 K in the V2.8Co0.2Si heat capacity coincides with the T* in
dꭓ/dT curves. We speculated that a structural phase transition may have occurred at T*
in the high-content cobalt-doping samples (x ≥ 0.15). Previous studies have shown a
martensitic cubic to tetragonal phase transition at the temperature of about 18.9 K in
the V3Si compound [16-19]. Besides, the hydrostatic pressure will gradually suppress
this martensitic phase transition [36,37]. Cobalt-doping reduces the lattice parameters,
which may be equivalent to applying external pressure. And the T* decreases with
increasing cobalt content (see Fig. 2(d)). The V2.8Co0.2Si sample may have undergone
a martensitic transformation at about 8.5 K. Furthermore, an in-depth study is warranted
to understand the present experimental findings.
Fig. 6 (a) Cp/T(T2) curves of V2.975Co0.025Si alloy without magnetic field. (b) Temperature
dependence of the electronic specific heat Cel of V2.975Co0.025Si alloy. (c) Cp/T(T2) curves of
V2.8Co0.2Si alloy at 0 T and 5 T field. The inset shows the Cp/T(T2) curves at low temperatures.
(d) Temperature dependence of the electronic specific heat Cel of V2.8Co0.2Si alloy.
Fig. 7 plots the Tc of V3Si1-xGax [30], V3Si1-xAlx [30], and V3-xCoxSi A15 structure
superconductors as a function of the electron/atom (e/a) ratio. Whether doping
gallium/aluminum on silicon or cobalt on vanadium will decrease the Tc of V3Si, when
considering the e/a ratio in the V3Si system, it can be found that the substitution of
gallium/aluminum for silicon reduces the e/a ratio and the substitution of cobalt for
vanadium increases the e/a ratio. We also illustrate the trend lines of the Tc of transition
metals and their alloys in crystalline form and as amorphous vapor-deposited films for
comparison [38]. It is often referred to as the Matthias rule, which shows the Tc
maximum occurs at around 4.7 e/a for transition metals, even though the maximum is
much broader than simple crystalline superconductors. As the e/a ratio increases, the Tc
variation trend of V3Si is as pronounced as in crystalline alloys and monotonically
follows the trend observed for amorphous superconductors. The V3Si has the maximum
Tc with electron count e/a = 4.7, which is the essential feature of the Matthias rule,
indicating that chemical doping makes it challenging to increase the Tc of V3Si bulk.
Furthermore, according to the rigid band model and the electronic structure calculations
of V3Si [39], cobalt doping at the vanadium site will increase the number of VECs in
the unit cell, resulting in the increase of the Fermi energy EF and the decrease of N(EF).
Fig. 7 valence electron count per atom dependency of the Tc of V3Si1-xAlx [30], V3Si1-xGax [30],
Conclusion
We have synthesized V3-xCoxSi alloys with x up to 0.3 by an arc melting method
and subsequent annealing. According to PXRD refinement data, the increase of cobalt-
doped content decreases the lattice parameter. Resistivity and susceptibility
measurements show an almost linear decrease in Tc with increasing cobalt content in
the V3-xCoxSi system. The V3Si has the maximum Tc with electron count e/a = 4.7,
which is an essential feature of the Matthias rule. The relationship between Tc and e/a
ratio in the V3-xCoxSi system is almost linear. The RRR values indicate that cobalt
doping introduces disorder in the V3-xCoxSi system, and the following leads to a
suppression of the critical temperature Tc. Further, with higher Co-doped content, V3-
xCoxSi (0.15 ≤ x ≤ 0.30) alloys may have superconducting and structural phase
transitions. The fitted data show that cobalt doping also reduces the critical field of the
V3-xCoxSi system. Type-II superconductivity is demonstrated on all V3-xCoxSi samples.
Acknowledgments
This work is supported by the National Natural Science Foundation of China (11922415,
12274471, 22205091), Guangdong Basic and Applied Basic Research Foundation
(2022A1515011168, 2019A1515011718, 2019A1515011337), the fund of State Key
Laboratory of Optoelectronic Materials and Technologies (OEMT-2022-ZRC-02), the
Key Research & Development Program of Guangdong Province, China
(2019B110209003), and the Pearl River Scholarship Program of Guangdong Province
Universities and Colleges (20191001).
References
[1] H Hosono, A Yamamoto, H Hiramatsu and Y W Ma 2018 Mater. Today 21
278-302
[2] G R Stewart 2015 Physica. C 514 28-35
[3] L R Testardi 1971 Phys. Rev. B 3 95-106
[4] R Viswanathan and H Luo 1971 Solid State Commun. (USA) 9 1733-36
[5] M Dayan, A M Goldman, C C Huang, M C Chiang and L E Toth 1979 Phys.
Rev. Lett. 42 335-38
[6] J R Gavaler, M A Janocko and C K Jones 1974 J. Appl. Phys. (USA) 45
3009-13
[7] L R Testardi, J H Wernick and W A Royer 1974 Solid State Commun. (USA)
15 1-4
[8] M Kim, C Z Wang and K M Ho 2019 Phys. Rev. B 99 235423
[9] J Muller 1980 Rep. Prog. Phys. (UK) 43 641-87
[10] J W Blezius and J P Carbotte 1986 Phys. Rev. B 33 3509-11
[11] M N Khlopkin 1999 JETP. Lett+ 69 26-30
[12] V G Kogan, C Martin and R Prozorov 2009 Phys. Rev. B 80 014507
[13] L R Testardi, J M Poate and H J Levinstein 1977 Phys. Rev. B, Solid State
(USA) 15 2570-80
[14] F M Muuller, D H Lowndes, Y K Chang, A J Arko, and R S List 1992 Phys.
Rev. Lett 68 3928-31
[15] W D Wu, A Keren, L P Le, G M Luke, B J Sternlieb, Y J Uemura, D C
Johnston, B K Cho and P Gehring 1994 Hyperfine Interact. (Switzerland) 86 615-21
[16] R Mailfert, B W Batterman and J J Hanak 1967 Phys. Lett. A 24 315-16
[17] A Sauer, D A Zocco, A H Said, R Heid, A Bohmer and F Weber 2019 Phys.
Rev. B 99 134511
[18] H M Tütüncü, H Y Uzunok, G P Srivastava, V Özdemir and G Uǧur 2018
Intermetallics 96 25-32
[19] R Viswanathan and D C Johnston 1976 Phys. Rev. B 13 2877-79
[20] G Shirane, J D Axe and R J Birgeneau 1971 Solid State Commun. (USA) 9
397-400
[21] M Yethiraj 2002 Appl. Phys. A-Mater 74 S1210-S12
[22] K Cho, M Konczykowski, S Ghimire, M A Tanatar, L L Wang, V G Kogan
and R Prozorov 2022 Phys. Rev. B 105 024506
[23] J Nagamatsu, N Nakagawa, T Muranaka, Y Zenitani and J Akimitsu 2001
Nature 410 63-64
[24] T D Vethaak, F Gustavo, T Farjot, T Kubart, P Gergaud, S L Zhang, F
Lefloch and F Nemouchi 2021 Microelectron. Eng. 244-246 111570
[25] W Zhang, A T Bollinger, R Li, K Kisslinger, X Tong, M Liu and C T Black
2021 Sci. Rep. 11 2358
[26] L Y Zeng, X W Hu, N N Wang, J P Sun, P T Yang, M Boubeche, S J Luo,
Y Y He, J G Cheng, D X Yao and H X Luo 2022 J. Phys. Chem. Lett. 13 2442-51
[27] L Y Zeng, Y Ji, D P Yu, S Guo, Y Y He, K Li, Y H Huang, C Zhang, P F
Yu, S J Luo, H C Wang and H X Luo 2022 J. Phys. Chem. C 126 3705-12
[28] B A Hatt, J K R Page and V G Rivlin 1973 J. Low Temp. Phys. 10 285-98
[29] B He, C Dong, L M Zeng, H R Liu, L H Yang and H Chen 2008 Supercond.
Sci. Tech. 21 035004
[30] G Otto 1969 Zeitschrift für Physik 218 52-55
[31] C Wang, Y K Li, Z W Zhu, S Jiang, X Lin, Y K Luo. S Chi, L J Li, Z Ren,
M He, H Chen, Y T Wang, Q Tao, G H Cao and Z A Xu 2009 Phys. Rev. B 79
051521
[32] P Yuan, J Han, P Cheng, R Ma, Q Xiao, J Ge, Z Feng, S Cao, J Zhang, W
Lu and F Chen 2021 J. Phys.: Condens. Mater 33 335601
[33] S Elizabeth, A Anand, S V Bhat, S V Subramanyam and H L Bhat 1999
Solid State Commun 109 333-38
[34] J Prakash, S J Singh, S Patnaik and A K Ganguli 2009 Solid State Commun
149 181-83
[35] R Prozorov and V G Kogan 2018 Phys. Rev. Applied 10 014030
[36] C W Chu and L R Testardi 1974 Phys. Rev. Lett. 32 766-69
[37] L R Testardi 1975 Rev. Mod. Phys. 47 637-48
[38] M M Collver and R H Hammond 1979 Phys. Rev. B, Condens. Matter
(USA) 19 525-26
[39] B M Klein, L L Boyer, D A Papaconstantopoulos and L F Mattheiss 1978
Phys. Rev. B 18 6411-38