Ph.D.

Registration Report
on

Synthesis and Study of Layered Metal

Chalcogenides and Antimonides

Submitted by

SUBHAM NAIK
ROLL NO. – 516CY1013

Under the Guidance of

Dr. Saroj L. Samal

Department of Chemistry
National Institute of Technology
Rourkela – 769008, Odisha, India
 CONTENTS

Subject Page No.

1. Abstract 3

2. Part I: Layered Metal Chalcogenides 4-13

o Introduction 4-5

o Research Objectives 5

o Materials and Methods 6

o Characterisation 6-7

o Results and Discussion 7-12

o Summary and Future work 13

3. Part II: Layered Metal Antimonides 14-16

o Introduction 14

o Research Objectives 15
o Synthesis and Characterisation 15

o Future work 16

4. References 16-20

5. Road map 21

6. Course work 22

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ABSTRACT
Layered materials have been widely explored and practically applied in various fields because
of their unique physical and chemical properties. These materials shows anisotropic physical
properties due to weak inter layer interactions. Among various types of layered materials, layered
metal chalcogenides (LMCs) are one of the type, which have potential applications in various
fields, such as superconductivity, electrocatalysis, thermoelectrics, photovoltaics etc.
Particularly, layered Transition Metal Dichalcogenides (LTMDs) with formula MX2 (M:
Transition Metals, X: S, Se, Te) shows exotic properties like superconductivity. For example
NbSe2 is a superconductor with Tc ranging from 5.5-7.5 K. Here in part I: we have synthesized
layered NbSe2 and Sn intercalated NbSe2 compounds. These compounds were characterised
using different characterisation tools and the effect of intercalation on the structural and electrical
properties, especially superconductivity, was studied. It was observed that the superconducting
transition temperature (Tc) of NbSe2 to be around 6.0 K, with Sn intercalation the Tc decreases
in SnxNbSe2. Several other layered ternary compounds, such as FeIn2Se4, FeIn2S4, and CuSbS2
were attempted and most of the compounds form mixture of phases. In part II, we have attempted
to synthesize layered metal antimonides with formula AMnSb2, (A: Ca/ Yb) and characterised
using PXRD and other characterisation tools. These antimonides shows highly anisotropic
electrical properties and magnetic properties from antiferromagnetic (CaMn2Sb2; AFM, TN = 85
K) to ferromagnetic ordering SrMnSb2; FM > 340 K.

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 Part I: Layered Metal Chalcogenides

Introduction

Layered materials have been known since early twentieth century. Till date many types
of layered materials has been discovered. The layered materials shows interesting properties due
to their structure where the layers are comprises of sandwich structures and stacked by weak van
der Waals forces1-3. Weak interaction makes it possible to vary the morphology from multi-layer
to few layers materials which can be of use for suitable applications4-9. The weak van der Waals
forces between layers creates anisotropic properties, the in-plane thermal, electrical and
mechanical properties overtake the out-of-plane properties10such that they can be excellent
materials for various application such as FET11,gas sensor12, photodetectors13-15, and other
applications.

Among various layered compounds, of the layered metal chalcogenides (LMCs) are of
special interest due variety of exotic properties such as superconductivity16, hydrogen
reduction17, thermoelectrics18. These materials are now in the frontline of scientific research for
innovating novel materials for practical applications. The layered transition metal
dichalcogenides (LTMDs) are most popular (MX2, M: Transition metal, X: Chalcogen). In the
layered structure the metal is sandwich between two layers of chalcogens as X-M-X type. The
layers are stacked by weak van der Waal interaction, which is the main factor for the anisotropic
properties. Superconductivity is one of the interesting characteristics of some LTMDs. There are
few reports superconductive layered compounds16-18. One of the most popular superconductor is
NbSe2 which have Superconductive transition temperature around 5.2K to 7.2 K19-24. The
structural details and the crystallographic details of NbSe2 has been reported by M. Marezio et.
al. 25 and A. Meerschaut et. al.26.

There are reports of intercalation in NbSe2 and its effect on the structural and electronic properties
(superconductivity). K. Motizuki et. al. have theoretically studied the effect of intercalation on
structural instability and superconductivity, inferred that donor type intercalant lowers Tc
whereas acceptor type intercalant raises Tc28. There are several other reports where NbSe2 has
been intercalated with alkali metals29-30, transition metals31-33, p-block elements34 and their effect
on structural and physical properties. There are few reports of doping in 2H-NbSe2 till date. Li
et. al. have reported the effect of Ta and Ti doping to the structural and electronic properties in

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NbSe235-36. Despite the fact that 2H-NbSe2 has been considered as a conventional
superconductor and there are many studies on the effect of intercalation on the superconducting
transition temperature of NbSe2, still the key reason behind the variation was stilled under
debate. Interestingly, very recent measurements of Tc in Cu intercalated 2H-NbSe2 showed an S-
shaped suppression of Tc. So study of various intercalation of NbSe2 required to establish a
relationship between the superconducting transition temperature and the intercalation. To
understand the origin of the superconductivity in NbSe2, we have tried to intercalate Sn, V and
W in NbSe2 and studied its effect on Tc.

Research Objectives

1. Synthesis of binary and ternary layered metal chalcogenides.

2. Extensive study of magnetic and transport properties and to understand the underlying
relationship among structure and properties.
3. Understanding of the effect of intercalation on the superconducting transition
temperature of NbSe2.
4. Doping/intercalation of the layered compounds at different sites with suitable elements
to tune these physical properties.
5. Theoretical Calculations (LMTO-ASA) on the selected suitable compounds to
understand the relationship between Fermi surface nesting, superconductivity and
structure.
6. Growth of single crystals of suitable compounds for extensive study.

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Materials and Methods:
Materials:
Niobium powder (~99%); Selenium powder (~99.5%) was purchased from Himedia and
Tin shots (~99.8%), purchased from Sigma, Tungsten Powder (99.5%), Vanadium powder
purchased from SRL. All the materials were kept in nitrogen filled (≤ 0.1 ppm H2O by volume)
glove box and used without further purification. Due to toxic nature of selenium caution should
be taken.

Synthesis of AxNbSe2 (A = Sn, W, V; x = 0, 0.02, 0.04, 0.06):

All the samples were prepared by high temperature solid state reaction method.
Stoichiometric ratios of materials were taken, well grinded and pelletized. The prepared pellets
were evacuated in a quartz tube (~10-3 Torr), sealed under dynamic vacuum, placed in a muffle
furnace and heated up to 700-800 oC for ~15 hrs and then quenched to room temperature. The
product was again grinded, palletized, evacuated, sealed and reheated at the same temperature to
improve the crystallinity and phase. A grey coloured powder was obtained which is used for
characterisation. An excess of selenium powder was taken such that during the reaction process
surplus selenium will evaporate and stick to the inner wall of the quartz tube without changing
the selenium content of the material.

Characterisation:

The XRD pattern of the synthesised powder materials were recorded on a Rigaku Ultima
IV multipurpose X-ray diffractometer using Cu Kα (λ=1.54Å) as source. Field emission scanning
electron microscopy (FESEM) images were acquired using JEOL JSM-6084 LV and NOVA
NANO SEM/FEI Source. DSC study was done with NETZSCH, STA409C instrument under
Argon environment from temperature range 25oC to 1000oC. Magnetic property measurements
were performed with SQUID Magnetometer. The resistivity vs temperature measurement and
field dependent resistivity vs temperature studies also has been done using four probe method.
To support our experimental data we have perform some theoretical calculation. Electronic
Structure Calculations: Self-consistent electronic structure calculations were performed by
means of tight binding linear-muffin-tin-orbital (TB-LMTO) methods within the atomic sphere
approximation (ASA) 37. The radii of the WIGNER-SEITZ spheres were assigned automatically

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 so that the overlapping potentials would be the best possible approximations to the full potential.
The radii were: Nb = 3.066 Å, Se = 2.769 Å, E = 2.929 Å and E1 = 2.060 Å. Two additional
empty spheres were needed subject to 18% overlap restriction between atom centred spheres.
Basis sets of Nb 5s, 5p and 4d; Se 4s, 4p and (4d) (down-folded orbitals in parentheses) were
employed, and the reciprocal space integrations were performed by means of the tetrahedron
method. Scalar relativistic corrections were included. The calculations were carried out at 8 × 8
× 12 k points in the irreducible wedge of the Brillouin zone. For bonding analysis, the energy
contributions of all filled electronic states for selected atom pairs were calculated by the crystal
orbital Hamilton population (COHP method) 38. These were given a weighted integration up to
the Fermi energy (EF) to provide ICOHP data, total Hamilton populations, which are
approximations of relative bond populations. The COHP analyses provide the contributions of
the covalent parts of particular interactions to the total bonding energy of the crystal.

Results and discussion

In an attempt to change Tc, we have tried to intercalate NbSe2 layers with V, W and Sn and
succeeded in case of Sn intercalation. The corresponding PXRD plots has been shown in figure
1. For W and V intercalation, we observed binary VSe2 and WSe2 phases along with NbSe2.
However, for Sn intercalation, we can able to intercalate till 4 mole% and attempt to intercalate
higher percentage lead to segregation of SnSe2 phase.

NbSe2
(a) NbSe (b) W xNbSe2
SnxNbSe2
VxNbSe2
Intensity (cps)
Intensity(cps)

10 20 30 40 50 60 70 80 10 20 30 40 50 60 70 80
Degree(2) Degree (2)

Figure 1: PXRD patterns of (a) SnxNbSe2 (x = 0, 0.04) and (b) MxNbSe2 (M: V, W; x = 0.1).

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 For SnxNbSe2 the X-ray data were collected in the 2θ range of 10-80o using scanning mode
step size of 0.02o. Figure 2 shows the PXRD data of SnxNbSe2 (x = 0.0, 0.02, 0.04, 0.06). The
collected data was matched with the JCPDS Card no: 72-1618. All the peaks were indexed in
hexagonal crystal structure with space group P63/mmc (194). The PXRD patterns of the samples
show a peak shift towards lower angle, as shown in figure 2(b), indicating increase in c lattice
parameter with Sn intercalation.

NbSe2
(a) (b)
Sn0.02NbSe2
Sn0.04NbSe2
Sn0.06NbSe2

Intensity(cps)
Intensity(cts)

Reference

10 20 30 40 50 60 70 80 66 67
2(Degree)
2(Degree)

Figure 2: (a) PXRD patterns of SnxNbSe2 (x=0.02, 0.04, 0.06) (b) showing peak shift in
SnxNbSe2 (x = 0.02, 0.04, 0.06)

The compounds NbSe2 crystallizes in hexagonal crystal structure having space group P63/mmc
(194). It is layered compound in which Nb is bonded to six selenium atoms in trigonal prismatic
geometry and each Se atom bonded to three niobium atoms. The structure of NbSe2 can be

(A) (B)

dintra = 3.3161 Å

d = 2.965 Å
inter

Figure 3: (A) Layered structure of NbSe2, (B) Unit cell of NbSe2 showing the intra and inter
layer distances.

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viewed as Se atoms form HCP arrangement and half of the octahedral voids are filled in such a
way that alternate layers are filled and empty. The intra and inter layer thickness are 3.316 Å and
2.965 Å, respectively. So the layered compound offers space for the intercalation of smaller
cations.

The lattice parameters of SnxNbSe2 (x = 0.0, 0.02, 0.04, 0.06) were refined using the WinXpow
software and are given in table 1. The c-lattice parameter gradually increase with increase in Sn
intercalation, whereas the variation of a-lattice parameter is not significant.

Table 1: Refine Lattice parameters of SnxNbSe2 (x=0.02, 0.04, 0.06).

Refined Cell parameters a(Å) c(Å)

Sample Name
NbSe2 3.4478(6) 12.561(2)
Sn0.02NbSe2 3.4459(3) 12.582(1)
Sn0.04NbSe2 3.4465(3) 12.593(2)
Sn0.06NbSe2 3.4476(6) 12.595(3)

Surface morphology of the compound has been observed by NOVA NANOSEM 450
Field Emission Scanning Electron Microscope and the micrograph shows layered morphology
of the compounds as shown in the figure 4.

Figure 4: FESEM micrograph of (a, b) NbSe2, (c) Sn0.02NbSe2, (d) Sn0.04NbSe2

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 The DSC plot shows a strong exothermic peak around 473 oC which may correspond to the
ordering of NbSe2 phase as shown in figure 5. To check the ordering in the NbSe2, further
reaction are in progress by annealing for longer duration at ~500 oC.

DSC/(mW/mg)
3.5

3.0

2.5
DSC/(mW/mg)

2.0

1.5

1.0

0.5

0.0
o
472.94 C
-0.5
200 400 600 800 1000
o
Temperature( C)

Figure 5: DSC plot of NbSe2

Electric Properties studies:

Figure 6(a) shows the resistivity vs temperature plot of NbSe2 and Sn0.04NbSe2. Both the
compound show metallic type resistivity trend in the normal state. At low temperature a sharp
drop of the resistivity value indicate superconducting state for both the compounds. The
superconducting transition temperature of pure NbSe2 compound was observed to be 6,2 K and
for Sn0.04NbSe2 is 3.1 K. There is drastic change in the superconducting transition temperature
(Tc) value with very small (4 mole %) intercalation of Sn in NbSe2. The origin of such decrease
in Tc is very difficult to rationalize in the present study. However, similar decrease in Tc value
were observed in Cu intercalation to 3 K33. Figure 6(b) shows the resistivity vs temperature plots
at variable applied magnetic field of Sn0.04NbSe2. The superconducting transition temperature
decreases with increase in applied magnetic field as expected in superconductors.

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 (b)
(a)

Figure 6: (a) Resistivity vs Temperature plot of SnxNbSe2 (x = 0, 0.04), (b) Field dependent
Resistivity vs Temperature plot of Sn0.04NbSe2

Magnetic Properties:

Figure 7 shows the temperature dependence of magnetization of SnxNbSe2. The diamagnetic

behaviour at low temperature for x = 0, 0.02 and 0.04 clearly indicate superconducting state. The
onset of the diamagnetism shifts towards lower temperature with increase in Sn intercalation
which corroborate the resistivity data. This suggest that Sn intercalation disrupt the
superconducting state of the NbSe2.

Figure 7: Temperature dependent zero field cooled (dc field 50 Oe) magnetization for SnxNbSe2
(0 ≤ x ≤ 0.04) revealing superconducting transition.

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 Theoretical calculations:

Figure 8. Results of LMTO-ASA calculations for NbSe2. (a) COHP of NbSe2 (b) Total densities
of states (DOS). Partial projections of orbital DOS are shown for (c) Nb 5s, 5p and 4d (d) Se 4s
and 4p.

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Figure 8 shows the COHP (a) and DOS (b, c, d) of NbSe2. Finite density of state at Fermi level
indicate the metallic ground state of NbSe2. 4d orbital of Nb and 4p orbital of Se largely
contributes at the Fermi level. The crystal orbital Hamiltonian population (COHP) is a tool in
the LMTO software package to investigate the covalent contribution of a chemical bond. The
COHP plot (Figure 8(a)) shows that all the bonding states are completely occupied.

Summary and Future Work:

In this report, we have synthesized SnxNbSe2 (x = 0, 0.02, 0.04, 0.06) via high
temperature solid state route using elemental forms of constituting elements and characterized
with different analytical tools. NbSe2 shows superconducting transition temperature (Tc) at 6.3
K. On Sn intercalation the Tc decreases. We have successfully intercalate up to 4 mole% and the
Tc shows a decreasing trend as we increase the intercalant concentration. We have performed
theoretical study to understand the electronic structure of the compound using LMTO-ASA
software. Intercalation of NbSe2 with electron poor and electron rich elements are in progress to
establish correlation and understand the relationship between the intercalation and
superconductivity in these layered NbSe2 compounds.
We have attempted to synthesize some ternary layered compounds, FeIn2Se4 and FeIn2S4,
but unable to get a pure phase compound. Although the PXRD data of FeIn2Se4 (Figure 9) seems
to be single phase, however, due to insufficient data and lack of literature details we were unable
to identify the peaks. Further we are trying to grow single crystals but not succeeded till now. In
future we are planning to synthesize pure phase compounds and study the effect of
doping/intercalation on different structural and physical properties and their application in
various fields.

Figure 9. PXRD pattern of FeIn2Se4 and FeIn2S4.

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 Part II: Layered Metal Antimonides

Introduction:
Another class of layered compounds are Layered Metal Antimonides (LMAs). LMAs are
new class in the layered material family. Metal antimonides are known since 1970s39 and shows
peculiar properties. These antimonides are of AMSb2 (A: Divalent Cation; M: Transition metals)
or AM2Sb2 types materials, the divalent cations can be alkaline earth metals41-50, transition
metals39,40 or rare earth metals51-53. These types of antimonide compounds are very interesting
due to their specific magnetic properties from antiferromagnetic (CaMn2Sb2 (AFM,TN = 85 K))
to ferromagnetic ordering SrMnSb2 (FM > 340 K).

In recent few years alkaline earth metal based antimonides have been in the line of interest
for researchers. J. B. He et. al. have prepared the single crystals of CaMnSb2 and studied the
magnetic and magneto-transport properties. They found that CaMnSb2 orders
antiferromagnetically below TN = 302 K and exhibits highly anisotropic magnetic and electrical
transport properties44. J. Liu et. al. have reported BaMnSb2 as a promising platform for seeking
novel exotic properties of massless Dirac fermions in low dimensions42. H. J. Park et. al. have
reported optical spectroscopic study of SrMnSb2 which is a low-carrier-density metal48. J.Y. Liu
et. al. report a new type of magnetic topological semimetal phase arising from 2D Sb layers in
Sr1-yMn1-zSb2 (y,z < 0.1) whose relativistic fermion behaviour47.

We are focused on AMnSb2 (A = Ca, Sr and Ba) due to its anisotropic magnetic and
electric properties. This compound was first synthesized by E. Brechtel, they have reported
detailed crystallographic studies on BaZnSb2, BaCdSb2, BaZnBi2, SrCdBi2 and BaCdBi2. These
materials crystallize in tetragonal system (S.G. I4/mmm) with SrZnBi2 structure54.

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Research Objectives
 Synthesis of layered metal antimonides of the type AMnSb2 in polycrystalline and single
crystalline form.

 Investigation of magnetic properties, transport properties.

 Tuning of different physical properties such as magnetic properties, transport properties

by doping.

 Theoretical calculations of some suitable compound to understand the interrelationship

among structure, bonding and properties.

Synthesis and Characterisation:

We have tried to synthesize YbMnSb2 and CaMnSb2 by reacting the stoichiometric
amount of constituent elements at high temperature. The PXRD pattern of these two compounds
are given below. By analysing these PXRD data it was observed that the desired phase was not
formed. Currently we are trying to optimize the reaction condition to get pure phases of these.

Figure 10. PXRD pattern of YbMnSb2 and CaMnSb2.

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 Future Work:
We have attempted to synthesize the above mentioned compounds using different
optimized synthesis condition but we were unable to get pure phase compounds. There are some
issues that we are trying to rectify. We are trying to optimize the reaction condition to synthesize
alkaline metal based, rare earth metal based layered compounds and study their different
properties. After successful synthesis we will attempt to dope these end membered compounds
with different suitable elements such that we can tune their properties according to our desire.

Reference:
1. J.A. Wilson & A.D. Yoffe; The Transition Metal Dichalcogenides Discussion and
Interpretation of the Observed Optical, Electrical and Structural Properties; Advances in
Physics, (1969), 18:73,193-335.
2. E. M. Vogel, J. A. Robinson, Two-dimensional Layered Transition-Metal Dichalcogenides
for Versatile Properties and Applications; MRS Bulletin, (2015), 40,558-563.
3. W. Tremel, H. Kleinke, V. Derstroff, C. Reisner, Transition Metal Chalcogenides: New
Views on an Old Topic; J. All. Com,(1995), 219, 73-82.
4. D. Chao, P. Liang, Z. Chen, L. Bai, H. Shen, X. Liu, X. Xia, Y. Zhao, S. V. Savilov, J.
Lin, Z. Xiang Shen; Pseudocapacitive Na-Ion Storage Boosts High Rate and Areal Capacity
of Self-Branched 2D Layered Metal Chalcogenide Nanoarrays; ACS Nano, (2016), 10,
10211-10219.
5. G. A. Muller, J. B. Cook, H. Kim, S. H. Tolbert, B. Dunn; High Performance
Pseudocapacitor Based on 2D Layered Metal Chalcogenide Nanocrystals, Nano Lett.,
(2015), 15(3), 1911-1917.
6. M. Chhowalla, H. S. Shin, G. Eda, L. Li, K. P. Loh, H. Zhang; The chemistry of two-
dimensional layered transition metal dichalcogenide nanosheets Nat. Chem. (2013), 5, 263-
275.
7. W. Choi, N. Choudhary, G. H. Han, J. Park, D. Akinwande, Y. H. Lee; Recent development
of two-dimensional transition metal dichalcogenides and their applications, Mater. Today,
(2017), 20(3), 116-130.
8. X. Congxin, L. Jingbo; Recent advances in optoelectronic properties and applications of
two-dimensional metal chalcogenides; J. Semicond., (2016), 37(5), 051001(1-9).

16 | P a g e
9. R. Schollhorn and H. Meyer; Cathodic reduction of layered Transition metal chalcogenides
Mat. Res. Bull., (1974), 9, 1237-1246.
10. F. Le´vy; Crystallography and Crystal Chemistry of Materials with Layered Structures.
(1976), Dordrecht: Springer Netherlands.
11. Y. Jiao, L. Zhou, F. Ma, G. Gao, L. Kou, J. Bell, S. Sanvito, A. Du; Predicting Single-Layer
Technetium Dichalcogenides (TcX2, X = S, Se) with Promising Applications in
Photovoltaics and Photocatalysis, ACS Appl. Mater. Interfaces, (2016), 8, 5385−5392.
12. Y. Kim, J. Song, Y. Ju Park, G. H. Ryu, S. J. Lee, J. S. Kim, P. J. Jeon, C. W. Lee, W. J.
Woo, T. Choi, H. Jung, H. Lee, J. Myoung, S. Im, Z. Lee, J. Ahn, J. Park, H. Kim, Self-
Limiting Layer Synthesis of Transition Metal Dichalcogenides; Sci. Rep., (2016), 6, 18754.
13. Y. Chen, H. Medina, S. Wang, T. Su, J. Li, W.Yen, K. Cheng, H. Kuo, G. Shen, Y. Chueh;
Low-Temperature and Ultrafast Synthesis of Patternable Few-Layer Transition Metal
Dichacogenides with Controllable Stacking Alignment by a Microwave-Assisted
Selenization Process, Chem. Mater. (2016), 28, 1147−1154.
14. P. A. Hu, Z. Wen, L. Wang, P. Tan, K. Xiao; Synthesis of Few-Layer GaSe Nanosheets for
High Performance Photodetectors, (2012), 6(7), 5988-5995.
15. Y. Zhou, B. Deng, Y. Zhou, X. Ren, J. Yin, C. Jin, Z. Liu, H. Peng; Low-Temperature
Growth of Two-Dimensional Layered Chalcogenide Crystals on Liquid, Nano Lett. (2016),
16, 2103−2107.
16. D. C. Johnston; The Puzzle of High Temperature Superconductivity in Layered Iron
Pnictides and Chalcogenides, Advances in Physics, (2010), 59:6, 803-1061.
17. A. Harvey, C. Backes, Z. Gholamvand, D. Hanlon, D. McAteer, H. C. Nerl, E.McGuire, A.
Seral-Ascaso, Q. M. Ramasse, N. McEvoy, S. Winters, N. C. Berner, D. McCloskey, J. F.
Donegan, G. S. Duesberg; Preparation of Gallium Sulfide Nanosheets by Liquid Exfoliation
and Their Application As Hydrogen Evolution Catalysts, Chem. Mater., (2015), 27,
3483−3493.
18. Z. Yao, J. Li, Z. D. Wang; Extended Hubbard Model of Superconductivity and Charge-
Density-Waves in the Layered 2H Transition Metal Dichalcogenides, Phys. Rev. B, (2006),
74, 212507.
19. E. Revolinsky, G. A. Spiering, D. J. Beerntsen; Superconductivity in the Niobium-Selenium
System, J. Phys. Chem. Solids, (1965), 26, 1029-1034.
20. E. Revolinsky, E. P. Lautenschlager, C.H. Armitage; Layer Structure Superconductor, Solid
State Commun. (1963), 1, 59-61.

17 | P a g e
21. Etienne Boaknin, M. A. Tanatar, Johnpierre Paglione, D. Hawthorn, F. Ronning, R.W. Hill,
M. Sutherland, Louis Taillefer, Jeff Sonier, S.M. Hayden, J.W. Brill; Heat Conduction in
the Vortex State of NbSe2: Evidence for Multiband Superconductivity, Phys. Rev. Lett.,
(2003), 90(11), 117003(1-4).
22. T. Yokoya, T. Kiss, A. Chainani, S. Shin, M. Nohara, H. Takagi; Fermi Surface Sheet-
Dependent Superconductivity in 2H-NbSe2, Science, (2001), 294, 2518.
23. Y. Noat, J. A. Silva-Guill´en, T. Cren, V. Cherkez, C. Brun, S. Pons, F. Debontridder, D.
Roditchev, W. Sacks, L. Cario, P. Ordej´on, A. Garc´ıa, E. Canadell; Quasiparticle Spectra
of 2H-NbSe2: Two-band Superconductivity and the Role of Tunneling Selectivity, Phys.
Rev. B, (2015), 92, 134510.
24. J. D. Fletcher, A. Carrington, P. Diener, P. Rodie`re, J. P. Brison, R. Prozorov, T. Olheiser,
R.W. Giannetta; Penetration Depth Study of Superconducting Gap Structure of 2H-NbSe2,
Phys. Rev. Lett., (2007), 98, 057003.
25. M. Marezio, P. D. Dernier; A. Menth, G. W. Hull Jr.; The Crystal Structure of NbSe 2 at
15°K, J. Solid State Chem., (1972), 4, 425-429.
26. A. Meerschaut, C. Deudon; Crystal structure studies of the 3R-Nb1.09S2 and the 2HNbSe2
Compounds: Correlation between Nonstoichiometry and Stacking Type (Polytypism),
Mater. Res. Bull., (2001), 36, 1721–1727.
27. F. Kadijk, R. Huisman, F. Jellinek, Niobium and Tantalum Diselenides; Recl. Trav. Chim.
Pays-Bas, (1964), 83(7), 768-775.
28. K. Motizuki, Y. Nishio, M. Shirai, N. Suzuki; Effect of Intercalation on Structural Instability
and Superconductivity of Layered 2H-Type NbSe2 and NbS2, J. Phys. Chem. Solids, (1996),
57(6-8), 1091-1096.
29. E. Hitz, J. Wan, A. Patel, Y. Xu, L. Meshi, J. Dai, Y. Chen, A. Lu, A. V. Davydov, L. Hu;
Electrochemical Intercalation of Lithium Ions into NbSe2 Nanosheets, ACS Appl. Mater.
Interfaces, (2016), 8, 11390−11395.
30. C. Lian, C. Si, J. Wu, W. Duan; First-principles Study of Na-Intercalated Bilayer NbSe2:
Suppressed Charge Density Wave and Strain-Enhanced Superconductivity, Phys. Rev. B,
(2017), 96, 235426.
31. Y. Koh, S. Cho1, J. Lee, L. Yan, Y. Zhang, C. He, F. Chen, D. Feng, M. Arita, K. Shimada,
H. Namatam, M. Taniguchi, C. Kim; Growth and Electronic Structure Studies of Metal
Intercalated Transition Metal Dichalcogenides MxNbSe2 (M: Fe and Cu), Jpn. J. Appl. Phys.
(2013), 52, 10MC15.

18 | P a g e
32. S. C. Ganguli, H. Singh, I. Roy, V. Bagwe, D. Bala, A. Thamizhavel, P. Raychaudhur;
Disorder-Induced Two-Step Melting of Vortex Matter in Co-intercalated NbSe2 Single
Crystals, Phys. Rev. B, (2016), 93, 144503.
33. H. Luo, J. Strychalska-Nowak, J. Li, J. Tao, T. Klimczuk, R. J. Cava; S-Shaped Suppression
of the Superconducting Transition Temperature in Cu-Intercalated NbSe2, Chem. Mater.,
(2017), 29 (8), 3704-3712.
34. M. Kars, A. G. Herrero, A. Rebbah, L.C. Otero-Dia´z; GexNbSe2 and GexNbS2 intercalation
compounds, Mater. Res. Bull., (2009), 44, 1601–1607.
35. H. Li, L. Chen, K. Zhang, J. Liang, H. Tang, C. Li, X. Liu, J. Meng, Z. Wang; Atomic
Structures and Electronic Properties of 2H-NbSe2: The Impact of Ti Doping, J. Appl. Phys.,
(2014), 116, 103709.
36. H. Li, S. Liu, L.Chen, J. Wu, P. Zhang, H. Tang, C. Li, X. Liu, Z. Wang, J. Meng; Atomic
structures and electronic properties of Ta-doped 2H-NbSe2, RSC Adv., (2014), 4, 57541.
37. Max-Plank-Institut für Festkörperforschung, Heisenbergstr. 1, D-70569 Stuttgart, Federal
Republic of Germany.
38. R. Dronskowski, P. E. Blöchl, J. Phys. Chem., (1993), 97, 8617-8624.
39. W. Scott, Preparation and some properties of ZnSnSb2; J. Appl. Phys., (1973), 44, 5165.
40. O. Zobač, J. Sopoušek, A. Kroupa; Calphad-type assessment of the Sb–Sn–Zn ternary
system; CALPHAD, (2015), 51, 51–56
41. Y. Wang, Q. Yu and T. Xia; Large Linear Magnetoresistance in a New Dirac Material
BaMnBi2, Chin. Phys. B, (2016), 25, 107503.
42. J. Liu, J. Hu, H. Cao, Y. Zhu, A. Chuang, D. Graf, D. J. Adams, S. M. A. Radmanesh, L.
Spinu, I. Chiorescu, Zhiqiang Mao; Nearly Massless Dirac Fermions Hosted by Sb Square
Net in BaMnSb2, (2016), Sci. Rep., 6, 30525.
43. D. E. McNally, J. W. Simonson, J. J. Kistner-Morris, G. J. Smith, J. E. Hassinger, L.
DeBeer-Schmitt, A. I. Kolesnikov, I. A. Zaliznyak, M. C. Aronson; CaMn2Sb2: Spin Waves
on a Frustrated Antiferromagnetic Honeycomb Lattice, Phys. Rev. B, (2015) 91, 180407(R).
44. J. B. He, Y. Fu, L. X. Zhao, H. Liang,1 D. Chen, Y. M. Leng, X. M. Wang, J. Li, S. Zhang,
M. Q. Xue, C. H. Li, P. Zhang, Z. A. Ren, G. F. Chen; Quasi-two-dimensional Massless
Dirac Fermions in CaMnSb2, Phys. Rev. B, (2017), 95, 045128.
45. A. Zhang, C. Liu, C. Yi, G. Zhao, T. Xia, J. Ji, Y. Shi, Rong Yu, X. Wang, C. Chen, Q.
Zhang; Interplay of Dirac Electrons and Magnetism in CaMnBi2 and SrMnBi2; Nat.
Commun., (2016), 7, 13833.

19 | P a g e
46. C. A. Bridges, V. V. Krishnamurthy, S. Poulton, M. P. Paranthaman, B. C. Sales, C. Myers,
S. Bobev; Magnetic Order in CaMn2Sb2 Studied via Powder Neutron Diffraction, J. Magn.
Magn. Mater. (2009), 321, 3653–3657.
47. J.Y. Liu, J. Hu, Q. Zhang, D. Graf, H.B. Cao, S.M.A. Radmanesh, D.J. Adams, Y.L. Zhu,
G.F. Cheng, X. Liu, W. A. Phelan, J. Wei1, D. A. Tennant, J. F. DiTusa, I. Chiorescu, L.
Spinu, Z.Q. Mao; Discovery of a magnetic topological semimetal Sr1-yMn1-zSb2 (y, z < 0.10),
Nat. Mater., (2017), 16(9), 905-910.
48. H. J. Park, Luke J. Sandilands, J. S. You, Hyo Seok Ji, C. H. Sohn, J. W. Han, S. J. Moon,
K. W. Kim, J. H. Shim, Jun Sung Kim, T. W. Noh; Thermally Activated Heavy States and
Anomalous Optical Properties in a Multiband Metal: The Case of SrMnSb2; Phys. Rev. B,
(2016), 93, 205122.
49. W. Ratcliff II, A. L. Lima Sharma, A. M. Gomes, J. L. Gonzale, Q. Huang, J. Singleton The
Magnetic Ground State of CaMn2Sb2; J. Magn. Magn. Mater. (2009), 321, 2612–2616.
50. S. Bobev, J. Merz, A. Lima, V. Fritsch, J. D. Thompson, J. L. Sarrao, M. Gillessen, R.
Dronskowski; Unusual Mn-Mn Spin Coupling in the Polar Intermetallic Compounds
CaMn2Sb2 and SrMn2Sb2, Inorg. Chem., (2006), 45(10), 4047.
51. A.V. Morozkina, P. Manfrinetti; Magnetic Structure of the YbMn2SbBi Compound, J.
Alloys Compd. (2011), 509, 3723–3725.
52. R. Kealhofer, S. Jang, S. M. Griffin, C. John, K. A. Benavides, S. Doyle, T. Helm, P. J. W.
Moll, J. B. Neaton, J. Y. Chan, J. D. Denlinger, J. G. Analytis; Observation of two-
dimensional Fermi Surface and Dirac Dispersion in YbMnSb2, Phys. Rev. B, (2018), 97,
045109.
53. X. Wang, W. Li, C. Wang, J. Li, X. Zhang, B. Zhou, Y. Chenb, Y. Pei; Single Parabolic
Band Transport in p-type EuZn2Sb2 Thermoelectrics; J. Mater. Chem. A, (2017), 5(46),
24185-24192.
54. E. Brechtel, G. Cordier, and H. Sch¨afer, J. Less Common Metals, (1981), 79, 131.

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 ROAD MAP FOR RESEARCH WORK

Date of Enrolment: 25th July 2016

Plan of Work Period

Jul Jan Jul Jan Jul Jan Jul Jan

2017 to
2016 to 2017 to 2018 to 2018 to 2019 to 2019 to 2020 to
Dec
Dec Jun Jun Dec Jun Dec Jun
2017
2016 2017 2017 2018 2019 2019 2020

Course work

Literature

Survey

Experimental

Work

Analysis of

Experimental

Work

Writing of

Manuscript

Writing of

Thesis and

Submission

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COURSE WORK

COURSE WORK (July 2016 – July 2017)

Subject Code Name of the Subject Credits Grade

CY611 Advanced Analytical Chemistry 03 B

CY636 Special Topics in Physical 03 B

Chemistry

CY616 Nuclear Magnetic Resonance 03 B

Spectroscopy

CY623 Catalysis-principles and 03 A

applications

CY621 Advanced Inorganic Chemistry 03 A

CY632 Chemistry of Nanomaterials 03 A

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