synthesis, structures, electronic structures and physical properties of quaternary alkali, alkaline

95 Pages·2015·2.87 MB·English

SYNTHESIS, STRUCTURES, ELECTRONIC STRUCTURES AND PHYSICAL
PROPERTIES OF QUATERNARY ALKALI, ALKALINE EARTH, RARE
EARTH AND TRANSITION METAL PNICTIDES

by
Yi Wang

A thesis submitted to the Faculty of the University of Delaware in partial fulfillment of
the requirements for the degree of Master of Science in Chemistry and Biochemistry

Summer 2015
 2015 Yi Wang
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SYNTHESIS, STRUCTURES, ELECTRONIC STRUCTURES AND PHYSICAL
PROPERTIES OF QUATERNARY ALKALI, ALKALINE EARTH, RARE
EARTH AND TRANSITION METAL PNICTIDES

by
Yi Wang

Approved: __________________________________________________________
Svilen S. Bobev, Ph.D.
Professor in charge of thesis on behalf of the Advisory Committee

Approved: __________________________________________________________
Murray V. Johnston, Ph.D.
Chair of the Department of Chemistry and Biochemistry

Approved: __________________________________________________________
George H. Watson, Ph.D.
Dean of the College of Arts and Sciences

Approved: __________________________________________________________
James G. Richards, Ph.D.
Vice Provost for Graduate and Professional Education
ACKNOWLEDGMENTS
Foremost, I would like to express the deepest appreciation to my advisor Dr. Bobev
for giving me the opportunity to study in his laboratory. His infectious passion and
professional attitude have been major driving forces through my graduate career in the
University of Delaware. I am extremely grateful for his guidance, suggestions and
persistent help in these years. Without his important contribution this thesis would not have
been possible.
I would like to thank the Department of Chemistry and Biochemistry at University
of Delaware for the financial support. And my sincere thanks also go for Dr. Burmeister
for his help, understanding and offering my summer teaching opportunity in the
Department.
I would like to thank the past and current members of Dr. Bobev’s group, Dr. Hua
He, Dr. Nian-Tzu Suen, Dr. Marion Schäfer, Dr. Jiliang Zhang, Dr. Stanislav Stoyko, Dr.
Julien Makongo, Mr. James Hoos, Mr. Matt Broda and Mr. Greg Darone. They always
support and help me in different ways and I really learn lots of experiences and
experimental skills from them.
In addition I would like to thank all researchers, technicians, and staffs, who provide
all kinds of support and help for me, especially to Dr. Yap, who helps me with single-
crystal X-ray diffractometer and Robert Schmidt, who helps me with Physical Property
measurement system (PPMS) measurements. And a thank you to all my friends in the
department of Chemistry and Biochemistry, I really appreciate their help and cherish our
friendships and time we spent together.

iii
Last but not least, I would like to acknowledge with the love and support of my
family—my parents Jianping Wang and Yiling Li and my husband Bin Fang. They all keep
me going through my life. Without their care and love, I could be who I am right now.

iv
TABLE OF CONTENTS
LIST OF TABLES……………………………………………………………………….vii
LIST OF FIGURES……………………………………………………………………….ix
ABSTRACT.......................................................................................................................xi

Chapter

1 INTRODUCTION……………...…………………………………………………1

1.1 Background…………………………………………………………………..1
1.2 Intermetallic Compounds and Zintl Phases………………………………….2
1.3 Cation Effect and Exploratory Studies of Quaternary Pnictides with Alkali-
Alkaline Earth or Rare-Earth Metals and Transition Metals…………..……6
1.4 Layout of The Thesis………………………………………………….....….8
REFERENCES………………………………………………………………..…10

2 QUATERNARY PNICTIDES WITH COMPLEX, NONCENTROSYMMETRIC
STRUCTURES. SYNTHESIS AND STRUCTURAL CHAACTERIZATION OF
THE NEW ZINTL PPASES Na Ca Al Sb , Na CaGaSb , AND
11 2 3 8 4 3
Na Ca In Sb …………………………………………………………………...12
15 3 5 12

2.1 Abstract……………………………………………………………………..12
2.2 Introduction…………………………………………………………………13
2.3 Experimental………………………………………………………………..14
2.4 Results and Discussion...................................................................................18
2.5 Conclusions…………………………………………………………………27

REFERENCES……………………………………………………………….….39

3 EFFICIENT TAILORING OF BAND GAP INDUCED BY RARE EARTH (RE)
METALS DOPINGDETERMINING STRUCTURE AND PROPERTIES OF
NARROWGAP SEMICONDUCTOR Ca RE Mn Sb (RE = La, Ce, Pr, Nd
9-x x 4 9
AND Sm)……………………………………………………………………...…42

3.1 Abstract…………………………………………………………………..…42
3.2 Introduction………………………………………………………………....42
3.3 Experimental……………………………………………………..…………44
3.4 Results and Discussion…………………………………………..…………48
3.5 Conclusions.…………………………………………..………………….…58

REFERENCES…………………….………………….…………………………75

4 CONLUSIONS……………………………………………..………………..…..79

v
4.1 Brief Summary of This Work…………………………………….………...79

4.2 Future Prospects…………………………………………………………….79

REFERENCES…………………………………………………………………..80

Appendix

A A HANDY LIST OF EIGHT NEW COMPOUNDS AND THEIR SPACE GROUP
INFORMATION……………………………………………………...…………81
B REPRINT PERMISSION LETTERS……………………………………….…….82

vi
LIST OF TABLES
Table 2.1: Selected Single-Crystal Data Collection and Structure Refinement
Parameters for Na Ca Al Sb , Na CaGaSb , and Na Ca In Sb …........29
11 2 3 8 4 3 15 3 5 12

Table 2.2: Atomic Coordinates and Equivalent Isotropic Displacement Parameters U
eq
for Na Ca Al Sb ……………………………………………………......30
11 2 3 8

Table 2.3: Atomic Coordinates and Equivalent Isotropic Displacement Parameters U
eq
for Na CaGaSb ………………………………………………………….31
4 3

Table 2.4: Atomic Coordinates and Equivalent Isotropic Displacement Parameters U
eq
for Na Ca In Sb ……………………………………………………….32
15 3 5 12

Table 2.5: Selected Interatomic Distances (Å) And Angles (degree) in Na Ca Al Sb ,
11 2 3 8
Na CaGaSb , and Na Ca In Sb ….…………………………………….33
4 3 15 3 5 12

Table 3.1: Selected Crystal Data and Structure Refinement Parameters for
Ca La Mn Sb ………………………………………………......59
8.27(1) 0.73(1) 4 9

Table 3.2: Selected Crystal Data and Structure Refinement Parameters for
Ca Ce Mn Sb ………………………………………………......60
8.16(1) 0.84(1) 4 9

Table 3.3: Selected Crystal Data and Structure Refinement Parameters for
Ca Pr Mn Sb …………………………………….…………......61
8.15(1) 0.85(1) 4 9

Table 3.4: Selected Crystal Data and Structure Refinement Parameters for
Ca Nd Mn Sb …………………………………………….….....62
8.11(1) 0.89(1) 4 9

Table 3.5: Selected Crystal Data and Structure Refinement Parameters for
Ca Sm Mn Sb ………………………………………………......63
7.88(1) 1.12(1) 4 9

Table 3.6: Atomic Coordinates and Equivalent Isotropic Displacement Parameters
(U ) for Ca La Mn Sb ……………………………………..…...64
eq 8.27(1) 0.73(1) 4 9

Table 3.7: Atomic Coordinates and Equivalent Isotropic Displacement Parameters
(U ) for Ca Ce Mn Sb …………….………………….………..65
eq 8.16(1) 0.84(1) 4 9

Table 3.8: Atomic Coordinates and Equivalent Isotropic Displacement Parameters
(U ) for Ca Pr Mn Sb ……………………………….…………66
eq 8.15(1) 0.85(1) 4 9

Table 3.9: Atomic Coordinates and Equivalent Isotropic Displacement Parameters
(U ) for Ca Nd Mn Sb ……………………………………....…67
eq 8.11(1) 0.89(1) 4 9

Table 3.10: Atomic Coordinates and Equivalent Isotropic Displacement Parameters
(U ) for Ca Sm Mn Sb …………………………………...……68
eq 7.88(1) 1.12(1) 4 9
vii
Table 3.11: Important Interatomic Distances (Å) and Angles (degree) for
Ca La Mn Sb and Ca Sm Mn Sb ……………..........…69
8.27(1) 0.73(1) 4 9 7.88(1) 1.12(1) 4 9

Table 3.12: Comparison between Measured and Expected Effective Moments in
Ca RE Mn Sb series (RE= La, Ce, Pr, Nd and Sm)…………………… 70
9-x x 4 9

viii
LIST OF FIGURES
Figure 2.1: Polyhedral views of the structures of Na Ca In Sb (a), Na CaGaSb (b),
15 3 5 12 4 3
and Na Ca Al Sb (c). The common atomsCa, Na, and Sb-are drawn as
11 2 3 8
blue, green, and orange spheres, respectively. The atoms centering the Sb
tetrahedra-In, Ga, and Al-are shown in light blue, pink, and red,
respectively…………………..……………………………………….….34

Figure 2.2: Detailed drawings in different orientations of a [In Sb ] cutout from the
4 12
layers of the Na Ca In Sb structure (a), a [Ga Sb ] cutout from the
15 3 5 12 4 13
chains in the Na CaGaSb structure (b), and the [Al Sb ] cluster in the
4 3 3 8
Na Ca Al Sb structure (c). The atoms are labeled, and the relevant
11 2 3 8
distances and angles are listed in Table 1.5……………………………….34

Figure 2.3: Polyanionic substructures of Na CaGaSb (a) and Na Ca Al Sb (b)
4 3 11 2 3 8
viewed as tetrahedral “hybrid layers”, made up of Ga, Na, Sb and Al, Na,
Sb, respectively. The atoms are labeled, and the relevant distances are listed
in Table 1.5……………………………………………………………….35

Figure 2.4: Structural relationships among Na Ca In Sb , Na CaGaSb , and
15 3 5 12 4 3
Na Ca Al Sb . Panel (a) shows the idealized, defect-free [InSb ]
11 2 3 8 2
polyanionic layers in Na Ca In Sb ; panel (b) depicts the hypothetical
15 3 5 12
hybrid [Ga Na Sb ] layers in Na CaGaSb ; panel c shows the imaginary
2/3 1/3 2 4 3
[Al Na Sb ] layers in Na Ca Al Sb . In all drawings, two different
1/2 1/2 2 11 2 3 8
orientations are shown, with the tetrahedra rendered in green corresponding
to the NaSb units………………………………………………………...36
4

Figure 2.5: Structural relationships among Na In Bi (TiNiSi structure type) [36] and
3 2 3
Na Ca In Sb , Na CaGaSb , and Na Ca Al Sb . Panel (a) shows the
15 3 5 12 4 3 11 2 3 8
three-dimensional framework of the parent structure with Na shown in
yellow, In shown in blue, and Bi shown in orange. Panels (b)-(d) depict the
structures of Na Ca In Sb , Na CaGaSb , and Na Ca Al Sb , where the
15 3 5 12 4 3 11 2 3 8
frameworks include the tetrahedrally coordinated Na atoms. To guide the
eye, the In−Sb, Ga−Sb, and Al−Sb bonds are colored with the respective
elemental colorsblue, pink, and redand the Na−Sb “bonds” are drawn as
gray cylinders……………..……..…………………………………….....37

Figure 2.6: Calculated total and partial DOS curves for Na Ca In Sb (a),
15 3 5 12
Na CaGaSb (b), and Na Ca Al Sb (c). The Fermi level is the energy
4 3 11 2 3 8
reference at 0 eV………………………………………………………….38

Figure 2.7: COHP curves for In−Sb, Ga−Sb, and Al−Sb (black lines) and for selected
Na−Sb interactions (red lines). Panel (a) refers to Na Ca In Sb , panel (b)
15 3 5 12
refers to Na CaGaSb , and panels (c) and (d) refer to Na Ca Al Sb . In
4 3 11 2 3 8
plots of the COHP curves, the COHP values were inverted (i.e., −COHP is
shown) so that the positive and negative regions represent bonding and
ix