Rational Synthesis Design of Low-Dimensional Bulk Materials

Article Cite This: Acc. Chem. Res. 2018, 51, 12−20

pubs.acs.org/accounts

Casting a Wider Net: Rational Synthesis Design of Low-Dimensional Bulk Materials Published as part of the Accounts of Chemical Research special issue “Advancing Chemistry through Intermetallic Compounds”. Katherine A. Benavides, Iain W. H. Oswald, and Julia Y. Chan* Department of Chemistry & Biochemistry, The University of Texas at Dallas, Richardson, Texas 75080, United States CONSPECTUS: The discovery of novel magnetic and electronic properties in low-dimensional materials has led to the pursuit of hierarchical materials with specific substructures. Low-dimensional solids are highly anisotropic by nature and show promise in new quantum materials leading to exotic physical properties not realized in three-dimensional materials. We have the opportunity to extend our synthetic strategy of the flux-growth method to designing single crystalline low-dimensional materials in bulk. The goal of this Account is to highlight the synthesis and physical properties of several low-dimensional intermetallic compounds containing specific structural motifs that are linked to desirable magnetic and electrical properties. We turned our efforts toward intermetallic compounds consisting of antimony nets because they are closely linked to properties such as high carrier mobility (the velocity of an electron moving through a material under a magnetic field) and large magnetoresistance (the change in resistivity with an applied magnetic field), both of which are desirable properties for technological applications. The SmSb2 structure type is of particular interest because it is comprised of rectangular antimony nets and rare earth ions stacked between the antimony nets in a square antiprismatic environment. LnSb2 (Ln = La−Nd, Sm) have been shown to be highly anisotropic with SmSb2 exhibiting magnetoresistance of over 50000% for H∥c axis and ∼2400% for H∥ab. Using this structure type as an initial building block, we envision the insertion of transition metal substructures into the SmSb2 structure type to produce ternary materials. We describe compounds adopting the HfCuSi2 structure type as an insertion of a tetrahedral transition metal−antimony subunit into the LnSb2 host structure. We studied LnNi1−xSb2 (Ln = Y, Gd−Er), where positive magnetoresistance reaching above 100% was found for the Y, Gd, and Ho analogues. We investigated the influence of the transition metal sublattice by substituting Ni into Ce(Cu1−xNix)ySb2 (y < 0.8) and found that the material is highly anisotropic and metamagnetic transitions appear at ∼0.5 and 1 T in compounds with higher Ni concentration. Metamagnetism is characterized by a sharp increase in the magnetic response of a material with increasing applied magnetic field, which was also observed in LnSb2 (Ln = Ce−Nd). We also endeavored to study materials that possess a transition metal sublattice with the potential for geometric frustration. An example is the La2Fe4Sb5 structure type, which consists of antimony square nets and an iron-based network arranged in nearly equilateral triangles, a feature found in magnetically frustrated systems. We discovered spin glass behavior in Ln2Fe4Sb5 (Ln = La−Nd, Sm) and evidence that the transition metal sublattice contributes to the magnetic interactions of Ln2Fe4Sb5. We investigated the magnetic properties of Pr2Fe4−xCoxSb5 (x < 2.3) and found that as the Co concentration increases, a second magnetic transition leads from a localized to an itinerant system. The La2Fe4Sb5 structure type is quite robust and allows for the incorporation of other transition metals, thereby making it an excellent candidate to study competing magnetic interactions in lanthanide-containing intermetallic compounds. In this manuscript, we aim to share our experiences of bulk intermetallic compounds to inspire the development of new low-dimensional materials.

1. BACKGROUND

pounds with specific structural units still remains elusive. Our group1,2 and others3−6 have found success in using low melting metals as fluxes to produce single crystals of new compounds, although the selection of systems to study remains a nontrivial task. When considering flux-growth, we can take advantage of low melting main group elements such as Ga, Sn, and Sb as part of the synthesis (the self-flux method)3 and in 2012, we

Developing novel, crystalline, inorganic materials is one of the central themes in solid-state chemistry and physics and has led to the discovery of novel quantum materials. It is by nature highly multidisciplinary, requiring efforts in condensed matter physics, chemistry, and materials science. Without new materials, we cannot drive fundamental understanding of physical phenomena. Crystal growth of intermetallic compounds is advantageous for determination of intrinsic magnetic and electrical properties. However, designing complex com© 2017 American Chemical Society

Received: September 18, 2017 Published: December 14, 2017 12

DOI: 10.1021/acs.accounts.7b00461 Acc. Chem. Res. 2018, 51, 12−20

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Accounts of Chemical Research

Figure 1. Incorporation of transition metal into the AuCu3-type subunit can serve as a building block for the ternary HoCoGa5 and Ho4PdGa12 structure types.

highlighted and surveyed the use of the flux-growth method to grow single crystals of rare earth transition metal intermetallic compounds with group 13−15 elements.1 The use of eutectic melting points has also been instrumental for the synthesis of metal-rich or high melting elements such as seen in the use of Gd/Co to grow single crystalline Gd117Co56Sn112 with low lattice thermal conductivity, one of the lowest for a bulk extended solid.7 Similarly, Ce/Co eutectic fluxes were used to grow single crystals of Ce10Co2.64B11.70C10, which is ferromagnetic at 15 K and possesses Ce ions that valence fluctuate as evidenced by a low total effective magnetic moment.8 1.1. Structure- and Property-Driven Synthesis Figure 2. Insertion of La into the Co2Al9 structure results in the formation of a stable ternary phase. Figure adapted with permission from ref 23. Copyright 2015 American Chemical Society.

We choose to study intermetallic compounds containing specific structural features such as cuboctahedra or layered motifs.2 Our interest in highly correlated magnetic systems drove us to note the local chemical environment of rare earth ions located in a cubic site symmetry such as Ce in AuCu3-type environment.9 We were particularly fascinated by the magnetically mediated superconducting compounds CeMIn5 (M = Co, Rh, Ir).10−12 In our pursuits of studying compounds containing the AuCu3-type subunit, we discovered large magnetoresistance (up to 900%) in Ln4MGa12 (Ln = Y, Tb−Er; M = Fe, Pd, Pt), which contains LnGa3 cuboctahedra and corner-sharing MGa6 octahedra.13,14 Figure 1 shows the AuCu3, ScFeGa5, and Ho4PdGa12 crystal structures.13−16 Another intermetallic family of compounds containing the AuCu3-type subunit is found in Ln3M4Ge13 (Ln = Y, Yb, Lu; M = Co, Ir, Rh, Os).17−20 These compounds exhibit a semimetallic state preceding a superconducting transition, which is quite exceptional. The structural disorder associated with the Ge site is closely tied to the resistivity and can be assessed numerically as a ratio of atomic displacement parameters.18 Our success incorporating transition metals into the host AuCu3-type structure led us to consider the role of the binary Co2Al921,22 as a means to describe LnCo2Al8 (Ln = La−Nd, Sm, Yb).23 Our initial fascination with this structure type was centered on the oxidation state of Ce, which is highly dependent on the nature of the transition metal. For CeCo2Al8, it was found that the Ce is in the Ce3+ oxidation state, but CeFe2Al8 exhibited valence fluctuation of Ce due to hybridization of the Ce 4f electrons, which resulted in a nonmagnetic compound.24,25 Considering the crystal structure of the binary CoAl9, we note the similar coordination environment of the CoAl9 polyhedra, and the structure can be viewed as an insertion of Ce into the framework of the LnCo2Al8 crystal structure. We highlight the similarities of these structures in Figure 2. The insertion of the rare earth element into this structure type makes this a way to understand the structure of

binary phases as building blocks in the growth of ternary phases. 1.2. Architecturally Fabricated Low-Dimensional Materials

Tremendous efforts have been dedicated to the preparation of phases in reduced dimensions because of the emergence of novel properties not seen in bulk. Although graphene arguably first generated interest in 2D materials, the breadth of the field has expanded to encompass 2D elemental materials such as silicene, phosphorene, and germanene.26 The study of 2D materials has also extended to transition metal dichalcogenides27 and multiferroic oxides28 as well as 2D transition metal carbides, carbonitrides, and nitrides.29 The synthetic methods used to produce these films with specific properties utilize strain and defect control as well as controlling the film thickness.28 An addition to the more established methods to produce epitaxially grown films is a recent effort utilizing ligand termination of a solid-state lattice to produce atomically thin structures.30 The top-down approach of mechanically exfoliating materials to produce atomically thin sheets was recently combined with DFT calculations to study CrI3,31 a compound composed of CrI3 slabs separated by van der Waals gaps. The coupling between the CrI3 layers is closely tied to the magnetism exhibited, and the ferromagnetic ordering of the bulk material was theorized to persist into the monolayer form based on DFT calculations.32 More recent experiments have confirmed monolayers and trilayers of CrI3 to be ferromagnetic, while the bilayers exhibit antiferromagnetic behavior, experimentally demonstrating that the magnetism is highly dependent on the layering of the material.33 Another example of atomically thin ferromagnetism is observed in Ce2Ge2Te6.34 Atomically thin layers were mechanically exfoliated, and the ferromagnetic 13


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Accounts of Chemical Research transition temperature increased monotonically from ∼30 to ∼68 K with increasing layer thickness, which is consistent with the transition temperature of the bulk material. It was also found that increasing the applied magnetic field from 0.065 to 0.3 T increased the bilayer flake transition temperature from 28 to 44 K, a feature not observed in the bulk material. We as intermetallic chemists ask the following, “Can we use bulk materials to mimic the highly desirable anisotropic properties exhibited by these low-dimensional materials without the need for mechanical exfoliation?”

gives rise to evidence of periodic modulations of charge, which are known as charge density waves.42 The charge density wave is made more apparent by the substitutional disorder created upon adding Ce and also eliminates the linear magnetoresistance. We wish to illustrate the incredible breadth of physical properties obtained when using the LnSb2 structure as a lowdimensional scaffold by highlighting known compounds with this subunit in Table 1. We note the specificities of the

1.3. Our Motivation

Table 1. Selected Compounds Featuring the LnSb2 Motif Containing Layered or Disordered Nets

Solid-state chemists have the opportunity to consider structure types that produce the anisotropic properties so sought after in these low-dimensional materials. One of the major themes surrounding the recent literature in solid-state chemistry and condensed matter is linking the specific symmetries of space groups and the types of topological electronic states that emerge as a consequence.35,36 One such study gives particular emphasis to the ability to tune a system between a 2D topological and trivial insulator through symmetry breaking elements.37 We seek to use specific structural units and crystal symmetries as building blocks to produce bulk compounds that exhibit the highly desirable physical properties so ubiquitous in 2D materials. A strategy for this endeavor is to consider rare earth pnictides, which can be used to build low-dimensional materials by inserting transition metal−antimony sublattices into existing low-dimensional antimony binary compounds.

structure type

space group

net type

properties

SmSb2 (Ln = La−Nd)

Cmca

rectangular

LnNi1−xSb2 (Ln = Y, Gd−Er) CeMSb2 (M = Mn, Fe, Ni, Pd, Cu, Zn)

P4/ nmm P4/ nmm

square

RAgSb2 (R = Y, La−Nd, Sm, Gd−Tm) LnNiSb3 (Ln = Ce, Pr, Nd, Sm) Sr1−yMn1−zSb2 (y, z < 0.1) Ca1−xLaxFeAs2

P4/ nmm Pbcm

buckled

Pnma

zigzag

La − Large MR;39 CDW in La1−xCexSb242 MR above 100% for Y, Dy, and Ho50 Mn orders ferromagnetically at 130 K51 MR ∼ 6000% for Sm; Dy metamagnetic52 Kondo behavior Ce;43 Pr, Nd, Sm AFM44 topological semimetal53

P21

zigzag

square square

superconducting at 34 K for x = 0.154

1.4. Antimonide Building Blocks

The orthorhombic, quasi-2D SmSb2 structure type38 can serve as a foundation for building low-dimensional materials that we can synthesize in bulk. As shown in Figure 3, this structure

antimony net type and highlight the properties of the compounds in this table. The antimony net motifs emphasized in this paper are the two most closely related to the SmSb2 structure type: rectangular nets and square nets. However, antimony bonds can also produce buckled nets43,44 and zigzag type chains45 in low-dimensional materials, as well as puckered nets as seen in the La6MnSb15 structure type that produce 3D materials.46−48 Other 3D and low-dimensional materials comprised of antimony nets that are not necessarily built from the SmSb2 structure type have been described elsewhere.49 Figure 4 displays some of the different net types observed in compounds with LnSb2 scaffold.

2. TETRAHEDRAL TRANSITION METAL−ANTIMONY NETWORKS Figure 5 illustrates the insertion of MSb4 (M = transition metal) tetrahedral slabs into the SmSb2 structure type leading to the HfCuSi2 structure type.55 The structure type consists of antimony square nets capped by rare earth elements, separated by tetrahedral slabs, which is stable for lanthanides and transition metals.56 The incorporation of transition metals is strongly influenced by the size of the lanthanides. For example, the nickel analogues are only stabilized for the latter rare earths, while mid-transition metal analogues are stabilized for most lanthanides. The highly anisotropic LnAgSb2 (Ln = Y, La−Nd, Sm, Gd−Tm) exhibits large magnetoresistance ranging from 90% to over 60000% along the c axis,52 and the antimony net has been attributed to the emergence of a magnetoresistance up to 2500% for LaAgSb2.57 We have endeavored to further elucidate the relationship between the transition metal sublattice and the antimony network in the HfCuSi2 structure type and grew single crystals of LnNi1−xSb2 (Ln = Y, Gd−Er) using the self-flux method to produce single crystals up to 2−5 mm along the ab-direction.50 The compounds order anti-

Figure 3. SmSb2 structure type is comprised of rectangular antimony sheets with Ln atoms capping the square nets.

consists of rare earth ions capping square nets and forming a square antiprismatic environment. Large magnetoresistance, the change in resistivity with an applied magnetic field, has been discovered for several analogues of the highly anisotropic LnSb2 (Ln = La−Nd, Sm) and notably, over 50000% for the H∥c direction of SmSb2.39 LaSb2 exhibits nonsaturating magnetoresistance up to 45 T40 and exhibits a crossover from a 2D superconductor to a 3D superconductor after application of uniaxial pressure.41 Substituting the La with Ce in La1−xCexSb2 14


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Figure 4. Three arrangements of antimony nets are displayed. The SmSb2 structure type possesses rectangular nets, the LnM1−xSb2 and La2Fe4Sb5 structures possess square nets, and the CeNiSb3 structure type is comprised of buckled nets.

Figure 5. An illustration of a tetrahedral slab inserted into the SmSb2 structure type.

and 9 T, and La(Cu0.2Ni0.8)ySb2 was shown to exhibit positive magnetoresistance of ∼300% at 3 K and 9 T along the c axis. Another recent compound to highlight is the magnetic topological semimetal phase Sr1−yMn1−zSb2 (y, z < 0.1).53 The symmetry of this compound is intriguing because the antimony nets are distorted to form a zigzag pattern. Sr1−yMn1−zSb2 (y, z < 0.1) orders ferromagnetically at 565 K, followed by a canting of Mn spins to order antiferromagnetically below 304 K. The stoichiometry is pertinent to the magnetic behavior. For y ∼ 0.08 and z ∼ 0.02, the magnetic moment of Mn is ∼0.1−0.6 μB/Mn. However, with small changes of y ∼ 0.01−0.04, z ∼ 0.04−0.1, the magnetic moment changes by 2 orders of magnitude (∼0.004−0.006 μB/Mn). In contrast to Sr1−yMn1−zSb2, the structurally related BaMnSb2 possesses undistorted Sb square nets as a consequence of

ferromagnetically due solely to the rare earth magnetic sublattice. LnNi1−xSb2 is metallic and the Y, Dy, and Ho analogues exhibit positive magnetoresistance reaching above 100% at 3 K and 9 T along the c axis. We also investigated the effects of incorporating two transition metals into the tetrahedral sublattice in single crystals of Ce(Cu1−xNix)ySb2 (y < 0.8).58 Polycrystalline samples of CeCuSb2 have been reported to be antiferromagnetic with a magnetoresistance of ∼12.5% at 4.5 K and 4.5 T.59,60 Upon substitution of Ni, metamagnetic transitions appear coincident with an increase in the distortion of the tetrahedra in the transition metal− antimony sublattice. The field dependent transitions are characterized by a sharp increase in magnetization appearing at ∼0.5 and 1 T. Single crystals of Ce(Cu1−xNix)ySb2 (x = 0.37 and 0.46) exhibit positive magnetoresistances above 70% at 3 K 15


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Figure 6. (a, b) Local environment of the edge sharing Fe2Sb2 tetrahedra in the La2Fe4Sb5 structure type and (c) the triangular network of Fe atoms. Red lines serve to guide the eye and emphasize the edge sharing tetrahedra in panel b. The antimony atoms are omitted in panel c for clarity.

Figure 7. An illustration of a geometrically frustrated subunit inserted into the SmSb2 structure.

frustration parameter (f ∼ 0.25) and 3D antiferromagnetism.66 Structurally similar to this is Yb2Pt2Pb, where Yb ions form ordered, tessellated triangles and rectangles.67 Yb2Pt2Pb is quasi-2D and exhibits strong anisotropy with χ[100]/χ[001] ∼ 30 and f ∼ 100 when the field is perpendicular to the layers. So far, we have discussed compounds that possess rare earth elements in frustrated environments. We now highlight the compounds CaMn2Sb268 and La21Fe8Sn7C12,69 where the transition metal is geometrically frustrated. The antiferromagnetic insulator CaMn2Sb2 consists of Mn in a corrugated honeycomb with capping antimony atoms, which is an ideal candidate to study magnetic frustration between next-nearest neighbors.70 The recently discovered La21Fe8Sn7C12 consists of perfect tetrahedra of Fe atoms capped with carbon, which are isolated by a surrounding La/Sn framework.69 The magnetization data indicate that La21Fe8Sn7C12 exhibits spin glass behavior, which is a “freezing” of the spins in random orientations at a critical temperature. The coexistence of

strong interactions between the Ba ions and Sb nets and antiferromagnetically orders below 283 K. BaMnSb2 serves as an analogue to compare spin−orbit coupling in related compounds.61 Both Sr1−yMn1−zSb2 and BaMnSb2 exhibit promise as platforms for studying new quantum states of matter.

3. GEOMETRICALLY FRUSTRATED TRANSITION METAL−ANTIMONY NETWORKS The triangular lattice is the ideal candidate to study geometric frustration leading to unsatisfied spin-disordered states.62−64 Frustration is defined as f = |θCW|/TN, where θCW is the Curie temperature, TN is the transition temperature, and f is the frustration parameter,65 where a value greater than 10 signifies a strong frustration effect. The search for magnetically frustrated materials, especially intermetallic compounds, is ongoing and nontrivial. For example, the compound GdPtPb possesses a network of Gd forming triangular prisms but exhibits a low 16


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Accounts of Chemical Research perfectly frustrated Fe atoms and spin glass behavior is unusual since conventional models for spin glass behavior dictate that the Fe must be structurally disordered for spin glass behavior to emerge. Motivated by the possibility of inserting geometrically frustrated subunits (especially triangular transition metal units) into the LnSb2 scaffold, we turned our attention to the La2Fe4Sb5 structure type.71 This structure type possesses a rare earth magnetic sublattice and a transition metal magnetic sublattice, which can potentially lead to multiple magnetic transitions. Figure 6 shows the transition metal−antimony network of the La2Fe4Sb5 structure type, which consists of Fe tetrahedrally coordinated to Sb atoms forming a “doubled” tetrahedral slab. The Fe atoms are also within bonding distance of each other, forming nearly equilateral triangles and the potential for frustration. Figure 7 demonstrates the insertion of the geometrically frustrated slab into the SmSb2 structure type to produce the La2Fe4Sb5 structure type. Using Bi as an inert flux, we were able to grow single crystals of Ln2Fe4Sb5 (Ln = La−Nd, Sm) that could be oriented for susceptibility measurements (∼2 mm). We note a divergence between the field-cooled and zero-field-cooled magnetic susceptibility measurements and determine that the bifurcation is due to spin glass behavior emerging from the spin interactions in the transition metal sublattice. As part of our transition metal substitution studies on materials with the base SmSb 2 -type building unit, we grew single crystals of Pr2Fe4−xCoxSb5 (x < 2.3). As the concentration of Co increases, the magnetic susceptibility measurements show a transition from localized to itinerant magnetism as evidenced by an additional magnetic transition in Pr2Fe4−xCoxSb5 (x ∼ 2). Hence, this compound is ideal to study the interplay of itinerant and local-moment magnetism in a lanthanidecontaining system. The exact nature of the relationship between the rare earth ions, transition metal network, and antimony square nets is the subject of ongoing research. Like CaMn2Sb268 and La21Fe8Sn7C12,69 the La2Fe4Sb5 structure type possesses transition metals in a geometric arrangement that has the potential for frustration with the added benefit of being built up from the SmSb 2 structure type with Sb-square nets. Furthermore, the La2Fe4Sb5 structure type is ideal to study the role of the dimensionality and the coupling of magnetic order with the antimony square nets.

It is important to consider that the discovery of new layered intergrowth compounds may be possible by using structural subunits as building blocks. In this Account, we have considered tetrahedral subunits and geometrically frustrated subunits as possible insertion layers, but there are other layers to consider such as an octahedrally coordinated transition metal−antimony slab. We are left with the question, “Can one take any two binary building blocks with similar lattice parameters to construct completely new intergrowth compounds?” If so, an entire new phase space of materials that can lead to exotic and most likely complex electrical and magnetic properties that can be tuned solely by selecting the desired structural subunits could be possible.

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AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

Julia Y. Chan: 0000-0003-4434-2160 Notes

The authors declare no competing financial interest. Biographies Katherine A. Benavides obtained her B.S. in Chemistry from Auburn University and is currently a doctoral student under the guidance of Prof. Julia Y. Chan at the University of Texas at Dallas. Her research is centered on antimonides, particularly those that contain antimony nets, and intermetallic compounds featuring structural disorder. Iain W. H. Oswald received his Ph.D. under the direction of Prof. Julia Y. Chan at the University of Texas at Dallas in 2017. His research interests include magnetocaloric and optical materials and elucidating structural disorder in complex intermetallic compounds and correlating physical properties. In addition, he has synthesized novel low-dimensional materials to exploit their anisotropic electronic properties. Julia Y. Chan received a Ph.D. under the direction of Prof. Susan Kauzlarich at the University of California at Davis in 1998. She then held a National Research Council postdoctoral fellowship at the Materials Science Division of the National Institute of Standards and Technology from 1998 to 2000. She is currently a Professor of Chemistry & Biochemistry at the University of Texas at Dallas and an associate editor for Science Advances.

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4. BEYOND ANTIMONIDES Tellurium containing compounds also form square nets, such as those observed in the rare earth telluride compounds LnTe2,72 LnTe3,73 and Ln2Te5.74 Each of these compounds feature corrugated LnTe layers sandwiched by square nets of tellurium. To compensate for deficiencies in valency associated with the Te ions, Te-square nets can become distorted leading to the formation of chains, single atoms, or other complex Teconnected shapes within the square nets.75,76 Pb3−xSb1+xS4Te2−δ, for example, exhibits a charge density wave at room temperature as a direct result of the structural distortion of the Te nets.77 Bismuth square nets have been attributed to large spin−orbit coupling, and as such, the quantum Hall effect of CaMnBi2 and SrMnBi2 is attributed to the bismuth nets.78,79 Similarly, when oxygen is doped in the Bi2− square nets of Y2O2Bi, superconductivity emerges as a result of increased interlayer distances and spin−orbit coupling.80

ACKNOWLEDGMENTS K.A.B. holds an American Fellowship from the American Association of University Women. We acknowledge NSF DMR-1360863 and DMR-1700030 for partial support of this project.

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REFERENCES

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