Molecular Construction Using (C3N3O3)3â Anions: Analysis and

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Molecular construction using (C3N3O3)3- anions: analysis and prospect for inorganic metal cyanurates nonlinear optical materials Fei Liang, Lei Kang, Xinyuan Zhang, Ming-Hsien Lee, Zheshuai Lin, and Yicheng Wu Cryst. Growth Des., Just Accepted Manuscript • Publication Date (Web): 01 Jun 2017 Downloaded from http://pubs.acs.org on June 4, 2017

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Crystal Growth & Design

1

Molecular construction using (C3N3O3)3- anions:

2

analysis and prospect for inorganic metal cyanurates

3

nonlinear optical materials

4

Fei Liang, †,‡ Lei Kang, † Xinyuan Zhang, † Ming-Hsien Lee, *,§ Zheshuai Lin, *,†,‡ and

5

Yicheng Wu †

6

† Center for Crystal Research and Development, Key Lab Functional Crystals and Laser

7

Technology of Chinese Academy of Sciences, Technical Institute of Physics and Chemistry,

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Chinese Academy of Sciences, Beijing 100190, PR China.

9

‡ University of Chinese Academy of Sciences, Beijing 100190, PR China

10

§ Department of Physics, Tamkang University, New Taipei 25137, Taiwan

11

Corresponding Author

12

Ming-Hsien Lee (E-mail: [email protected] )

13

Zheshuai Lin (E-mail: [email protected] )

14 15

ACS Paragon Plus Environment

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ABSTRACT

2

Molecular construction using good optically active microscopic units is vital to efficiently

3

explore good nonlinear optical (NLO) materials, a type of important optoelectronic functional

4

materials. In this work, we highlight the planar (C3N3O3)3- anion, the main fundamental building

5

block in inorganic metal cyanurates, as an outstanding candidate of building blocks for NLO

6

materials. Several non-centrosymmetric metal cyanurates containing the (C3N3O3)3- groups are

7

studied by the first-principles calculations for the first time. It is shown that these materials

8

possess wide bandgaps (Eg > 5.5 eV), high SHG coefficients (d22>2×BBO) and large

9

birefringence values (∆n>0.1), thus have good potentials in the ultraviolet NLO applications.

10

Moreover, the key role of the (C3N3O3)3- groups to the good NLO performance in the cyanurates

11

is elucidated. Based on the first-principles analysis, some possible searching directions of good

12

NLO materials containing (C3N3O3)3- groups are proposed.

13 14

INTRODUCTION

15

Nonlinear optical (NLO) crystals have very important applications in many advanced

16

scientific and technological fields, such as laser frequency conversion,1 biological tissue

17

imaging,2 environmental monitoring,3 and minimally invasive medical surgery.4 In the last three

18

decades, the search for NLO materials has made great progress,5 and some outstanding

19

ultraviolet (UV) and deep-UV inorganic NLO crystals have been discovered, including β-

20

BaB2O4 (BBO),6 LiB3O5 (LBO),7 CsLiB6O10 (CLBO)8 and KBe2BO3F2 (KBBF).9 In particular,

21

BBO crystal has been used widely in second-, third-, fourth-, and fifth-harmonic generation, as


2

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well as in optical parametric oscillators (OPO) and optical parametric amplifiers (OPA),10 owing

2

to its short UV cutoff edge (190 nm), high transparency from 0.2 to 2.6 µm (T > 50%), high

3

SHG coefficients (d22=4.1×KDPd36), large birefringence (∆n=0.12 @ 1064nm) and high damage

4

threshold.6 Recently, BBO crystals have been also used for pairs of entangled photons generation

5

in quantum information experimental system11 and micro-/nanoscale optical modulation.12 It is

6

well known that the excellence of NLO properties in BBO comes from the planar (B3O6)3- anions,

7

a typical delocalized π-conjugated anionic group. First principles calculations demonstrated that

8

the contribution of (B3O6)3- units to SHG coefficients for BBO is more than 80%, while to

9

birefringence is more than 85%.13 This strongly suggests that the molecular construction using

10

large π-conjugated groups would be a very efficient way for searching new materials with good

11

NLO performance.

12

According to valance bond theory,14 some key points about large π-conjugated groups should

13

be clarified: (i) all atoms should be in the planar or essentially planar configuration; (ii) all atoms

14

should provide parallel p orbitals by each other; (iii) the number of p electrons should be less

15

than twice the number of conjugated p orbitals; (iv) the overlap between pπ-pπ orbitals should be

16

large as much as possible, which means large electron population of the conjugated π-orbital

17

systems. Note that the large π-conjugated (B3O6)3- groups are very rarely found: the planar

18

(B3O6)3- units only exist in BBO,6 KBO2,15 Ba2Mg(B3O6)2,16 CsZn2B3O7,17, 18 γ-KBe2B3O7,19 and

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LiB6O9F.20 This urges us to search other types of large π-conjugated groups as the fundamental

20

building blocks (FBBs) for inorganic NLO materials, especially for those possessing high SHG

21

effect and large birefringence.

22 23

On the base of a thorough survey in the inorganic crystal structure database (ICSD, 2016-2, Version

1.9.8,

by

Fachinformationszentrum

Karlsruhe,

Germany),

we

find

that


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cyclotrinitridoborate (B3N6)9-, oxonitridoborate (B3N3O3)6- and cyanuric (C3N3O3)3- units are

2

possible candidates.21-23 Nonetheless, the compounds containing (B3N6)9- unit are usually

3

crystallized in centrosymmetric space group,21 and (B3N3O3)6- unit is distorted from planar

4

geometric configuration.22 In comparison, (C3N3O3)3- anion is formed by three linear (OCN)-

5

units linked with cyclic (C3N3) moiety and three exocyclic oxygen atoms,24 which is isoelectric

6

with (B3O6)3- units, and contains large delocalized π-conjugated electron orbitals. Till now, the

7

organic derivatives of cyanuric acid have found many industrial applications, but its inorganic

8

derivatives have not yet been paid wide attention as NLO materials.24 To the best of our

9

knowledge, only one research group (Meyer et al.) has focused on this system and succeeded in

10

synthesizing several non-centrosymmetric (NCS) metal cyanurates, including Ca3(C3N3O3)2

11

(CCY),25 α-Sr3(C3N3O3)2 (α-SCY),26 β-Sr3(C3N3O3)2 (β-SCY),27 and Eu3(C3N3O3)2 (ECY).27

12

These metal cyanurates were prepared by oxygen-free high temperature solid-state reactions

13

between metal chlorides and Li(OCN)/K(OCN) at temperatures of around 500 °C.28 DSC

14

measurements showed that SCY is a congruent melting compound with onset points at 628 °C

15

for melting and 634 °C for recrystallization.26 So it is possible to grow large size SCY crystals by

16

Bridgman methods. In addition, Meyer has given a binary phase diagram of SCY and K(OCN)

17

with different molar ratios, thus suggesting that this simple system with excess K(OCN) can be

18

intended as a flux medium for crystal growth.29 Especially, CCY, α-SCY and β-SCY exhibited

19

stronger SHG response than that of BBO under 800 nm irradiations in the primary

20

experiments.25-27,

21

cyanurates, should be suitable as the outstanding NLO active microscopic unit. However, up to

22

now the importance of (C3N3O3)3- group has not attracted attention, and the analysis and prospect

23

of the inorganic metal cyanurates NLO materials is also very lack.

29

This, actually, implies that the (C3N3O3)3- group, the FBB in metal


4

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In this work, we take β-SCY and CCY as the representative examples in the NCS inorganic

2

cyanurates to demonstrate the key role of (C3N3O3)3- anions to their NLO performance. Based on

3

the first principles electronic structure calculations, the optical properties in β-SCY and CCY are

4

obtained, which are in good agreement with the available experimental results. The dominant

5

contribution of (C3N3O3)3- groups to SHG effect is elucidated by the real-space atom-cutting

6

method and the SHG-density analysis. Moreover, the prospect of the NLO materials containing

7

(C3N3O3)3- groups are discussed.

8 9 10

Figure 1. Crystal structures of β-SCY (a), BBO (b). Comparison of (C3N3O3)3− anions in β-SCY and (B3O6)3− anions in BBO is shown in (c).


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COMPUTATIONAL METHODS

2

CASTEP package30 is employed to calculate the electronic band structures as well as linear

3

and nonlinear optical properties of the metal cyanurates. The optimized norm-conserving

4

pseudopotentials31 and GGA-PBE functional32 are used to simulate ion-electron interactions for

5

all constituent elements and exchange-correlation potential, respectively. A kinetic energy cutoff

6

of 880 eV is chosen with Monkhorst-Pack k-point meshes spanning less than 0.04/Å3 in the

7

Brillouin zone.33 The scissors operator correction34 is adopted to calculated linear and nonlinear

8

optical properties.

9

The second order susceptibility χ() and SHG coefficient ( =1/2 () ) are calculated using

10

an expression originally proposed by Rashkeev et al35 and developed by Lin et al:13 χ = χ (VE) + χ (VH) + χ (two bands)

(1)

11

where χ (VE), χ (VH) and χ (two bands) denote the contributions from virtual-electron

12

(VE) processes, virtual-hole (VH) processes and two band processes, respectively. Moreover, the

13

real-space atom-cutting method and the SHG-density analysis developed in our group36 are used

14

to analyze and elucidate the microscopic origins of optical properties. (More computational

15

method details see Supporting Information).

16

RESULTS AND DISCUSSION

17

The crystal structures of β-SCY and CCY are isotypic to that of BBO crystallizing with the

18

NCS R3c space group (Figure 1a and 1b).25, 27 They contain planar (C3N3O3)3- cyanurate rings

19

that formed by the cyclic (C3N3) moiety and three exocyclic oxygen atoms. There are two

20

crystallographically distinct cyanurate rings in β-SCY and they are isoelectronic and isostructural


6

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1

to the (B3O6)3- units in BBO. These cyanurate anions stack on top of each other along the c-axis

2

to form columns following the similar motif of hexagonal closest packing, whereas alkaline-

3

earth metal cations locating in tunnels between cyanurate columns.

4

For simplicity, the structure of (C3N3O3)3- groups in β-SCY is discussed in detail as a

5

representative. As shown in Figure 1c, the bond lengths of the (C3N3O3)3− rings in SCY are

6

slightly shorter than those of cyanuric acid molecule37 (C-N bonds:1.37 Å, 1.35 Å; C-O bonds:

7

1.24 Å ), showing a structural change takes place due to ionization. In addition, the interatomic

8

distances in cyanurate rings are shorter than that of oxoborate (B3O6)3- anions, indicating the

9

larger overlapping between C 2p, N 2p and O 2p orbitals, which results in stronger pπ-pπ

10

interaction in the (C3N3O3)3- anion. Furthermore, the C atom (2s22p2) has one more electron

11

compared with B atom (2s22p1). So, B atom only provides an empty pz orbital, otherwise, C atom

12

can provide a pz orbital as well as an extra p electron. This is also favourable for obtaining

13

stronger π-conjugated interaction in (C3N3) ring than that in (B3O3) ring. Accordingly, it is

14

expected that the microscopic susceptibility of (C3N3O3)3- groups would be larger than that of

15

(B3O6)3- units.

16

The structural parameters of β-SCY, CCY and BBO are summarized in Table S1, which

17

offers a comparison of our calculated data with experimental results found in the literature. The

18

agreement between the lattice constants calculated in the present work and those from

19

experiments at ambient pressure is very good. It should be noted that the GGA-obtained lattice

20

constant is slightly greater than the experimental values, which is a common observation for this

21

type of calculation. Owing to larger radius of Sr2+, β-SCY have larger unit cell volume and lower

22

spatial density of (C3N3O3)3- groups than that of CCY, thus may lead to some influence on

23

optical properties owing to “Volume Effect”, just as that in ABBF family (A=K, Rb, Cs).38


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1

The GGA electronic band structures of β-SCY and CCY along the lines of high symmetry

2

points in the Brillouin zone, are displayed in Figure 2a and 2c. The valance band maximum

3

(VBM) and conduction band minimum (CBM) positions of β-SCY locate at Γ and F points,

4

respectively, while those of CCY both locate at Brillouin zone center (Γ point). Accordingly, β-

5

SCY has an indirect bandgaps while CCY has a direct band gap. The hybrid functionals (HSE06)

6

calculations show that the band gaps in β-SCY and CCY are 5.57 eV (UV absorption cutoff ~

7

222 nm) and 5.63 eV (~ 220 nm), respectively. These values are consistent with the previous

8

density functional theory results that the energy gaps of organic cyanuric acid molecules are

9

5.53-5.56 eV.39 (The detailed discussion on band gap calculations see Table S2). Interestingly,

10

quite a few non-bonding states (i.e., dangling bonds) are presented on the terminal O atoms in

11

(C3N3O3)3- groups. These electronic states can be eliminated by forming the strong covalent

12

bonds with the cations such as B, Be, Al,40 and the bandgap of compound can be extended to

13

deep-UV region (λcutoff < 200 nm).

14

The partial density of state (PDOS) projected on the constitutional atoms of β-SCY and CCY

15

is shown in Figure 2b, 2d and Figure S1. Clearly, the upper part of the VB (−10 to 0 eV)

16

consists of C 2p, N 2p and O 2p orbitals, and the strong hybridization between oxygen and the

17

neighbor C atoms is exhibited. However, the VBM (−2 to 0 eV) is exclusively occupied by O 2p

18

and N 2p orbitals. The CBM contains the orbitals of all atoms in β-SCY and CCY while C and O

19

atoms make a major contribution. Since the optical effects of a crystal are mainly determined by

20

the optical transition between the electronic states close to the bandgap,41 it is anticipated that

21

they are dominantly contributed from the (C3N3O3)3- groups. Electron density map (Figure S2)

22

exhibits that the charge densities strongly localize around the (C3N3O3)3- groups, so it is not

23

surprising that the anionic group contributes much more to the optical response than alkaline-


8

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1

earth metal does. In addition, the valancy electrons of Sr atoms have obvious overlap with O and

2

C atoms in (C3N3O3)3- groups, while the electron populations of Ca atoms are relatively more

3

local. This can be attributed to large-radius 3d orbitals of Sr atoms (Figure S1). Accordingly, we

4

expect that alkaline-earth metal cations will also make a weak influence on optical properties of

5

metal cyanurates.

6 7

Figure 2. Band structure and total/partial electron density of states of β-SCY (a,b) and CCY

8

(c,d), the red dot line represents the Fermi level.

9 10

Taking β-SCY and CCY as example, they are negative uniaxial crystal because of no>ne. The

11

Z dielectric axis is superposed on the c crystallographic axis and the XY principal plane is

12

parallel to the ab plane. Figure 3 is the dispersion of the calculated linear refractive indices of β-

13

SCY and CCY. In the region of 250−2000 nm, the calculated birefringence is about 1.20 −0.35.

14

In the region of 250−2000 nm, the calculated birefringence is about 1.20 −0.35. These


9


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Page 10 of 22

1

birefringence values are much larger than that of BBO (e.g., at 589.3 nm, β-SCY: 0.374, CCY:

2

0.372 vs. BBO: 0.118).6 The large birefringence is very favourable for achieving the phase-

3

matching condition in SHG process. Indeed, the shortest phase-matching wavelengths in both β-

4

SCY and CCY can arrive at their UV absorption cutoffs: these compounds are very feasible to

5

generate the fourth harmonic generation (@266 nm) of Nd:YAG laser. As one may know, the

6

birefringence value of crystal is strongly dependent on the anisotropic polarizability. For planar

7

π-conjugated (C3N3O3)3- groups, the out-of-plane polarizability is dominated by delocalized pπ-pπ

8

orbitals while in-plane polarizability is dominated by sp2 hybrid σ-bonds between C and N atoms

9

or C and O atoms. Every C and N atom can provide a non-bond pz electron, forming into a large

10

π-conjugated orbital, thus resulting in strong anisotropy between the c axis and ab plane.

11

The birefringence values of β-SCY and CCY are also larger than those of common

12

birefringence crystals, including calcite crystal (0.171@633 nm)42 and α-BBO (0.122@532

13

nm),43 which suggests that metal cyanurates can also be used as a kind of promising material for

14

polarized components applications in UV region.

15


10

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1

Figure 3. Dispersion of the linear refractive indices for β-SCY (a) and CCY (b) calculated by

2

GGA-PBE functional

3

According to anion group theory,44 large NLO effects can be expected in metal cyanurates if

4

the SHG-active (C3N3O3)3− building units occur in high spatial density and co-parallel alignment.

5

As measured by Meyer’ group, the SHG effect of β-SCY is stronger than that of CCY under the

6

same condition.29 This is in agreement with our calculated results, in which the d22 of β-SCY

7

increases by approximately 10% compared with CCY. In order to analyze the origin of optical

8

properties, the real-space atom-cutting results for the birefringence and SHG coefficients in β-

9

SCY, CCY and BBO are listed in Table 1, from which several conclusions can be summarized:

10

(i) The sum of the SHG coefficients from the respective covalent anions and cations is larger

11

than the original values. This can attributed to unlocal NLO effects, where the total SHG

12

coefficients cannot be considered as the simple summation of contributions from local electronic

13

subsystems.13 (ii) In the three crystals, the birefringence and SHG coefficient d11, dominantly

14

come from the strong planar covalent (C3N3O3)3- or (B3O6)3− groups (contribution > 75%). This

15

is in agreement with the conclusions of anion group theory and the strong covalent atomic

16

orbitals close to the bandgap in PDOS. (iii) Compared with alkaline metal ions in ABBF (A= K,

17

Rb, Cs) family,38 alkaline-earth metal cations make more contribution to optical properties in

18

metal cyanurates because of their higher electron density in VBM and CBM. However, the

19

contributions of the Sr2+ and Ca2+ cations to SHG coefficients and birefringence are still

20

negligibly small compared with planar (C3N3O3)3- groups.

21

Table 1. Calculated SHG coefficients and birefringence (∆[email protected] µm) of β-SCY and CCY (The

22

experimental and calculated values of BBO are listed as reference)


11


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Exp

Cal

Page 12 of 22

Real-space atom-cutting results

(original) β-SCY

(C3N3O3)3-

Sr2+

SHG d22

>BBOa

3.93

3.80

1.30

∆n

No data

0.36

0.32

0.081

(C3N3O3)3-

Ca2+

CCY SHG

>BBOa

3.46

3.45

0.31

No data

0.35

0.32

0.064

(B3O6)3-

Ba2+

d22 ∆n BBO

1

SHG d22

±1.6b

1.61

1.50

0.36

∆n

0.11b

0.12

0.116

0.001

a,

measured by powder Kurtz-Perry methods;25, 27 b, measured by single crystal6

2

Moreover, in order to investigate the origin of SHG coefficients visually, the SHG-densities of

3

occupied and unoccupied states in SCY are displayed in Figure 4 and Figure S3 as a

4

representative example. The SHG densities of electron states show that the contribution of

5

occupied orbitals to SHG is dominant, while those of unoccupied orbitals are very small. This is

6

consistent with the conclusion in BBO.36 For the occupied states (Figures 4(a)), the VE process

7

is mainly originated from the strong hybridization between N and O atomic orbitals in the

8

(C3N3O3)3- groups at VBM. In comparison, the VH process (Figures 4(c)) is primarily come

9

from the overlap of C and O 2p orbitals at CBM. The SHG densities around the alkaline earth

10

cations (Sr2+ and Ca2+) are negligibly small, and thus not shown in Figure 4.

11


12

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1 2

Figure 4. SHG weighted electron densities of β-SCY crystal (a) occupied and (b) unoccupied

3

VE process, (c) occupied and (d) unoccupied VH process along (C3N3O3)3- cross-section. The C,

4

N, and O atoms are represented by gray, blue and red balls, respectively.

5

On the basis of the above discussion, some opportunities for developing the NLO materials

6

containing (C3N3O3)3- groups seem ready to come out: (i) the trivalent metal cations, such as Y3+,

7

La3+ and Bi3+, are good metal elements for searching new NLO cyanurates. Especially, yttrium

8

cyanurate YC3N3O3·H2O possess perfect structural arrangement within perfect configuration of

9

co-planar (C3N3O3)3- anion units as well as ultra-high spatial density (see Figure S4).24 One may

10

find that the cyanurate anion is symmetrically surrounded by three yttrium cations, thus making a

11

large polarization of 2D layers. In addition, it should be paid attention to the cyanurate structure

12

similar to 2D organic topological insulators (TIs), such as Bi(C6H5)3 and Pb(C6H5)3,45 which may

13

exhibit some exciting optoelectronic properties. (ii) Other functional SHG-active groups could

14

been also added into the metal cyanurates, such as (BO3)3-, (B3O6)3-, (CO3)2-, (NO3)- etc. The

15

combination and cooperation of multi anions would provide a new way for finding strong SHG


13


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Page 14 of 22

1

response materials. In fact, some successful examples have been provided as the driving

2

inspiration,

3

Pb2(BO3)(NO3) (9.0×KDP).48 (iii) (C3N3O3)3- anion may be considered as a new functional group

4

for organic Terahertz (THz) NLO crystals. It is anticipated that this group would not only exhibit

5

large bandgap, relating to high LDT, but also be more compatible with organic chromophores. If

6

one could combine (C3N3O3)3- anions with the organic ionic groups in the known organic THz

7

crystals, such as methyl pyridine in DAST49 and DSTMS,50 some unprecedented semi-organic

8

NLO materials will be expected. (iv) Last but not least, BBO crystals have been widely used for

9

pairs of entangled photons generation by spontaneous parametric down-conversion in modern

10

quantum information experimental system.11 Similarly, SCY and CCY crystals would also have

11

possible applications in coherent entangled photons generation owing to their higher SHG

12

coefficients and larger birefringence compared with BBO.

13

CONCLUSION

such

as

Ba2(BO3)1−x(CO3)xCl1+x,46

Pb7O(OH)3(CO3)3(BO3)

(4.5×KDP),47

14

In summary, the ab initio calculations have been carried out to investigate the crucial role of

15

(C3N3O3)3- anions in determining the optical properties in organic metal cyanurates. It is shown

16

that these materials have good potentials in the ultraviolet NLO applications owing to wide

17

bandgaps (Eg > 5.5 eV), high SHG coefficients (d22>2×BBO) and large birefringence values

18

(∆n>0.1). Good agreement between experimental and theoretical results is obtained. Taking the

19

β-SCY and CCY as example, the delocalized π-conjugated orbitals of cyanuric anions are

20

highlighted and it makes the main contribution to large SHG effects and strong optical

21

anisotropy (contribution > 75%). The (C3N3O3)3- group can be regarded as an outstanding

22

fundamental building block for the molecular construction, which we believe has important

23

implications for the research and design of new materials with good NLO performances.


14

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1

ASSOCIATED CONTENT

2

Supporting Information

3

These materials are available free of charge via the Internet at http://pubs.acs.org. The

4

optimized lattice parameters, electronic band structure, electron density of states, electron density

5

map and weighted SHG-density of β-SCY and CCY (PDF)

6

AUTHOR INFORMATION

7

Corresponding Author

8

*E-mail: [email protected]

9

*E-mail: [email protected]

10

Notes

11

The authors declare no competing financial interest.

12

ACKNOWLEDGMENT

13

This work was supported by China “863” project (No. 2015AA034203) and the National

14

Natural Science Foundation of China under Grant No. 91622118, 91622124, 11174297 and

15

51602318. Ming-Hsien Lee thanks equipment support from KeyWin. Inc. and Database service

16

of NCHC.

17

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Page 20 of 22

1

For Table of Contents Use Only

2

Molecular construction using (C3N3O3)3- anions: analysis and prospect for inorganic metal

3

cyanurates nonlinear optical materials

4

Fei Liang, †,‡ Lei Kang, † Xinyuan Zhang, † Ming-Hsien Lee, *,§ Zheshuai Lin, *,†,‡ and Yicheng Wu †

5

† Center for Crystal Research and Development, Key Lab Functional Crystals and Laser Technology of Chinese Academy of

6

Sciences, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, PR China.

7

‡ University of Chinese Academy of Sciences, Beijing 100190, PR China

8

§ Department of Physics, Tamkang University, New Taipei 25137, Taiwan

9 10 11

Synopsis


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1

Based on the first-principles analysis, some good NLO materials containing (C3N3O3)3- groups

2

are proposed and they show excellent potentials in the ultraviolet NLO applications.


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Table of contents 101x104mm (300 x 300 DPI)


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Molecular Construction Using (C3N3O3)3â Anions: Analysis and

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