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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
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Molecular construction using (C3N3O3)3- anions:
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analysis and prospect for inorganic metal cyanurates
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nonlinear optical materials
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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
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Technology of Chinese Academy of Sciences, Technical Institute of Physics and Chemistry,
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Chinese Academy of Sciences, Beijing 100190, PR China.
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‡ University of Chinese Academy of Sciences, Beijing 100190, PR China
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§ Department of Physics, Tamkang University, New Taipei 25137, Taiwan
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Corresponding Author
12
Ming-Hsien Lee (E-mail:
[email protected] )
13
Zheshuai Lin (E-mail:
[email protected] )
14 15
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ABSTRACT
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Molecular construction using good optically active microscopic units is vital to efficiently
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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
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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-
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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
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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
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SHG coefficients (d22=4.1×KDPd36), large birefringence (∆n=0.12 @ 1064nm) and high damage
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threshold.6 Recently, BBO crystals have been also used for pairs of entangled photons generation
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in quantum information experimental system11 and micro-/nanoscale optical modulation.12 It is
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well known that the excellence of NLO properties in BBO comes from the planar (B3O6)3- anions,
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a typical delocalized π-conjugated anionic group. First principles calculations demonstrated that
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the contribution of (B3O6)3- units to SHG coefficients for BBO is more than 80%, while to
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birefringence is more than 85%.13 This strongly suggests that the molecular construction using
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large π-conjugated groups would be a very efficient way for searching new materials with good
11
NLO performance.
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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
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(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
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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
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synthesizing several non-centrosymmetric (NCS) metal cyanurates, including Ca3(C3N3O3)2
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(CCY),25 α-Sr3(C3N3O3)2 (α-SCY),26 β-Sr3(C3N3O3)2 (β-SCY),27 and Eu3(C3N3O3)2 (ECY).27
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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
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intended as a flux medium for crystal growth.29 Especially, CCY, α-SCY and β-SCY exhibited
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stronger SHG response than that of BBO under 800 nm irradiations in the primary
20
experiments.25-27,
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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
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of the inorganic metal cyanurates NLO materials is also very lack.
29
This, actually, implies that the (C3N3O3)3- group, the FBB in metal
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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
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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.
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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)
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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
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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
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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
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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-
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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
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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
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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)
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Exp
Cal
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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
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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
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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.
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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
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This work was supported by China “863” project (No. 2015AA034203) and the National
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Natural Science Foundation of China under Grant No. 91622118, 91622124, 11174297 and
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51602318. Ming-Hsien Lee thanks equipment support from KeyWin. Inc. and Database service
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of NCHC.
17
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For Table of Contents Use Only
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Molecular construction using (C3N3O3)3- anions: analysis and prospect for inorganic metal
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cyanurates nonlinear optical materials
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Fei Liang, †,‡ Lei Kang, † Xinyuan Zhang, † Ming-Hsien Lee, *,§ Zheshuai Lin, *,†,‡ and Yicheng Wu †
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† Center for Crystal Research and Development, Key Lab Functional Crystals and Laser Technology of Chinese Academy of
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Sciences, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, PR China.
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‡ University of Chinese Academy of Sciences, Beijing 100190, PR China
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§ Department of Physics, Tamkang University, New Taipei 25137, Taiwan
9 10 11
Synopsis
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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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