Nonlinear optical inorganic sulfates: The improvement of the phase matching ability driven by the structural modulation

Shang, Yanran; Xu, Jun-Yu; Sha, Hongyuan; Wang, Zujian; He, Chao; Su, Rongbing; Yang, Xiaoming; Long, Xifa

doi:10.1016/j.ccr.2023.215345

Cited by 16 publications

(9 citation statements)

References 98 publications

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“…Generally, for an NLO crystal, appropriate birefringence (0.05–0.10@1064 nm) is required to guarantee the frequency-doubling conversion efficiency of the fundamental laser, since a birefringence that is too small will shrink the phase-matching range of a crystal, while an excessive one will produce a walk-off effect. , The birefringence test was carried out by using a cross-polarization microscope with a white light source. A Zn-LT thin plate with a thickness of 17.3 μm was picked for test.…”

Section: Resultsmentioning

confidence: 99%

Two Acentric Zn-Based l-Tartrates with Moderate Second Harmonic Generation Responses and Large Birefringence

Yu,

Wan,

Yang

et al. 2024

Inorg. Chem.

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The discovery of novel organic−inorganic hybrid nonlinear optical (NLO) crystal materials holds great potential in advancing laser science and technology as they offer a wide range of benefits including easy synthesis, structural versatility, and high hyperpolarizability. Herein, the integration of L-tartaric acid (L-C 4 H 6 O 6 ) and ZnSO 4 gave rise to two acentric Zn-based organic− inorganic hybrid crystals, namely, Zn 2 (, water molecule, or [SO 4 ] tetrahedron. Interestingly, they possess moderate secondorder NLO effects of 0.28 × KH 2 PO 4 (Zn-LT) and 0.57 × KH 2 PO 4 (Zn-LTS), large birefringence of 0.075 (Zn-LT) and 0.069 (Zn-LTS), suggesting that the introduction of [SO 4 ] groups with intrinsically weak polarizability and weak optical anisotropy induces the enhancement of the NLO effect while without reducing birefringence much. In addition, both of them display UV cutoff edges near 210 nm, indicating their potential as NLO crystals applied in the UV and solar-blind region.

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Section: Resultsmentioning

confidence: 99%

Two Acentric Zn-Based l-Tartrates with Moderate Second Harmonic Generation Responses and Large Birefringence

Yu,

Wan,

Yang

et al. 2024

Inorg. Chem.

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“…Sulfate crystals are receiving increasing attention in the research of optoelectronic functional materials due to their tetrahedral building unit, wide optical band gap, short UV cutoff edge, and easy crystal growth. , The long overlooked SO 4 tetrahedron has been found to be a good type of functional unit used in nonlinear optical materials. , However, the highly symmetrical SO 4 groups often result in a low birefringence of sulfates, such as LiNH 4 SO 4 (0.0078@532 nm) and LiKSO 4 (0.00025@546 nm) . Such a small birefringence prevents many sulfates from achieving phase matching by a direct second-harmonic generation process, hindering the application of sulfate crystals. , …”

Section: Introductionmentioning

confidence: 99%

Hg₄(Te₂O₅)(SO₄): A Giant Birefringent Sulfate Crystal Triggered by a Highly Selective Cation

Li,

Hu,

et al. 2024

J. Am. Chem. Soc.

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Sulfate crystals are often criticized for their low birefringence. The small anisotropic SO 4 group is becoming the biggest bottleneck hindering the application of sulfates in optical functional materials. In this study, we report a new method to significantly enhance the birefringence of sulfates. The title compound increases the birefringence recording of sulfates to 0.542@546 nm, which is significantly larger than that of the commercial birefringent crystal of TiO 2 (0.306@546.1 nm). At the infrared wavelength, the birefringence of Hg 4 (Te 2 O 5 )(SO 4 ) can be up to 0.400@1064 nm, which is also much larger than the infrared birefringent crystal of YVO 4 (0.209@1064 nm). In addition, it also has a wide transparency range, high thermal stability, and excellent environmental stability, making it a potential birefringent material. Hg 4 (Te 2 O 5 )(SO 4 ) features a novel two-dimensional layered structure composed of [Hg 4 (Te 2 O 5 )] 2+ layers separated by isolated (SO 4 ) 2− tetrahedra. This compound was designed by introducing a highly selective cation in a tellurite sulfate system. The low valence low coordination cations connect with tellurite groups only, making the sulfate isolated in the structure. The steric repulsive action of the isolated SO 4 tetrahedra may regulate the linear and lone pair groups arranged in a way that favors large birefringence. This method can be proven by theoretical calculations. PAWED studies showed that the large birefringence originated from the synergistic effect of (Hg 2 O 2 ) 2− , (Te 2 O 5 ) 2− , and (SO 4 ) 2− units, with a contribution ratio of 42.17, 37.92, and 19.88%, respectively. Our work breaks the limitation of low birefringence in sulfates and opens up new possibilities for their application as birefringent crystals.

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“…The representative crystals are K(H 3 C 3 N 3 O 3 )(NO 3 ), LiZn(OH)CO 3 , CaZn 2 (BO 3 ) 2 , and so on. Nonetheless, achieving a broad and deep ultraviolet (DUV) transparency window has been challenging, primarily due to constraints imposed by the π-conjugate effect, particularly arising from the terminal hanging oxygens. , Compared with π-conjugated groups, non-π-conjugated groups have larger highest occupied molecular orbital–least unoccupied molecular orbital band gaps, which is favorable for obtaining the wider DUV transparency window. The representative crystals are BPO 4 , LiCs 2 PO 4 , LiKSO 4 , and so on.…”

Section: Introductionmentioning

confidence: 99%

AYSO₄F₂ (A = K, Rb): [YO₄F₄] Polyhedra Enhancement of Birefringence in Non-π-Conjugated Sulfate Systems

Wu,

Li,

Hou

et al. 2024

Inorg. Chem.

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A mild hydrothermal method was employed to successfully synthesize two new sulfate fluorides, namely, AYSO 4 F 2 (A = K, Rb). They are isomorphic, and both contain [YO 4 F 4 ] polyhedra and [SO 4 ] tetrahedra in the structure. Theoretical calculations and experimental tests show that AYSO 4 F 2 (A = K, Rb) have large band gaps (7.79 and 7.82 eV) and moderate birefringence (0.015 and 0.02 @ 546.1 nm), with significantly enhanced birefringence and band gaps as compared to that of the single alkali metal sulfates A 2 SO 4 (A = K, Rb). Furthermore, theoretical calculations show that [YO 4 F 4 ] polyhedra are the main reason for the band gap and birefringence enhancement. This work contributes to the advancement of structural chemistry in the field of rare-earth sulfates, offering a novel approach for the design of sulfates characterized by large birefringence.

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Nonlinear optical inorganic sulfates: The improvement of the phase matching ability driven by the structural modulation

Cited by 16 publications

References 98 publications

Two Acentric Zn-Based l-Tartrates with Moderate Second Harmonic Generation Responses and Large Birefringence

Two Acentric Zn-Based l-Tartrates with Moderate Second Harmonic Generation Responses and Large Birefringence

Hg₄(Te₂O₅)(SO₄): A Giant Birefringent Sulfate Crystal Triggered by a Highly Selective Cation

AYSO₄F₂ (A = K, Rb): [YO₄F₄] Polyhedra Enhancement of Birefringence in Non-π-Conjugated Sulfate Systems

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Nonlinear optical inorganic sulfates: The improvement of the phase matching ability driven by the structural modulation

Cited by 16 publications

References 98 publications

Two Acentric Zn-Based l-Tartrates with Moderate Second Harmonic Generation Responses and Large Birefringence

Two Acentric Zn-Based l-Tartrates with Moderate Second Harmonic Generation Responses and Large Birefringence

Hg4(Te2O5)(SO4): A Giant Birefringent Sulfate Crystal Triggered by a Highly Selective Cation

AYSO4F2 (A = K, Rb): [YO4F4] Polyhedra Enhancement of Birefringence in Non-π-Conjugated Sulfate Systems

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Product

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Hg₄(Te₂O₅)(SO₄): A Giant Birefringent Sulfate Crystal Triggered by a Highly Selective Cation

AYSO₄F₂ (A = K, Rb): [YO₄F₄] Polyhedra Enhancement of Birefringence in Non-π-Conjugated Sulfate Systems