Perovskite ferroelectrics with prominent nonlinear optical absorption have attracted great attention in the field of photonics. However, they are traditionally dominated by inorganic oxides and exhibit relatively small nonlinear optical absorption coefficients, which hinder their further applications. Herein, we report a new organic-inorganic hybrid bilayered perovskite ferroelectric, (CHNH)(NHCHNH)PbBr (1), showing an above-room-temperature Curie temperature (∼322 K) and notable spontaneous polarization (∼3.8 μC cm). Significantly, the unique quantum-well structure of 1 results in intriguing two-photon absorption properties with a giant nonlinear optical absorption coefficient as high as 5.76 × 10 cm GW, which is almost two-orders of magnitude larger than those of mostly traditional all-inorganic perovskite ferroelectrics. To our best knowledge, 1 is the first example of hybrid ferroelectrics with giant two-photon absorption coefficient. The mechanisms for ferroelectric and two-photon absorption are revealed. This work will shed light on the design of new ferroelectrics with two-photon absorption and promote their potentials in the photonic application.
The non-π-conjugated sulfate system has long been overlooked as potential deep-UV nonlinear optical (NLO) materials. Here we report two asymmetric anhydrous sulfates, namely, NH 4 NaLi 2 (SO 4 ) 2 (Ι) and (NH 4 ) 2 Na 3 Li 9 (SO 4 ) 7 (Π), which consist of non-πconjugated [SO 4 ] 2− anions. Their single crystals can be readily grown by a facile evaporation method from water solution. Both sulfates are transparent down to the deep-UV region. Interestingly, there is a large NLO gap between I and Π, with phase-matching NLO responses of 1.1 and 0.5 times that of the benchmark KH 2 PO 4 , respectively. The first-principles studies reveal that the non-π-conjugated [SO 4 ] 2− anions are the dominate NLOactive groups, and the large NLO gap between I and Π can be ascribed to the nonbonding O 2p orbitals of different orientations in the crystallographically independent S1O 4 groups. This work provides an innovative non-πconjugated source that is distinct from the traditional πconjugated ones for deep-UV NLO materials.
A beryllium-free deep-ultraviolet (deep-UV) nonlinear optical (NLO) material K3Ba3Li2Al4B6O20F is developed mainly by the element substitution of Be for Al and Li from Sr2Be2B2O7 that was considered as one of the most promising deep-UV NLO materials. K3Ba3Li2Al4B6O20F preserves the structural merits of Sr2Be2B2O7 and thus exhibits no layering growth tendency and possesses the optical properties required for deep-UV NLO applications, including deep-UV transparency, phase-matchability, and sufficiently large second-harmonic generation (1.5 × KH2PO4). Furthermore, it overcomes the structural instability problem of Sr2Be2B2O7, which is confirmed by the obtainment of large single crystals and phonon dispersion calculations. These attributes make it very attractive for next-generation deep-UV NLO materials. The substitution of Be for Al and Li in beryllium borates provides a new opportunity to design beryllium-free deep-UV NLO materials with good performance.
Nonlinear optical (NLO) materials are of great importance in laser science and technology, as they can expand the wavelength range provided by common laser sources. Few NLO materials, except KBe 2 BO 3 F 2 (KBBF), can practically generate deep-ultraviolet coherent light by direct second-harmonic generation process, limited by the fundamental requirements on the structure-directing optical properties. However, KBBF suffers a strong layering tendency and high toxicity of the containing beryllium, which hinder the commercial availability of KBBF. Here we report a new beryllium-free borate, Li 4 Sr(BO 3 ) 2 , which preserves the structural merits of KBBF, resulting in the desirable optical properties. Furthermore, Li 4 Sr(BO 3 ) 2 mitigates the layering tendency greatly and enhances the efficiency of second-harmonic generation by more than half that of KBBF. These results suggest that Li 4 Sr(BO 3 ) 2 is an attractive candidate for the next generation of deep-ultraviolet NLO materials. This beryllium-free borate represents a new research direction in the development of deep-ultraviolet NLO materials.
Metal‐halide perovskites are recently emerging as the promising alternative for CPL detection owing to their CPL‐sensitive property induced by chiral organics and efficient charge transport of inorganic frameworks. However, most of these reported chiral perovskites involve high concentrations of toxic Pb which will become the potential bottleneck for their further application. Herein, we successfully developed two lead‐free halide double perovskites, [(R)‐β‐MPA]4AgBiI8 ((R)‐β‐MPA=(R)‐(+)‐β‐methylphenethylammonium, 1‐R), and [(S)‐β‐MPA]4AgBiI8 ((S)‐β‐MPA=(S)‐(−)‐β‐methylphenethylammonium, 1‐S). Circular dichroism measurements reveal that these perovskites exhibit notable chirality induced by organic cations to distinguish different polarization states of CPL photons. Significantly, they present unique chiral polar photovoltaic, and resulting self‐powered CPL detection without an external power source is unprecedentedly achieved. Furthermore, an anisotropy factor up to 0.3 is acquired for the self‐powered CPL detection, reaching the highest value among reported chiral perovskites. This work suggests hybrid double perovskites are promising photoelectronic candidates, and provides a new approach for exploring new “green” circularly polarized light‐sensitive materials with high performance.
It is challenging to explore deep-ultraviolet (deep-UV) nonlinear optical (NLO) materials that can achieve a subtle balance between deep-UV transparency and high NLO activity. Known deep-UV NLO materials are almost exclusively limited to borates, except few newly discovered phosphates despite their small NLO activities. Here we report two asymmetric phosphates, RbBa2(PO3)5 (I) and Rb2Ba3(P2O7)2 (II), which feature [PO3]∞ chains and [P2O7](4-) dimers formed by condensation of [PO4](3-) units, respectively. Remarkably, I achieves the desired balance, with the shortest deep-UV absorption edge at 163 nm and the largest NLO activity of 1.4 × KDP (KH2PO4) in deep-UV NLO phosphates. According to first-principles calculations, the enhanced macroscopic SHG response of I can be attributed to the [PO3]∞ chains which exhibit significantly larger microscopic SHG coefficients as compared with the [P2O7](4-) dimers.
Perovskite-type ferroelectrics composed of organometallic halides are emerging as a promising alternative to conventional photovoltaic devices because of their unique photovoltaic effects (PVEs). A new layered perovskite-type photoferroelectric, bis(cyclohexylaminium) tetrabromo lead (1), is presented. The material exhibits an exceptional anisotropy of bulk PVEs. Upon photoexcitation, superior photovoltaic behaviors are created along its inorganic layers, which are composed of corner-sharing PbBr6 octahedra. Semiconducting activity with remarkable photoconductivity is achieved in the vertical direction, showing sizeable on/off current ratios (>10(4) ), which compete with the most active photovoltaic material CH3 NH3 PbI3 . In 1 the temperature-dependence of photovoltage coincides fairly well with that of polarization, confirming the dominant role of ferroelectricity in such highly anisotropic PVEs. This finding sheds light on bulk PVEs in ferroelectric materials, and promotes their application in optoelectronic devices.
A new beryllium-free borate Rb3Al3B3O10F has been synthesized and characterized by single-crystal X-ray diffraction. It features a framework structure consisting of alveolate [Al3(BO3)3OF]∞ layers tightly bound via Al-O and Al-F bridged bonds, with the in-layer [BO3](3-) groups in nearly coplanar and aligned arrangement. This compound is transparent down to 200 nm and is phase-matchable with a powder second-harmonic generation efficiency of 1.2 times that of KH2PO4. Remarkably, it exhibits a strong interlayer bonding which is about one order larger than that of the benchmark KBe2BO3F2, thus no layering tendency was observed during the crystal growth. In addition, it is nonhygroscopic and thermally stable up to ∼1462 K. These attributes make Rb3Al3B3O10F a promising nonlinear optical crystal in the deep-ultraviolet region. First-principles calculations, combined with the anionic group theory, were adopted to rationalize the optical properties.
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