Photoluminescence

光致发光
  • 文章类型: Journal Article
    金属卤化物钙钛矿CsPbI3量子点(QD)由于其有趣的光电特性而引发了广泛的研究。然而,CsPbI3量子点由于油酸盐(OA-)/油胺(OAm+)的弱结合能力而发生不可避免的老化和发光猝灭,阻碍了进一步的实际应用。在这里,我们已经实现了老化的CsPbI3QD的超快复兴,这些QD已经失去了基于1-十二烷硫醇(DDT)表面配体的光致发光性能,以恢复出色的红光发射,具有25至90%的高光致发光量子产率(PLQY)。此外,经DDT表面处理的CsPbI3QD即使在35天后仍保持立方相和高PLQY值。DDT配体可以与Pb2+形成强键并钝化I-离子空位,增强辐射复合效率,从而改善QD的PLQY。DDT覆盖的CsPbI3QD的稳定但易于接近的表面被成功地用作白光LED,并表现出相当大的增强的发光性能。表明在固态照明领域的应用前景广阔。
    Metal halide perovskite CsPbI3 quantum dots (QDs) have sparked widespread research due to their intriguing optoelectronic. However, the CsPbI3 QDs undergo inevitable aging and luminescence quenching caused by the weak binding ability of oleate (OA-)/oleylammonium (OAm+), hindering further practical application. Herein, we have realized ultrafast rejuvenation of the aged CsPbI3 QDs that have lost their photoluminescence performance based on a 1-dodecanethiol (DDT) surface ligand to restore the outstanding red light emission with a high photoluminescence quantum yield (PLQY) from 25 to 90%. Furthermore, CsPbI3 QDs with DDT surface treatment maintain a cubic phase and high PLQY value even after 35 days. The DDT ligands can form a strong bond with Pb2+ and passivate I- ion vacancies, enhancing radiative recombination efficiency and thereby improving the PLQY of the QDs. The stable yet easily accessible surface of the DDT-capped CsPbI3 QDs was successfully employed as white LEDs and exhibited considerable enhanced luminous performance, suggesting promising application in solid-state lighting fields.
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  • 文章类型: Journal Article
    有机-无机杂化卤化锰(II)(OIMnHs)由于其出色的光学性能而在广泛的研究领域引起了极大的兴趣,丰富的结构多样性,低成本的解决方案可加工性,低毒性,这使得它们非常适合用作各种光电应用的新型发光材料。在过去的几年里,大量具有不同结构维度和多功能的OIMnH,如高效光致发光(PL),放射性发光,圆偏振发光,机械发光是通过对有机阳离子和无机Mn(II)多面体的明智筛选而新产生的。具体来说,通过精确的分子和结构工程,一系列具有接近统一的PL量子产率的OIMnHs,高抗热淬火性能,以及在恶劣条件下的出色稳定性已被设计和探索用于发光二极管(LED)的应用,X射线闪烁体,多模式防伪,和荧光传感。在这次审查中,总结了OIMnHs作为高效发光材料发展的最新进展,从基本的物理化学特性到先进的光电应用,重点是结构和功能设计,特别是LED和X射线检测和成像。还设想了当前挑战和未来努力来释放这些有前途的材料的潜力。
    Organic-inorganic hybrid manganese(II) halides (OIMnHs) have garnered tremendous interest across a wide array of research fields owing to their outstanding optical properties, abundant structural diversity, low-cost solution processibility, and low toxicity, which make them extremely suitable for use as a new class of luminescent materials for various optoelectronic applications. Over the past years, a plethora of OIMnHs with different structural dimensionalities and multifunctionalities such as efficient photoluminescence (PL), radioluminescence, circularly polarized luminescence, and mechanoluminescence have been newly created by judicious screening of the organic cations and inorganic Mn(II) polyhedra. Specifically, through precise molecular and structural engineering, a series of OIMnHs with near-unity PL quantum yields, high anti-thermal quenching properties, and excellent stability in harsh conditions have been devised and explored for applications in light-emitting diodes (LEDs), X-ray scintillators, multimodal anti-counterfeiting, and fluorescent sensing. In this review, the latest advancements in the development of OIMnHs as efficient light-emitting materials are summarized, which covers from their fundamental physicochemical properties to advanced optoelectronic applications, with an emphasis on the structural and functionality design especially for LEDs and X-ray detection and imaging. Current challenges and future efforts to unlock the potentials of these promising materials are also envisioned.
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  • 文章类型: Journal Article
    宽带近红外(NIR)磷光体是用于各种智能光谱学应用的NIR磷光体转换发光二极管(pc-LED)源的关键组分。然而,开发一个高效的,可调,和具有足够的光谱覆盖的廉价宽带NIR磷光体仍然是一个巨大的挑战。在这项工作中,选择具有高结构刚性的立方磷酸盐K2AlTi(PO4)3作为Cr3取代的主体材料,以产生有效的NIR发射。合成这种化合物,所获得的材料表现出覆盖700-1200nm的宽带NIR发射,其峰值波长范围为820至860nm,这取决于Cr3+取代浓度。Cr3浓度优化的样品具有76.4%的光致发光量子产率(PLQY),发射峰以857nm为中心,在464nm下的半峰全宽(fwhm)为184nm,展示了一个有效的和相对长波长的近红外发射与宽光谱覆盖范围。这种宽带近红外发射主要来自光谱分析推导出的单个发射中心,发光动力学,和第一原理计算。使用这种材料,制造的NIRpc-LED器件具有出色的NIR输出功率和NIR光电转换效率,使这种材料在夜视和生物成像的实际应用中具有吸引力。因此,这项工作不仅提供了一种低成本的宽带近红外材料,效率高,宽范围可调性,宽光谱覆盖范围,和光谱应用的相对长波长近红外发射,但也突出了发现这种材料的一些线索。
    Broadband near-infrared (NIR) phosphors are crucial components of NIR phosphor-converted light-emitting diode (pc-LED) sources for various smart spectroscopy applications. However, developing an efficient, tunable, and inexpensive broadband NIR phosphor with sufficient spectral coverage remains a great challenge. In this work, a cubic phosphate K2AlTi(PO4)3 with highly structural rigidity was chosen as host material for Cr3+ substitution to create an efficient NIR emission. Synthesizing this compound, the obtained material exhibits a broadband NIR emission covering 700-1200 nm with a peak wavelength ranging from 820 to 860 nm depending on the Cr3+ substituting concentration. The Cr3+ concentration optimized sample possesses a photoluminescence quantum yield (PLQY) of 76.4% with an emission peak centered at 857 nm and a full width at half-maximum (fwhm) of 184 nm under 464 nm exaction, demonstrating an efficient and relatively long-wavelength NIR emission with wide spectral coverage. This broadband NIR emission is mainly derived from a single kind of emission center deduced from spectral analysis, luminescence dynamics, and first-principle calculations. Using this material, the fabricated NIR pc-LED device presents an excellent NIR output power and NIR photoelectric conversion efficiency, making this material attractive in practical applications of night-vision and bioimaging. Therefore, this work not only provides a broadband NIR material with superiorities of low cost, high efficiency, wide-range tunability, wide spectral coverage, and relatively long-wavelength NIR emission for spectroscopy applications but also highlights some clues to discover this kind of materials.
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  • 文章类型: Journal Article
    采用高温固相法制备了新型红色荧光粉Lu3(1-x)Sc2Ga3O12:xEu3+(0≤x≤0.3)。Lu2.4Sc2Ga3O12:0.2Eu3+荧光粉表现出较高的内部量子效率和热稳定性,分别为64.79%和87.0%,分别。基于Lu2.4Sc2Ga3O12:0.2Eu3+荧光粉,Gd3+/Y3+离子对宿主中Lu3+离子的部分替代改变了Eu3+离子的局部晶体场环境,导致发光中心的奇妙变化,593nm处的发光强度分别提高了3.66和3.54倍,分别。从动力学角度分析了Eu3+离子的衰减时间,并从荧光粉结构和Eu3+离子周围的晶体场效应两个方面详细讨论了部分取代Lu3+离子后发光增强的原因。此外,用Gd3+/Y3+离子取代,样品的热稳定性为90.3%/89.4%,具有优异的低热淬火性能。通过结合德拜温度和活化能来描述热淬火机理。样品还具有高的内部量子效率IQE=79.03%/78.24%。最后,在365nm芯片的激发下,Lu2.34Sc2Ga3O12的荧光粉:0.2Eu3+,0.02Gd3+和Lu2.34Sc2Ga3O12:0.2Eu3+,0.02Y3+合成R-LED器件具有极高的显色指数,Ra为78.23/77.15,色温为1640.38K/1642.97K。实验结果表明,Lu2.34Sc2Ga3O12:0.2Eu3+,制备的0.02Gd3+/Y3+荧光粉在w-LED器件中具有广阔的应用前景。
    A novel red phosphor Lu3(1-x)Sc2Ga3O12: xEu3+(0 ≤ x ≤ 0.3) was successfully prepared by high temperature solid state method. The Lu2.4Sc2Ga3O12: 0.2Eu3+ phosphor shows strong high internal quantum efficiency and thermal stability with values of 64.79 % and 87.0 %, respectively. Based on Lu2.4Sc2Ga3O12: 0.2Eu3+ phosphor, the partial replacement of Lu3+ ions in the host by Gd3+ / Y3+ ions changes the local crystal field environment of Eu3+ ions, resulting in wonderful changes in the luminous center, and the luminous intensity at 593 nm is increased by 3.66 and 3.54 times, respectively. The decay time of Eu3+ ions is analyzed from the perspective of dynamics, and the reasons for the enhancement of luminescence after partial replacement of Lu3+ ions are discussed in detail from two aspects of phosphor structure and crystal field effect around Eu3+ ions. In addition, with the substitution of Gd3+ / Y3+ ions, the thermal stability of the sample is 90.3 %/89.4 % with excellent low thermal quenching. The thermal quenching mechanism is described by combining Debye temperature and activation energy. The sample also has a high internal quantum efficiency IQE=79.03 % / 78.24 %. Finally, under the excitation of 365 nm chip, the phosphors of Lu2.34Sc2Ga3O12: 0.2Eu3+, 0.02Gd3+ and Lu2.34Sc2Ga3O12: 0.2Eu3+, 0.02Y3+ synthesized R-LED device has extremely high color rendering index, Ra is 78.23/77.15 and color temperature is 1640.38 K/1642.97 K. The experimental results show that the Lu2.34Sc2Ga3O12: 0.2Eu3+, 0.02Gd3+ / Y3+ phosphors prepared has a wide application prospect in w-LED devices.
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  • 文章类型: Journal Article
    电子和空穴对的迁移行为决定了光致发光和光催化活性,这是半导体材料的两种不同性质。在合成方法的影响下,半导体材料的光致发光和光催化活性也表现出强烈的方法依赖性行为。在这次审查中,MMoO4、MWO4和MMoO4/MWO4的合成方法(M=Mg,Ca,首次综述了Sr和Ba)异质结复合材料及其光致发光和光催化活性。还综述了不同M离子对MMoO4/MWO4异质结复合材料光致发光和光催化活性的影响。还讨论了光致发光和光催化活性之间的内在相关机制。不同的M离子导致MMoO4/MWO4异质结复合材料中不同的配位环境,导致不同MMoO4/MWO4异质结复合材料的光致发光和光催化机理不同。该综述为今后MMoO4/MWO4异质结复合材料的研究提供了理论参考和技术指导。
    The migration behavior of electron and hole pairs determines both photoluminescence and photocatalytic activity, which are two distinct properties of semiconductor materials. The photoluminescence and photocatalytic activity of semiconductor materials also exhibit strong method-dependent behavior under the influence of synthesis methods. In this review, the synthesis methods of MMoO4, MWO4 and MMoO4/MWO4 (M = Mg, Ca, Sr and Ba) heterojunction composites and their photoluminescence and photocatalytic activities are reviewed for the first time. The effects of different M ions on the photoluminescence and photocatalytic activity of MMoO4/MWO4 heterojunction composites are also reviewed. There is also a discussion about the intrinsic correlation mechanism between photoluminescence and photocatalytic activity. Different M ions result in different coordination environments in MMoO4/MWO4 heterojunction composites, which leads to different photoluminescence and photocatalytic mechanisms of different MMoO4/MWO4 heterojunction composites. This review provides theoretical reference and technical guidance for future research on MMoO4/MWO4 heterojunction composites.
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  • 文章类型: Journal Article
    具有光刺激响应特性的光致发光金属聚合物正在成为有前途的材料,在光可重写图案中具有广泛的应用,可穿戴紫外线传感器,和光学加密防伪。然而,将这些材料集成到需要快速响应时间的实际应用中,轻巧的品质,抗疲劳性,和多种加密功能带来了挑战。在这项研究中,通过聚合物链之间的Ln-Tpy配位键和H键交联三吡啶(Tpy)和螺吡喃(SP)官能化聚氨酯链,开发了具有快速自修复性能的发光光致变色镧系元素(Ln)金属聚合物。所得产品具有一系列有趣的特征:i)使用螺吡喃单体而不使用其他掺杂剂的光刺激响应性;ii)由于Ln-Tpy和开环螺吡喃部分,在紫外光下具有双重发射性能;iii)令人满意的机械性能和聚合物链的自我修复能力;iv)通过光刺激或进料比调整对发光颜色进行多种控制开关。利用这些属性,开发的材料为光书写应用带来了新的机会,高级信息加密,紫外线感应可穿戴设备,以及为未来设计多功能智能材料的见解。
    Photoluminescent metallopolymers displaying photo-stimuli-responsive properties are emerging as promising materials with versatile applications in photo-rewritable patterns, wearable UV sensors, and optical encryption anti-counterfeiting. However, integrating these materials into practical applications that require fast response times, lightweight qualities, fatigue resistance, and multiple encryption capabilities poses challenges. In this study, luminescent photochromic lanthanide (Ln) metallopolymers with rapid self-healing properties are developed by cross-linking terpyridine (Tpy)- and spiropyran (SP)- functionalized polyurethane chains through Ln-Tpy coordination bonds and H-bonds among polymer chains. The resulting products exhibit a range of intriguing features: i) photo-stimuli responsiveness using spiropyran monomers without additional dopants; ii) dual-emitting performance under UV-light due to Ln-Tpy and open-ring spiropyran moieties; iii) satisfactory mechanical properties and self-healing abilities from polymer chains; iv) multiple control switches for luminescence colors through photostimulation or feed ratio adjustments. Leveraging these attributes, the developed material introduces novel opportunities for light-writing applications, advanced information encryption, UV-sensing wearable devices, and insights into designing multifunctional intelligent materials for the future.
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  • 文章类型: Journal Article
    等离子体纳米粒子能够操纵和增强深亚波长尺度的光场,导致结构和器件的不同应用在光学。尽管杂化等离子体材料由于纳米接近的组分之间的相互作用而显示出显著的光学特性,在单晶基体内可扩展地生产等离子体纳米结构以获得理想的等离子体-晶体界面仍然具有挑战性。这里,提出了一种新的方法来实现晶格内等离子体纳米粒子的有效操纵。采用超快激光驱动等离子体纳米光刻技术,在钇铝石榴石(YAG)晶体的晶格中精确定义了具有可控形貌的金属纳米颗粒。通过直接离子注入,产生了由嵌入在亚表面无定形YAG层中的纳米颗粒组成的混合等离子体材料。随后,飞秒激光脉冲引导等离子体纳米颗粒的形成和重塑从非晶层沿着光传播的方向进入单晶基质,由等离子体激元介导的激光能量沉积演化促进。通过定制共振模式和优化结构化粒子组件之间的耦合,一系列的应用,包括偏振相关的吸收和非线性,可控光致发光,并证明了结构颜色的产生。这项研究引入了一种制造具有晶格内等离子体纳米结构的先进光学材料的新方法,为多种功能光子器件的发展铺平了道路。
    Plasmonic nanoparticles enable manipulation and enhancement of light fields at deep subwavelength scales, leading to structures and devices for diverse applications in optics. Despite hybrid plasmonic materials display remarkable optical properties due to interactions between components in nanoproximity, scalable production of plasmonic nanostructures within a single-crystalline matrix to achieve an ideal plasmon-crystal interface remains challenging. Here, a novel approach is presented to realize efficient manipulation of in-lattice plasmonic nanoparticles. Employing ultrafast-laser-driven plasmonic nanolithography, metallic nanoparticles with controllable morphology are precisely defined in the crystalline lattice of yttrium aluminum garnet (YAG) crystal. Through direct ion implantation, hybrid plasmonic material composed of nanoparticles embedded in a sub-surface amorphous YAG layer is created. Subsequently, femtosecond laser pulses guide formation and reshaping of plasmonic nanoparticles from the amorphous layer into the single-crystalline matrix along direction of light propagation, facilitated by a plasmon-mediated evolution of laser energy deposition. By tailoring resonance modes and optimizing the coupling between structured particle assemblies, a range of applications including polarization-dependent absorption and nonlinearity, controllable photoluminescence, and structural color generation is demonstrated. This research introduces a new approach for fabricating advanced optical materials featuring in-lattice plasmonic nanostructures, paving the way for the development of diverse functional photonic devices.
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  • 文章类型: Journal Article
    奥洛他定(OLP)被广泛用作有效的抗组胺药物,用于减轻与过敏性结膜炎相关的眼部瘙痒。由于它在药店的频繁使用,迫切需要一种具有成本效益的,容易实现,高灵敏度的环境可持续检测方法。这项研究提出了一种新颖的荧光信号检测方法,用于检测纯形式和房水的OLP。所提出的方法依赖于增强OLP的弱本征荧光发射,与固有荧光相比,实现高达680%的显着增加。通过使用乙酸盐缓冲液(pH3.6)并掺入十二烷基硫酸钠(SDS)表面活性剂的溶液在质子化的OLP周围形成胶束来实现这种增强。在OLP的浓度与1.0至100.0ngmL-1的荧光强度之间观察到强相关性(R=0.9996),检测限为0.22ngmL-1。该方法成功地用于定量粉末形式和药物滴眼剂的OLP。此外,它在确定人工房水中的OLP方面表现出稳健的性能,回收率为99.05±1.51,基质干扰物的干扰最小。此外,评价所述方法的绿色度。
    Olopatadine (OLP) is widely utilized as an effective antihistaminic drug for alleviating ocular itching associated with allergic conjunctivitis. With its frequent usage in pharmacies, there arises a pressing need for a cost-effective, easily implementable, environmentally sustainable detection method with high sensitivity. This study presents a novel signal-on fluorimetric method for detecting OLP in both its pure form and aqueous humor. The proposed approach depends on enhancing the weak intrinsic fluorescence emission of OLP, achieving a remarkable increase of up to 680% compared to its intrinsic fluorescence. This enhancement is achieved by forming micelles around protonated OLP using an acetate buffer (pH 3.6) and incorporating a solution of sodium dodecyl sulfate (SDS) surfactant. A strong correlation (R = 0.9996) is observed between the concentration of OLP and fluorescence intensities ranging from 1.0 to 100.0 ng mL-1 with a limit of detection of 0.22 ng mL-1. This described method is successfully employed for quantifying OLP in both its powder form and pharmaceutical eye drops. Furthermore, it demonstrates robust performance in determining OLP in artificial aqueous humor with a percentage recovery of 99.05 ± 1.51, with minimal interference from matrix interferents. Moreover, the greenness of the described method was evaluated.
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  • 文章类型: Journal Article
    通过调节金属离子的配位构型来控制卤化物钙钛矿材料的光学活性是重要的。在这里,一种新型的锰基卤化物,特别是二水合三(甲基二苯基氧化膦)四氯化锰(II),[Mn(C13H13OP)4(H2O)2][MnCl4]或[Mn(MDPPO)4(H2O)2][MnCl4](MDPPO是甲基二苯基膦氧化物),通过MnCl2与中性分子MDPPO的溶剂热反应合成。在这个化合物中,[Mn(MDPPO)4(H2O)2]2+作为阳离子,而[MnCl4]2-作为阴离子,使四面体和八面体结构在同一系统内共存。值得注意的是,该化合物在662nm处表现出有效的红光发射,不同于通常在MnX4基卤化物中观察到的绿光发射。理论计算表明,红色发射来自从MDPPO到[MnCl4]2-的Mn2+的电荷转移。这项工作为具有独特结构的发红光的锰基卤化物的设计和合成提供了新的视角。
    Controlling the optical activity of halide perovskite materials through modulation of the coordination configurations of the metal ions is important. Herein, a novel manganese-based halide, specifically diaquatetrakis(methyldiphenylphosphine oxide)manganese(II) tetrachloridomanganate(II), [Mn(C13H13OP)4(H2O)2][MnCl4] or [Mn(MDPPO)4(H2O)2][MnCl4] (MDPPO is methyldiphenylphosphine oxide), was synthesized through the solvothermal reaction of MnCl2 with the neutral molecule MDPPO. In this compound, [Mn(MDPPO)4(H2O)2]2+ acts as the cation, while [MnCl4]2- serves as the anion, enabling the co-existence of tetrahedral and octahedral structures within the same system. Remarkably, the compound exhibits efficient red-light emission at 662 nm, distinct from the green-light emission typically observed in MnX4-based halides. Theoretical calculations show that the red emission comes from the charge transfer from the MDPPO to the Mn2+ of [MnCl4]2-. This work provides a new perspective for the design and synthesis of red-light-emitting manganese-based halides with unique structures.
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  • 文章类型: Journal Article
    设计和合成具有近紫外(NUV)光激发的高能发射(<500nm)的多功能混合卤化铜仍然具有挑战性。这里,一对宽带激发的高能异构体,即,α-/β-(MePh3P)2CuI3(MePh3P=甲基三苯基鳞),是合成的。首先发现了在475nm处具有蓝色发射峰值的α-(MePh3P)2CuI3,其中其结构包含规则的[CuI3]2-三角形,并在中心对称空间群P21/c中结晶。而具有扭曲的[CuI3]2平面三角形的β-(MePh3P)2CuI3显示出反转对称性破坏并在非中心对称空间群P21中结晶,该空间群表现出青色发射峰值在495nm处,具有显着的近统一光致发光量子产率和激发带范围从200到450nm。有趣的是,β-(MePh3P)2CuI3表现出0.54×KDP的相位匹配二次谐波产生响应和0.06@1064nm的合适双折射。此外,β-(MePh3P)2CuI3也可以通过X射线放射发光激发,具有16193光子/MeV的高闪烁光产量和47.97nGy/s的超低检测极限,这只是标准医学诊断(5.5μGy/s)的0.87%。这项工作不仅促进了固态照明的发展,激光频率转换和X射线成像,同时也为构建多功能混合金属卤化物提供了参考。
    Designing and synthesizing multifunctional hybrid copper halides with near ultraviolet (NUV) light-excited high-energy emission (< 500 nm) remains challenging. Here, a pair of broadband-excited high-energy emitting isomers, namely, α-/β-(MePh3P)2CuI3 (MePh3P = methyltriphenylphosphonium), were synthesized. α-(MePh3P)2CuI3 with blue emission peaking at 475 nm is firstly discovered wherein its structure contains regular [CuI3]2‒ triangles and crystallizes in centrosymmetric space group P21/c. While β-(MePh3P)2CuI3 featuring distorted [CuI3]2‒ planar triangles shows inversion symmetry breaking and crystallizes in the noncentrosymmetric space group P21, which exhibits cyan emission peaking at 495 nm with prominent near-unity photoluminescence quantum yield and the excitation band ranging from 200 to 450 nm. Intriguingly, β-(MePh3P)2CuI3 exhibits phase-matchable second-harmonic generation response of 0.54 × KDP and a suitable birefringence of 0.06@1064 nm. Furthermore, β-(MePh3P)2CuI3 also can be excited by X-ray radioluminescence with a high scintillation light yield of 16193 photon/MeV and an ultra-low detection limit of 47.97 nGy/s, which is only 0.87% of the standard medical diagnosis (5.5 μGy/s). This work not only promotes the development of solid-state lighting, laser frequency conversion and X-ray imaging, but also provides a reference for constructing multifunctional hybrid metal halides.
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