非线性超构器件——从等离激元到介电质

林蓉 ,  姚金 ,  王志辉 ,  陈子亭 ,  蔡定平

Engineering ›› 2025, Vol. 45 ›› Issue (2) : 17 -27.

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Engineering ›› 2025, Vol. 45 ›› Issue (2) : 17 -27. DOI: 10.1016/j.eng.2024.11.021
研究论文

非线性超构器件——从等离激元到介电质

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摘要

超构器件显著推动了非线性光学现象的研究进展。在纳米尺度下,基波与谐波之间的相位失配问题可大幅缓解。本文综述了等离激元与介电质材料诱导非线性光学特性的理论框架,并探讨了能够激发强共振模式以提升效率的等离激元与介电质非线性超构器件。我们总结了多种用于调控辐射方向图的策略,旨在增强对超构器件发出的非线性信号的收集能力。此外,我们还讨论了如何通过超构器件中的非线性相位调制,整合效率提升与辐射调控的优势,这不仅提升了非线性信号的能量密度,也扩大了其应用范围。最后,本文展望了该领域的潜在研究方向。

Abstract

Meta-devices have significantly revitalized the study of nonlinear optical phenomena. At the nanoscale, the detrimental effects of phase mismatching between fundamental and harmonic waves can be substantially reduced. This review analyzes the theoretical frameworks of how plasmonic and dielectric materials induce nonlinear optical properties. Plasmonic and dielectric nonlinear meta-devices that can excite strong resonant modes for efficiency enhancement are explored. We outline different strategies designed to shape the radiation pattern in order to increase the collection capability of nonlinear signals emitted from meta-devices. In addition, we discuss how nonlinear phase manipulation in meta-devices can integrate the benefits of efficiency enhancement and radiation shaping, not only boosting the energy density of the nonlinear signal but also facilitating a wide range of applications. Finally, potential research directions within this field are discussed.

关键词

非线性光学 / 纳米光子学 / 超构器件 / 超构表面 / 等离激元 / 介电质

Key words

Nonlinear optics / Nanophotonics / Meta-devices / Metasurfaces / Plasmonic / Dielectric

引用本文

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林蓉,姚金,王志辉,陈子亭,蔡定平. 非线性超构器件——从等离激元到介电质[J]. 工程(英文), 2025, 45(2): 17-27 DOI:10.1016/j.eng.2024.11.021

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1 引言

非线性光学本质上源于光与物质之间的非线性相互作用。1961年,研究人员在激光照射下首次观测到二次谐波信号,表明某些介质在高电场强度作用下会产生非线性响应[1]。这一具有里程碑意义的发现推动了非线性光学领域的快速发展。自那以后,人们开始研究众多非线性光学过程,包括四波混频(FWM)[23]、光学整流[4]、三次谐波生成(THG)[5]、非线性光致发光[6]、光学参量放大(OPA)[7]、自发参量下转换(SPDC)[8]以及电光效应[9]等。随着纳米技术的发展,非线性光学领域焕发出新的活力[1012]。在纳米尺度下,由于光传播距离极短,基波与谐波之间的相位失配对非线性响应的负面影响被大大削弱。此外,借助先进的纳米制造技术[1315],研究人员可以通过对等离激元材料的表面或界面进行几何结构改性,人为打破其反演对称性,从而激发出二阶非线性光学过程。

虽然在非线性极化率方面,等离激元材料也许不如传统非线性晶体出色,但是等离激元超构器件(无论是单个粒子还是阵列结构)[1622]能在材料表面附近实现电磁场的局域限制与增强,从而提升非线性响应。这一增强效应得益于局域或非局域的共振模式[2330],包括表面等离极化激元(SPP)、局域表面等离激元共振(LSPR)、法诺共振以及表面晶格共振(SLR)。必须指出,等离激元超构器件存在一些固有局限性,如热效应、高反射率、对非线性发射信号的吸收以及有限的光穿透深度。而介电质纳米结构逐渐展现出克服这些问题的潜力。许多介电材料[3132]本身具有非反演对称性的晶体结构,有利于二阶非线性过程的发生。值得注意的是,在介电超构器件[3336]中,光约束体积可延伸至表面以下。通过耦合多种共振模式[3740],如米氏共振、晶格共振、导模共振以及连续谱束缚态(BIC),可进一步提升非线性转换效率。

除了从激发机制增强非线性响应之外,另一种有效策略是通过调控辐射方向图来提高非线性信号的收集效率[4143]。该方法能削弱相邻纳米结构之间的破坏性干涉,并增强超构器件中非线性响应的单向性。此外,非线性过程的阶数以及纳米结构的旋转对称群将共同决定非线性波的相位特性。因此,通过相位调制,非线性超构器件能够融合共振模式与辐射调控的双重优势,进一步提升非线性信号的能量密度。这一方法使非线性过程具备更高维度的调控能力,为波束整形[4445]、成像[4647]、全息摄影[4849]、手性传感[50]、涡旋光束生成[51]以及边缘检测[52]等多种应用开辟了新路径。

在本文中,我们探讨了非线性光学领域的最新进展,内容涵盖从等离激元超构器件到介电质超构器件的发展,本文结构如图1所示[5361]。第2节回顾了用于研究超构器件非线性光学特性的理论框架,并介绍了常用材料的非线性特性;第3节讨论了不同共振模式对提升超构器件非线性效率的贡献;第4节介绍了通过调控辐射方向图来提高超构器件所产生的非线性信号收集效率的不同策略;第5节总结了非线性相位调制所带来的多样化应用前景;第6节总结了全文,并对未来的研究方向进行了展望。

2 非线性激发——天然型与人工型

材料的光学响应本质上由其极化 P 的激发过程所决定。为了精确描述材料的非线性响应,将极化 P 表示为电场 E 的幂级数展开,形式如下:

P = ε0χ1·E+ε0χ2:EE+ε0χ3EEE+
P(1) = ε0χ1·E
P(2) = ε0χ2:EE
P(3) = ε0χ(3)EEE

式中,ε0表示真空介电常数; χ(i)是第i阶非线性极化率张量。在等式(1)中, P(1)P(2)P(3)分别代表不同阶次的激发项。第一项 P(1)描述材料对 E 的线性响应;第二项 P(2)涉及二阶非线性过程,包括二次谐波产生(SHG)、差频产生(DFG)、和频产生(SFG)及光学整流,这些过程均涉及 E 的平方项响应,能够产生新频率或改变光的传播特性;第三项 P(3)则对应三阶非线性过程,如THG和FWM,其响应与 E 的立方项相关。

需要强调的是,非线性过程本质上与所用材料的晶体结构密切相关。具体而言,在具有反演对称性的材料中,其二阶极化率 χ(2)为零;相比之下,三阶极化率 χ(3)则不受这种对称性的影响。

2.1 等离激元的天然非线性

尽管大多数金属元素(如金等贵金属)具有反演对称性晶体结构,抑制了二阶非线性响应,但由于其三阶极化率 χ(3) [6263]不受这种对称性的影响,它们天生具备非线性特性。在本节中,我们将从数学角度简要说明这一现象。根据反演对称性的性质,可以推导出两种变换关系。其中,电场 E 的变换行为为 E → - E。随之,根据等式(4),三阶极化项 P(3)变换为

P(3)  ε0χ(3)-E-E-E= -ε0χ(3)EEE

而三阶极化项 P(3)本身也应变换为

P(3)-P(3)=-ε0χ(3)EEE

显然,这两种变换所得的结果是一致的。这种对反演对称性的不变性表明,三阶极化项其符号保持不变。因此,等离激元系统中的三阶极化率 χ(3)可以为非零,从而发生三阶非线性响应。相较于二阶非线性效应,这种三阶非线性通常更为显著,其具有多种实际应用,包括等离激元逻辑门[64]和纳米尺度宽带光源[65]等。

2.2 等离激元的人工非线性

为了在等离激元超构器件中激发二阶非线性过程,必须人为打破反演对称性,这可通过对材料的表面或界面进行几何结构改性来实现。更具体而言,常用的有效策略包括:构建异质结构或界面、组装多种纳米粒子组合以及设计非中心对称的纳米结构。

需要指出的是,在具有反演对称性的介质中, P(2)包含两个组分:表面分量和体相分量。其中,表面分量[Psurf2]仅在材料表面几层原子范围内产生,其表达式如下[66]:

Psurf2(2ω,r)= ε0χsurf2E(ω,r)E(ω,r)δ(r-rsurf)

式中,ω是基频;χsurf2是表面二阶非线性极化率; r 是空间位置矢量; rsurf表示表面位置;狄拉克δ函数则体现了非线性极化的表面特性。

具体来说,由于介质表面存在一个各向同性的镜像对称平面,表面二阶极化率χsurf2通常仅表现出三个独立分量。这三个分量分别是χnnn2surf(ω1, ω2, ω3)、χntt2surf(ω1, ω2, ω3)和χtnt2surf(ω1, ω2, ω3) = χttn2surf(ω1, ω2, ω3),其中,符号nt分别表示法向和切向,这些分量的数值取决于相互作用光波的频率。需要指出的是,前述三个分量主要存在于多晶金属薄膜中;而在单晶贵金属中,各向异性分量[6769]则变得显著。

材料内部产生的体相分量[Pbulk2]表达形式如下:

Pbulk22ω,r=γEω,r·Eω,r+                            δ'Eω,r·Eω,r+                            β·Eω,rEω,r+                 ςEω,r·Eω,r

式中,参数γδβϛ定义了材料性质[70]。

值得注意的是,由于材料的均匀性特征,分析体相分量时通常会忽略第二项和第三项。因此,体相分量响应主要依赖于参数γϛ的数值。在贵金属的特定情况下,参数ϛ通常可以忽略,简化了体相分量的分析和表征[71]。

2.3 介电质的天然非线性

具有天然非中心对称晶体结构的介电质材料可用于构建具备二阶非线性效应的超构器件。常用于二阶非线性过程的介电材料包括氧化锌(ZnO)、磷化镓(GaP)、砷化镓(GaAs)、铝镓砷(AlGaAs)、铌酸锂(LiNbO3)以及二硫化钼(MoS2)等。相较于二阶非线性,三阶非线性不需要特定的晶体对称性,因此硅(Si)和二氧化钛(TiO2)是较为合适的选择,且在构建超构器件时通常采用其非晶态形式。

需要特别指出的是,非线性极化率的数值并不是唯一需要考虑的参数。在设计非线性超构器件时,基频和谐频下的吸收损耗、器件的制备难度以及材料的可调控性等因素也同样关键。Vabishchevich和Kivshar [72]对用于非线性超构器件的各种介电材料进行了详细探讨,因此此处不再赘述这些材料。

3 非线性效率增强

在非线性超构器件中,非线性效率是一个关键问题,它取决于非线性材料内部或其表面的局部电磁场强度。非线性超构器件通过引入强共振响应来集中和增强电场,能够在亚波长尺度上显著提升非线性效率,且无需满足体相晶体[73]中对相位匹配的要求。为增强非线性效率,人们激发了多种共振模式,如在等离激元超构表面中激发的LSPR [74]、SPP [75]和SLR [76];在介电超构表面中激发的米氏共振[77]、法诺共振[55]以及BIC [7880]。

等离激元纳米结构是增强外部电场的良好候选材料,有助于提升其表面非线性以及集成非线性材料的光学非线性响应[8183]。尽管以往的研究大多单独利用等离激元纳米结构来增强非线性,但近期研究发现,复合纳米结构能够进一步放大这种效应。Deng等[84]开发了一种混合超构表面,集成等离激元超原子与近零介电常数(ENZ)纳米薄膜,SHG强度能提升104倍,见图2(a)。这一性能提升归因于入射光在金属超原子附近的矢量特性变化以及与ENZ薄膜的增强相互作用。超构表面中的非局域效应在增强光学相互作用并激发多种非线性效应方面发挥了关键作用[8586]。

除了通过不同材料层之间的耦合来增强电磁场外,引入能够激发集体响应的非局域效应也可实现类似的增强效果。Sharma等[87]展示了在含扭曲向列型液晶(LC)层的非线性非局域超构表面中SHG的显著电调制和全光调制,如图2(b)所示。LC层通过SLR引发了强烈的非局域SHG响应。在共振条件下,SHG增强表现出超过25 dB的电调制振幅以及由全光诱导的相变过程,从而进一步影响SHG。

值得注意的是,金属材料固有的损耗限制了这些非线性纳米结构的工作频带。上述样品的基本工作频率位于近红外波段,而其所产生的SHG则落在可见光谱范围内。短波长光,尤其是真空紫外(VUV)波段的光,在技术应用上有广阔前景,但由于金属材料存在较大的损耗,且其对器件制备要求也较高,因此难以用金属材料产生[88]。然而介电超构表面与纳米谐振器因具有高品质因子的共振模式,可适用于提升非线性转换效率。这些高品质因子(Q-factor)共振来源于材料本身较高的折射率与较大的非线性系数[8993],ZnO因其优异的性能成为了一种不错的选择。既有研究表明,ZnO不仅能够产生近紫外光,还在基频处表现出近零的消光系数。Semmlinger等[94]设计了一种全介电超构表面,专用于在VUV波段产生非线性光。他们采用在394 nm泵浦波长下可表现出米氏共振的ZnO纳米谐振器,成功产生了197 nm的二次谐波,如图2(c)所示[94]。该非线性超构表面所实现的有效系数约为棱镜耦合氟代硼铍酸钾(KBBF)晶体的三倍。

除了利用基本的二次或三次谐波外,还可以考虑使用高次谐波来产生紫外光。Zalogina等[95]利用由AlGaAs材料制成的单个亚波长谐振器,实现了高次谐波产生(HHG),其谐波阶数最高至第七次谐波[图2(d)]。研究人员使用泵浦波长为λ =3.7 μm的方位极化聚焦光束激活了与准BIC相关的共振光学模式。该谐振器体积约为 0.1λ³,展示了将固态高次谐波光源微型化至亚波长尺寸的可行性。尽管该研究仅在实验中观察到第七次谐波,理论分析表明在约400 nm处还存在第九次谐波。我们认为,这一发现有望为短波长光的产生提供新的启发。

除了产生短波长光外,非线性手性超构光子学与量子非线性效应近年来也受到了广泛关注。与线性手性光学效应相比,非线性手性光学效应更为显著,这是由于手性光激发产生的光学谐波对分子及结构不对称性具有极高的敏感性[9697]。这种高灵敏度与高品质因子共振密切相关,而BIC便是其中的典型代表。Shi等[98]提出了一种支持BIC的手性超构表面设计。图2(e)[98]展示了该设计的实验手性光学响应,具有超高品质因子以及高达0.9的圆二色性(CD)。在同一手性超构表面中,该设计实现了近场的强增强、近乎完美的非线性CD以及本征圆偏振特性。

在非线性超构表面中,可以通过SPDC过程产生量子纠缠光子对[99102],这是参数波的经典非线性产生的逆过程。在量子效应方面, Santiago-Cruz等[103]利用SPDC过程,在GaAs超构表面中激发含高品质因子的准BIC共振,从而产生纠缠光子,如图2(f)所示。这些超构表面增强了量子真空场,在多个窄带内显著提升了非简并纠缠光子发射效率,而这些窄带分布于较宽的光谱范围内。通过在不同波长激发单个或多个共振模式,可生成包括簇态在内的多频量子态。该方法在发展高维量子纠缠光学器件方面展现出巨大潜力。

4 非线性辐射调控

需要注意的是,非线性超构器件产生的谐波会衍射到不同的衍射级次中,导致能量分散[104106]。通过调控辐射方向图,非线性超构器件能够实现非线性光的定向辐射,这有助于提高非线性光能量的收集效率,从而增强非线性光利用效率[107110]。

谐波远场辐射方向图会受到超原子内部局域场分布的影响。改变泵浦光的偏振状态会引起局域场分布的变化,从而产生不同的非线性位移电流[116119],进而激发出不同的非线性模式。Carletti等[111]证明,通过调节泵浦光的偏振状态可以控制二次谐波的辐射方向,如图3(a)所示。当泵浦光分别为x偏振、45°偏振、y偏振以及圆偏振时,AlGaAs圆柱超构表面会表现出不同的二次谐波远场辐射模式,其中45°偏振下的非线性模式可视为由x偏振和y偏振泵浦光激发模式的叠加。在此种情况下,可以通过调控辐射方向图来减小谐波信号的角度发散,从而确保即使利用数值孔径较低的透镜,也能有效收集产生的所有非线性光。

单向性这一特性也可以通过设计具有特定非线性张量的材料来实现。Xu等[112]的研究表明,不同晶向的GaAs非线性超构表面在晶轴方向与泵浦光偏振方向的相对方向上存在差异,因此会产生不同的非线性多极干涉。由于(110)-GaAs纳米天线仅发生奇数方位角序数的多极干涉[120121],该类超构表面表现出较强的前向或后向辐射强度。通过调节泵浦光的偏振状态,可以实现前向和后向辐射的切换,如图3(b)所示[112]。另一种非线性辐射方向图调控策略是将偏离纳米结构表面法向传播的谐波重新导回法向。Ghirardini等[113]利用非对称全息光栅调控了AlGaAs圆柱纳米天线的二次谐波辐射方向。两个半圆形光栅在空间上相互错位,使得纳米圆柱发射的二次谐波从掠射角重新导向法线方向,如图3(c)所示[113]。除了引入面内非对称光栅外,Gigli等[56]还采用了轴向非对称的纳米椅谐振器来激发具有法线辐射方向的非线性模式,如图3(d)所示。由于纳米椅谐振器内基频与非线性共振的相互作用,轴向非对称谐振器相比于圆柱形谐振器表现出较强的中心发射瓣。

改变结构所处的平面也会影响辐射方向图。Tsai等[114]研究了垂直开环谐振器(VSRR)和面内开环谐振器(PSRR)超构表面的二次谐波光学调控。通过改变开环谐振器的排列方式,可以调控超构表面的辐射方向图。VSRR超构表面的二次谐波在六个方向上辐射,而PSRR超构表面的二次谐波主要沿前向或后向辐射,垂直于入射光方向的辐射相对较弱,如图3(e)所示[114]。此外,Okhlopkov等[115]同时激发了硅构超表面的高品质因子米氏共振和准BIC模式,产生了一种新的混合共振模式,支持更高的衍射效率且对入射泵浦光角度具有敏感性。高效定向辐射仅在泵浦光的特定入射角(22°)出现,如图3(f)所示[115]。

5 非线性相位调制

为了进一步调制非线性超构器件的远场辐射方向图,可以引入非线性相位调制,该方法融合了非线性效率增强和辐射调控的优势。已有研究报道了非线性几何相位、传播相位和谐振相位的应用,可用于灵活的波前调控[36,122128]。在旨在提升效率的超构表面设计中引入相位调控,能够进一步提高非线性的功率密度。Tseng等[129]展示了一种既能产生又能聚焦二次谐波VUV光的超构透镜。该超构透镜由厚度为150 nm、具有C3对称性的ZnO纳米谐振器构成,利用非线性几何相位将394 nm的光转换为197 nm的聚焦光束,形成直径为1.7 µm的聚焦光斑,其功率密度较超透镜表面提升了21倍,如图4(a)所示[129]。

除了提升非线性功率密度之外,超构透镜还能够实现谐波成像。Schlickriede等[130]利用一种介电非线性超构透镜研究物体成像,该透镜利用米氏纳米谐振器产生非线性传播相位,如图4(b)所示。研究人员用红外光照射物体,并在可见光谱的谐波波长处获取成像。通过重新审视经典透镜理论,他们结合了实验和理论分析,提出并验证了一种适用于非线性成像的广义高斯成像公式。实验还展示了非线性超构透镜促进的高阶空间相关性,揭示了更多的图像特征。

全息显示是呈现图像的另一种重要方法。Gao等[116]利用具有C形超构原子的硅基超构表面,提出了一种非线性全息超构表面的新机制,如图4(c)所示。这些纳米天线在泵浦激光波长处增强了基频谐振,同时通过高阶谐振将THG信号重新定向到气隙区域。该方法显著降低了谐波波长处的吸收损耗,取得了高达230倍的增强因子。研究人员引入突变的非线性谐振相位变化,利用该超构表面实验生成了高效的青色和蓝色THG全息图。该研究展示了对共振相位的控制及降低非线性全介电超构表面损耗的潜力。

各种扩展功能和应用也得到了发展,如太赫兹(THz)波的产生与复用功能[72,131133]。如图4(d)所示,McDonnell等[134]在具有几何相位的非线性超构表面中引入了宽带太赫兹辐射。该太赫兹发射器通过实验展示了宽带单周期太赫兹脉冲可调谐线偏振、自旋态与太赫兹频率的空间分离以及具有时间偏振色散特性的少周期脉冲的产生。研究人员还利用太赫兹波的自旋控制进行了氨基酸的CD光谱测量。Wang等[135]提出,基于几何相位的非线性手性光学超构表面可以生成自旋解锁的轨道角动量(OAM),如图4(e)所示。他们的设计包含两种具有相反手性的等离激元超构原子,增强了自旋依赖的CD效应。通过将特定的相位奇点和相位梯度编码到不同通道,实验证明了在SHG中实现自旋解锁的波束操控能力。这一进展为OAM光的灵活调制开辟了新的途径。

非线性相位控制既需要具有高品质因子的强共振增强,也需要稳定的非线性相位控制,以确保非线性超构器件的高性能[136]。然而,将高品质因子共振与相位控制相结合存在挑战,因为相位控制通常是单个超构原子的局域响应,而高品质因子共振通常需要多个超构原子之间强烈的非局域相互作用[137139]。Hail等[140]展示了一种基于高阶米氏共振的局域高品质因子超构表面,实现了对THG的显著增强和精确空间控制,如图4(f)所示。实验结果表明,THG的产生效率为3.25 × 10-5,同时非线性超构透镜展现出高效聚焦能力,并在± 11°入射角范围内仍能保持稳定且与角度无关的非线性响应。这种兼具局域相位控制和高效谐波产生的能力,解决了平衡局域相位控制与非局域共振激发的难题,为先进的非线性相位调制器件提供了良好前景。

6 总结与展望

本文对非线性超构器件领域的最新发展进行了全面综述。激发二阶非线性响应的基本要求是不含反演对称性,这可以通过两种途径实现:一是在等离激元超构器件中人为引入对称性破缺;二是选择本身具有非反演对称晶体结构的介电材料。超构器件的一大优势在于其能够支持强谐振模式,这些模式能够显著聚集并增强电磁场,从而提升非线性效率。此外,远场辐射调控正逐渐成为提升非线性信号收集能力的有效策略。非线性相位控制则兼具效率提高与辐射调控的双重优势,对非线性成像、传感等应用大有裨益。

需要强调的是,目前研究中所采用的纳米结构设计通常都比较简单。然而,集成谐振单元(IRU)[141]能够将多种超构原子和谐振模式集成于单一构建单元内,并实现内部耦合,其功能和性能已被证明均优于单一超原子结构,包括高效率、灵活的相位调制以及宽工作频带等。尽管目前有关IRU的研究主要集中在线性超构器件领域,但其在非线性研究中同样具有巨大潜力。我们认为,这一概念有望显著增强非线性响应,并为可调谐[142]与选择性超构器件等非线性应用开辟新的可能性。此外,还需注意的是,大量非线性超构器件的研究忽视了线性响应的作用。开发能够在线性与非线性条件下均可运行的超构器件,将有助于提升其整体功能性。

尽管本文已讨论了非线性超构器件的多种应用,但仍有一些具体方向值得进一步发展。迄今为止,研究主要集中在二阶与三阶非线性响应,而HHG也应当得到更多关注[58,143145]。HHG可将谐波激发范围从可见光扩展至深紫外甚至X射线波段。此外,单个超构器件能够产生多种谐波,这一能力为非线性波长复用功能提供了可能性。我们必须承认,目前HHG的效率仍不理想,其主要挑战在于如何在高谐波频率下增强场约束。此外,由于HHG过程通常伴随低阶过程,因此还须解决选择特定谐波频率并抑制串扰的问题。

调制多维度能力依然是非线性超构器件的重要评估指标。非互易性已成为一种颇具前景的策略[146149]。例如,Kruk等[90]利用介电超构器件在三阶非线性过程中实现了非对称成像;Boroviks等[59]则开发了用于诱导非对称SHG的等离激元超构器件。除了提升空间域的调制能力外,时间尺度同样不可忽视。非线性时变超构器件已实现对谐波偏振特性的超快调制,涵盖了线偏振[60]和圆偏振[150]之间的切换。

此外,研究领域正从经典光学拓展至量子光学[151152]。大量研究[153155]已展示了通过非线性超构器件中的SPDC产生纠缠光子对的可行性。该方法不仅实现了量子系统的微型化,还促进了高维量子光源的产生[61],有望提升量子成像[156]、传感[157]和计算[158]的性能。我们相信非线性超构器件将在诸多应用领域持续展现其巨大潜力。

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