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体光伏效应是一种二阶非线性光电响应, 指非中心对称结构材料在均匀光辐照下产生稳态的光电流. 体光伏效应由于开路电压不受半导体能隙限制, 并且功率转换效率可以突破Shockley-Queisser极限, 因此引发广泛关注. 此外, 体光伏效应与固体的量子几何性质(如Berry曲率和量子度规)密切相关, 是一种研究晶体电极化、轨道磁化和量子霍尔效应的有效手段. 二维材料具有丰富的电、光、磁、拓扑性质及相互作用机制, 可有效提高体光伏器件性能(如拓展体光伏效应响应范围等), 对探索基础物理问题亦具有重要的研究价值. 本文概述了体光伏效应的发展历程及其几种物理机制, 重点讨论了二维材料中体光伏效应取得的研究进展, 包括单一成分二维材料、二维材料堆垛工程(如二维材料同质结和异质结), 以及在此基础上通过外界作用(如磁场、应变工程)实现产生或调控体光伏效应响应. 最后对二维体光伏效应的发展前景进行了展望.The bulk photovoltaic effect is a second-order nonlinear photoelectric response, which refers to a phenomenon that non-centrosymmetric structural material generates a steady-state photocurrent under uniform light irradiation. The bulk photovoltaic effect has attracted widespread attention due to its open-circuit voltage is not limited by the semiconductor bandgap and power conversion efficiency breaks through the Shockley-Queisser limit. In addition, the bulk photovoltaic effect is closely related to the quantum geometric properties (such as Berry curvature and quantum metric) of solids, thus making it an effective means to study crystal polarization, orbital magnetization, and quantum Hall effects. Two-dimensional (2D) materials are rich in electrical, optical, magnetic, topological properties and their interactions, which can effectively improve the performances of bulk photovoltaic devices (such as expanding response range of bulk photovoltaic effect) and have important research value for exploring basic physical problems. This paper reviews the development process of bulk photovoltaic effect and its physical mechanism. The research progress of bulk photovoltaic effect in 2D materials is discussed in detail, including single component 2D materials, 2D material stacking engineering (such as 2D material homojunctions and heterojunctions), and other factors (such as magnetic field, strain engineering) to generate or regulate the bulk photovoltaic effect response. Finally, the development prospect of two-dimensional bulk photovoltaic effect is prospected.
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Keywords:
- bulk photovoltaic effect /
- spatial inversion symmetry /
- two-dimensional materials /
- stacking engineering
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图 2 体光伏效应的几种介观模型 (a) 楔形反对称散射中心[40]; (b) 光激发载流子在非对称势阱中的不对称散射[40]; (c) Rashba自旋轨道耦合[40]; (d) 金属/铁电体/金属结构中的退极化场机理示意图[41,42]
Fig. 2. Several mesoscopic models for the bulk photovoltaic effect: (a) Asymmetric carrier scattering centers[40]; (b) asymmetric potential well at a carrier generation center[40]; (c) the minimum band splitting arising from spin-orbit coupling[40]; (d) schematic diagram of depolarization field in a metal/ferroelectric/metal structure[41,42].
图 4 WS2 纳米管体光伏响应 (a) 单层WS2和(b) WS2 纳米管器件的短路电流与激光光斑在器件不同位置的依赖关系; (c) 不同辐照强度条件下WS2纳米管的I-V变化曲线; (d)不同激发波长下短路电流随激光功率密度变化关系, 插图为不同波长激发的可能跃迁路径[56]
Fig. 4. Bulkphotovoltaic response for WS2 nanotubes: The dependence of Isc on the position of the laser spot in a WS2 monolayer device (a) and WS2 nanotube device (b); (c) I–V characteristics recorded at different illumination intensities; (d) dependence of Isc on Plaser for three different wavelengths. The bottom right inset illustrates possible excitation paths from the valence band (VB) to the conduction band (CB) for each wavelength[56].
图 5 (a) 二维CuInP2S6 BPVE器件图像及器件表面短路电流分布图; (b) 二维CuInP2S6 BPVE器件在明暗条件下的J-V输出曲线; (c) 二维CuInP2S6器件分别在经过正向极化、 无极化和反向极化后的J-V输出曲线; (d) BPVE性能随CuInP2S6厚度的变化关系; (e) 开路电压随温度的变化关系[57]
Fig. 5. (a) The optical image and corresponding short-circuit photocurrent density mapping of the two dimensional CuInP2S6 BPVE device; (b) the characteristic output I-V curves of the two dimensional CuInP2S6 BPVE device at dark and bright conditions; (c) output J-V curves at specific poling voltages with the positively, zero voltage, and negatively poled respectively; (d) the thickness dependent BPVE in CuInP2S6; (e) the open-circuit voltage as a function of the temperature, the Voc vanishes when the temperature increases to the phase transition temperature at about 315 K[57].
图 6 (a) 单层1Td WTe2晶体结构示意图及对称性分析; (b) 双栅极单层WTe2器件的结构示意图及光学图像; (c) 红、黑和蓝3个位置处, 光电流$I_{\hat{a}} $随激光偏振态的依赖关系, 插图分别为光电流$I_{\hat{a}} $与${\hat{a}}\text{-}{\hat{b}} $平面内位置关系; (d) 不同位移场极化下的圆偏振光伏效应电流, T = 20 K[58]
Fig. 6. (a) Crystal structure monolayer 1Td WTe2; (b) schematic and optical image of a dual-gated monolayer WTe2 device; (c) polarization-dependent $I_{\hat{a}} $ with the light spot fixed at the red, black, and blue dots shown in the inset, inset depicts the photocurrent along ${\hat{b}} $ with linear polarized light as a function of the beam spot location in the ${\hat{a}}\text{-}{\hat{b}} $ plane; (d) polarization-dependent circular photo galvanic effect currents for different displacement fields at T = 20 K[58].
图 7 TDBG光探测器输运特性 (a) TDBG光探测器示意图; (b) 在不同栅极偏置电压(VBG, VTG)条件下线性BPVE光伏电压随激发光源偏振角度依赖关系; (c) T = 79 K, λ = 5 μm时, 不同栅极偏置电压下TDBG中的可调谐圆偏振BPVE; (d) 5 μm椭圆偏振光(χ = 36.5°, ψ = 110°)激发产生光电压(Vph)分布图, 插图中χ 和 ψ分别为偏振椭圆的椭圆率和方位角[62]
Fig. 7. Transport properties of the TDBG photodetector: (a) Schematic of the TDBG photo detector; (b) linear BPVE voltage(Vph) as a function of polarization angle at a set of fixed gate voltage biases (VBG, VTG), the data are fitted by using Vph=VCcos(2ψ)+VS sin(22ψ)+Vconst; (c) circular BPVE photovoltage (Vph) as a function of the angle of the quarter-wave plate (θ) at different gate voltage biases(VBG, VTG), measured at T = 79 K and λ = 5 μm; (d) photovoltage mapping excited by elliptically polarized light at 5 μm, with χ = 36.5° and ψ = 110°. χ and ψ are the ellipticity and orientation angles of the polarization ellipse in the inset, respectively[62]
图 8 (a) 双层MoS2的不同堆叠方式(2H和3R)晶体结构及石墨烯/3R-MoS2/石墨烯异质结隧道结器件结构示意图; (b) 双层3R-MoS2器件图片及光电流分布图像(白色虚线内部); (c) 双层3R-MoS2的两种可能堆叠畴结构(左)及器件中不同畴位置处光电流分布图像(右); (d) AB畴位光电流大小随着偏置电压及激光强度的依赖关系[63]
Fig. 8. (a) Schematic of H stacking (2H) and R stacking (3R) of bilayer MoS2 and the tunneling junction device (composed of graphene/3R-MoS2/graphene heterostructure); (b) optical image of the BPVE device and scanning photovoltaic current map of BPVE device (consisting of one, two and three layers); (c) schematic of two possible stacking domains (AB and BA) of a 3R bilayer MoS2 (left) and the scanning photo voltaic current map of device (right), the positive and negative photo response areas correspond to the AB and BA domains with almost symmetric responsivity; (d) bias voltage dependence of the photovoltaic current in the AB domain at different laser powers between 10 and 70 µW[63].
图 9 (a)单层WSe2/BP异质结晶体结构示意图; WSe2/BP异质结器件图像(b)和沿着器件中ab直线的光电流分布关系(c); WSe2/BP异质结器件图像(d)与器件沿E1-E2光电流分布(e); (f) 线偏振体光伏光电流与激光功率的依赖关系[64]
Fig. 9. Schematic illustrations of hetero interface of WSe2/BP (the mirror planes of both WSe2 and BP are parallel); WSe2/BP device (b) and photocurrent mapping in device along ab direction (c); WSe2/BP device (d) and photocurrent mapping in device along the E1 and E2 electrodes (e); (f) laser power P dependence of the photocurrent I for two different wavelengths of 632.8 nm and 532 nm[64].
图 10 CrI3器件的光伏响应 (a) 4层CrI3(AFM基态)异质结器件示意图; (b) 4层CrI3异质结器件的光电流随外磁场强度的变化曲线; (c) 3层CrI3异质结器件中光电流随1/4玻片角度变化曲线; (d) 差分光电流$I_{\rm ph}(\sigma^+) - I_{\rm ph} (\sigma^-) $随外磁场的变化曲线[65]
Fig. 10. Photocurrent response of CrI3 junction device: (a) Schematic of a four layer CrI3 junction device in AFM ground state (↑↓↑↓); (b) photocurrent as a function of external magnetic field (H) measured from the four layer CrI3 junction device; (c) photocurrent as a function of quarter-wave plate angle for ↑↑↑ state (2 T) and ↓↓↓ state (–2 T) measured from the trilayer CrI3 junction device; (d) the change in photocurrent $I_{\rm ph}(\sigma^+) - I_{\rm ph} (\sigma^-) $as a function of μ0H measured from the same device[65].
图 11 (a) 相变材料混合系统中二维材料应变梯度工程示意图及二维材料中的应变梯度曲线; (b) VO2/MoS2异质结中MoS2拉曼$ {\text{E}}_{{\text{2g}}}^{1} $模式映射图; (c) VO2/MoS2异质结器件结构示意图及器件在激光照射下光斑1 (Laser@1)和光斑2 (Laser@2)及暗态时的I-V曲线; (d) 405 nm激光照射下器件中 3 (Laser@3)和4 (Laser@4)处短路电流的偏振依赖性[44]
Fig. 11. (a) Strain-gradient engineering of a 2D material by using a phase-change material in a hybrid system, on a reversible structural phase transition between phase I and phase II, strain gradients are generated in the 2D material at the edge of the phase-change material, inducing shifts of electron charge centers (dipole moments), the strain plot illustrates strain gradients in the 2D material(bottom panel); (b) Raman mapping of $ {\text{E}}_{{\text{2g}}}^{1} $ mode of MoS2 on a VO2/MoS2 device; (c) the schematic diagram of VO2/MoS2 device and current-voltage curves of the device under laser illumination at spot 1 (Laser@1) and 2 (Laser@2) and dark conditions; (d) light polarization dependence of the short-circuit current under laser (405 nm) illumination at spots 3 (Laser@3) and 4 (Laser@4) in a device[44].
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Google Scholar
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Google Scholar
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Google Scholar
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Google Scholar
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