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石墨烯异质结及其光电器件的研究进展

韩天亮 唐利斌 左文彬 姬荣斌 项金钟

韩天亮, 唐利斌, 左文彬, 姬荣斌, 项金钟. 石墨烯异质结及其光电器件的研究进展[J]. 红外技术, 2021, 43(12): 1141-1157.
引用本文: 韩天亮, 唐利斌, 左文彬, 姬荣斌, 项金钟. 石墨烯异质结及其光电器件的研究进展[J]. 红外技术, 2021, 43(12): 1141-1157.
HAN Tianliang, TANG Libin, ZUO Wenbin, JI Rongbin, XIANG Jinzhong. Research Progress of Graphene Heterojunctions and Their Optoelectronic Devices[J]. Infrared Technology , 2021, 43(12): 1141-1157.
Citation: HAN Tianliang, TANG Libin, ZUO Wenbin, JI Rongbin, XIANG Jinzhong. Research Progress of Graphene Heterojunctions and Their Optoelectronic Devices[J]. Infrared Technology , 2021, 43(12): 1141-1157.

石墨烯异质结及其光电器件的研究进展

基金项目: 

国家重点研发计划 2019YFB2203404

云南省创新团队项目 2018HC020

自然科学基金项目 11864044

详细信息
    作者简介:

    韩天亮(1995-),男,硕士研究生,研究方向是光电材料

    通讯作者:

    唐利斌(1978-),男,研究员级高级工程师,博士生导师,主要从事光电材料与器件的研究。E-mail:sscitang@163.com

    项金钟(1963-),男,教授,主要从事低维物理、纳米结构材料及光电应用研究。E-mail:jzhxiang@ynu.edu.cn

  • 中图分类号: TN204

Research Progress of Graphene Heterojunctions and Their Optoelectronic Devices

  • 摘要: 石墨烯是具有高迁移率、高热导率、高比表面积、高透过率及良好的机械强度等特性的二维材料,在光电子器件领域被广泛用作透明电极及电荷传输层等。但由于石墨烯是零带隙材料,为半金属性,限制了其在半导体光电子器件领域的应用。为更加切合半导体产业应用的要求,构建异质结已经成为相关领域实现应用的重要途径。国际上已有较多团队开展了石墨烯异质结相关研究,目前已有较多报道。本文从石墨烯的性质出发,讲述了石墨烯异质结的发展历程,制备方法,并从材料制备与器件结构的角度总结了基于石墨烯异质结光电子器件的研究进展。最后,对石墨烯异质结在光电子器件领域的发展进行了展望。
  • 图  1  几种石墨烯结构、形貌的表征图:(a) CVD制备石墨烯的高分辨透射电镜(high resolution transmission electron microscopy, HRTEM)图像[15];(b) 石墨烯纳米片的扫描电镜(scanning electron microscopy, SEM)形貌图[16];(c) 石墨烯量子点的TEM表征图[17];(d) 石墨烯纳米线的SEM形貌图[18];(e) 外延生长石墨烯的莫尔图案[19];(f) 石墨烯纳米棒的SEM形貌图[20];(g) 石墨烯/TiO2/Ag团簇的SEM表征图[21];(h) 石墨烯/TiO2/Ag团簇的TEM表征图[21];(i) CVD石墨烯薄膜的实物图[22]

    Figure  1.  Characterizations of several graphene structures and morphologies: (a) HRTEM image of CVD graphene[15]; (b) SEM image of graphene nanosheets[16]; (c) TEM image of graphene quantum dots[17]; (d) SEM image of graphene nanowires[18]; (e) Epitaxially grown graphene Moiré pattern[19]; (f) SEM image of graphene nanorods[20]; (g) SEM image of graphene/TiO2/Ag clusters[21]; (h) TEM image of graphene/TiO2/Ag clusters; (i) Optical image of CVD transferred graphene film[22]

    图  2  石墨烯异质结的结构:(a) 单层石墨烯(SLG)与TiO2纳米棒异质结光电探测器[28];(b) SLG与TiO2纳米棒异质结截面SEM图[28];(c) β-Ga2O3与石墨烯异质结光电探测器[33];(d) 石墨烯纳米沟道光电探测器[34];(e) 石墨烯/MoTe2异质结光电探测器[35];(f) 石墨烯/钙钛矿异质结光电探测器[36];(g) 石墨烯/Si异质结光电探测器[37];(h) 石墨烯/GeSn异质结光电探测器[38];(i) 范德瓦尔斯异质结叠放结合示意图[39]

    Figure  2.  The structures of graphene heterojunctions: (a) Single-layer graphene (SLG) and TiO2 nanorod heterojunction photodetector[28]; (b) Cross-section SEM image of SLG and TiO2 nanorod heterojunction[28]; (c) β-Ga2O3 and graphene heterojunction photodetector[33]; (d) Graphene nanochannel photodetector[34]; (e) Graphene/MoTe2 heterojunction photodetectors[35]; (f) Graphene/perovskite heterojunction photodetectors[36]; (g) Graphene/Si heterojunction photodetector[37]; (h) Graphene/GeSn heterojunction photodetector[38]; (i) Diagram of van der Waals heterojunction stacking and combining[39]

    图  3  石墨烯异质结对能带结构的调制:(a) 石墨烯/碳纳米管(CNT)异质结场效应晶体管器件结构示意图[40];(b) 石墨烯/碳纳米管异质结能带图,其中VGS表示出了其能带的弯曲变化情况[40];(c) 石墨烯-碳纳米管异质结电容随电压变化图[40];(d) WS2/石墨烯异质结器件示意图[41];(e) WS2/石墨烯异质结器件中低于WS2能级的两种不同的载流子激发机制[41];(f) 加入不同层数石墨烯的瞬态吸收光谱图[41];(g) MoS2/graphene/WSe2PGN异质结的器件结构示意图[42];(h) MoS2/graphene/WSe2异质的能带示意图,其中画出了载流子运输机制[42];(i) MoS2/graphene/WSe2PGN异质结器件的响应率和探测率随波长的变化图[42]

    Figure  3.  Modulations of the energy band structure of graphene heterojunctions: (a) Schematic diagram of graphene/carbon nanotube (CNT) heterojunction field effect transistor device structure[38]; (b) Diagram of graphene/carbon nanotube heterojunction energy band, where VGS shows the bending change of its energy band[38]; (c) C-V curves of graphene/carbon nanotube heterojunction[38]; (d) Device structure of WS2/graphene heterojunction[41]; (e) Two carrier excitation mechanisms below the WS2 band gap of WS2/ graphene heterojunction[41]; (f) TA spectrum with different layer graphene[41]; (g) Device structure of MoS2/graphene/WSe2 PGN heterojunction[42]; (h) Energy band of the MoS2/graphene/WSe2 heterojunction and carrier transport mechanisms[42]; (i) R-λ and D*-λ curves of MoS2/graphene/WSe2 PGN heterojunction[42]

    图  4  石墨烯异质结的光电特性:(a) ZnO纳米棒的SEM图[43];(b) 覆盖有石墨烯的ZnO纳米棒的Mapping图[43];(c) 加入石墨烯与未加石墨烯样品的PL光谱图[43];(d) CsPbBr3/石墨烯异质结的器件示意图[44];(e)和(f)分别为CsPbBr3/石墨烯异质结产生的PPC、NPC效应的能带解析图[44];(g) CsPbBr3/石墨烯异质结在紫外光照下的光电响应图谱[44];(h) CsPbBr3/石墨烯异质结在不同的可见光波段下的光电响应图[44]

    Figure  4.  Optoelectronic characteristics of graphene heterojunctions: (a) SEM image of ZnO nanorods[43]; (b) Mapping images of ZnO nanorods covered with graphene[43]; (c) PL spectrum of samples with and without graphene[43]; (d) Structures of CsPbBr3/graphene heterojunction device[44]; (e) and (f) The energy band analysis diagrams of PPC and NPC effects of CsPbBr3/graphene heterojunctions[44]; (g) Photoelectric response of CsPbBr3/graphene heterojunctions under radiation of ultraviolet light[44]; (h) Photoelectric response of CsPbBr3/graphene heterojunction in different visible light bands[44]

    图  5  石墨烯异质结的热力、力学特性:(a) 磷烯/石墨烯异质结器件两端放置在冷场和热场的示意图[45];(b) 磷烯/石墨烯异质结界面处温度特性[45];(c) 室温下磷烯/石墨烯异质结在不同界面构型处的ITC变化情况[45];(d) C3N/石墨烯异质结结区温度特性[46];(e) C3N/石墨烯异质结器件能量-时间曲线[46];(f) MoS2/石墨烯器件结构图[47];(g) MoS2/石墨烯异质结构中和无张力的双层石墨烯中石墨烯的面内声子谱Gi (ω)的比较[47];(h)MoS2/石墨烯异质结的热声子对比[47]

    Figure  5.  Thermal and mechanical properties of graphene heterojunctions: (a) The schematic diagram of phosphorene/graphene heterojunction device, which ends are placed at the cold and hot fields[45]; (b) The temperature characteristics of the phosphorene/grapheme heterojunction interfaces[45]; (c) ITC changes of phosphorene/grapheme heterojunction with different interfacial configurations at room temperature[45]; (d) Temperature characteristics of junction area of C3N/graphene heterojunction[46]; (e) Energy-Time curves of C3N/graphene heterojunction device[46]; (f) Structure diagram of MoS2/graphene device[47]; (g) Comparison of in-plane phonon spectrum Gi(ω) of graphene in MoS2/graphene heterostructure and in bilayer graphene without tension[47]; (h) Comparisons of thermophonons in MoS2/graphene heterojunction[47]

    图  6  石墨烯异质结器件的结构和表征:(a) 石墨烯/MoS2/石墨烯垂直异质结构示意图[64];(b) 石墨烯/MoS2/石墨烯器件的光学照片[64];(c) SiC/Graphene异质结器件示意图[67];(d) 石墨烯纳米片光电器件示意图,右图为单元纳米片的截面SEM图[65];(e) Bi2Te3/石墨烯异质结器件示意图[66];(f) 石墨烯/GeOI异质结近红外光电探测器的结构示意图和原子力显微镜(Atom force microscopy, AFM)表征图及石墨烯/GeOI肖特基结能带结构[68];(g) GaAs/Al2O3/Graphene器件结构示意图[69]

    Figure  6.  Structures and characterizations of grapheme heterojunction devices: (a) Schematic diagram of the vertical hetero structure of graphene/MoS2/graphene[64]; (b) Optical photo of graphene/MoS2/graphene device[64]; (c) Structure diagram of SiC/graphene heterojunction device[67]; (d) Diagram of graphene nanosheet photoelectric device, the right picture is the cross-sectional SEM image of the unit nanosheet[65]; (e) Structure diagram of Bi2Te3/graphene heterojunction device[66]; (f) Schematic illustration of the graphene/GeOI heterojunction near infrared photodetector, AFM image of the device and the energy band structure of graphene/GeOI Schottky junction[68]; (g) Structure diagram of GaAs/Al2O3/graphene device[69]

    图  7  几种外延生长制备的石墨烯异质结器件:(a) 水热法组装WS2/石墨烯光电探测器示意图[62];(b) WS2/Graphene异质结器件SEM图[62];(c) 石墨烯外延生长的AFM图[61];(d) 在石墨烯基底上气相沉积WS2的器件制备示意图[61];(e) Si纳米线/石墨烯异质结样品TEM图[70];(f) Si纳米线/石墨烯异质结器件Raman表征[70];(g) Si纳米线/石墨烯异质结制备图[70]

    Figure  7.  Several graphene heterojunction devices prepared by epitaxial growth: (a) Diagram of WS2/Graphene photodetector prepared by hydrothermal method[62]; (b) SEM image of WS2/graphene heterojunction device[62]; (c) AFM image of graphene epitaxial growth[61]; (d) Diagram of device preparation by vapor deposition WS2 on graphene substrate[61]; (e) TEM image of Si nanowire/graphene heterojunction sample[70]; (f) Raman spectrum of Si nanowire/graphene heterojunction device[70]; (g) Diagram of preparation of Si nanowire/graphene heterojunction[70]

    图  8  石墨烯异质结场效应管的研究进展:(a) WS2/graphene垂直异质结场效应管显微图像[71];(b) 柔性透明衬底上的WS2/graphene异质结场效应管实物图[71];(c) WS2/graphene异质结的对数I-V特性曲线[71];(d) WSe2/graphene/WS2范德瓦尔斯异质结场效应管光电探测器[72];(e) WSe2/graphene/WS2异质结结构图[72];(f) WSe2/graphene/WS2与WSe2/WS2异质结的I-V曲线对比图[72];(g) 石墨烯/Si范德瓦尔斯异质结中THz光谱产生过程示意图[73];(h) 石墨烯/Si异质结发射的THz波幅与CW泵浦功率的关系图[73];(i) 石墨烯/C60/石墨烯异质结场效应管示意图[74]

    Figure  8.  Research progresses of graphene heterojunction field effect transistors (FET): (a) Micrograph of WS2/ graphene vertical heterojunction FET[71]; (b) Photo of WS2/graphene heterojunction FET on flexible and transparent substrate[71]; (c) Log I-V curves of WS2/graphene heterojunction[71]; (d) WSe2/graphene/WS2 van der Waals (vdWs) heterojunction FET photodetector[72]; (e) Structure of WSe2/graphene/WS2 heterojunction[72]; (f) Comparison of I-V curves of WSe2/graphene/WS2with WSe2/WS2 hetero - junction[72]; (g) Schematic of the THz generation process from the graphene/Si vdWs heterostructure[73]; (h) Dependence of the graphene/Si heterojunction emitted THz amplitude on the CW pump power[73]; (i) Diagram of graphene/C60/graphene heterojunction FET[74]

    图  9  石墨烯异质结在太阳能电池中的应用:(a) Al离子电池中MoSe2/N-石墨烯异质结结构电极[76];(b) N-石墨烯调制Al离子电池测试[76];(c) MoSe2/N-石墨烯异质结器件电容测试[76];(d) 复合石墨烯太阳能电池器件结构示意图[78];(e) MoS2/graphene异质结太阳能电池器件结构示意图[79];(f) 石墨烯作为Si异质结p-i-n结构电极[80];(g) 复合石墨烯太阳能电池器件的J-V曲线[78];(h) MoS2/graphene异质结太阳能电池的J-V曲线[79];(i) 有石墨烯的Si异质结p-i-n结构太阳能电池J-V曲线[80]

    Figure  9.  Applications of graphene heterojunctions in solar cells: (a) MoSe2/N-graphene heterojunction structure electrode in Al ion battery[76]; (b) Test of Al ion battery with N-graphene modulation[76]; (c) Capacitance test of MoSe2/N-graphene device[76]; (d) Schematic diagram of composited graphene solar cell device structure[78]; (e) Schematic diagram of MoS2/graphene heterojunction solar cell device structure[79]; (f) Graphene used as p-i-n structure electrode of Si heterojunction[80]; (g) J-V curves of composited graphene solar cell device[78]; (h) J-V curve of MoS2/graphene heterojunction solar cell[79]; (i) J-V curves of Si heterojunction p-i-n structure solar cell with graphene[80]

    图  10  石墨烯异质结在光电探测器中的应用:(a) Graphene/PdSe2/Ge异质结光电探测器结构示意图[81];(b) Graphene/n-Si异质结光电探测器结构示意图[82];(c) Graphene/n-Si异质结光电探测器能带图[82];(d) 非晶MgGaO/graphene异质结紫外光伏器件结构示意图[83];(e) ReSe2/graphene异质结DUV光电探测器结构示意图[84];(f) 石墨烯纳米壁/Si杂化异质结器件示意图[85];(g) 具有类金刚石中间碳层(DLC)的Graphene/Si异质结光电探测器结构示意图[86];(h) Graphene/DLC/Si器件SEM形貌图[86]

    Figure  10.  Applications of graphene heterojunction in photodetectors: (a) Structure diagram of graphene/PdSe2/Ge heterojunction photodetector[81]; (b) Structure diagram of graphene/n-Si heterojunction photodetector[82]; (c) Energy band diagram of graphene/n-Si heterojunction photodetector[82]; (d) Structure diagram of amorphous-MgGaO/graphene heterojunction ultraviolet photovoltaic device[83]; (e) Structure diagram of ReSe2/graphene heterojunction DUV photodetector[84]; (f) Diagram of graphene nanowall/Si hybrid heterojunction device[85]; (g) Structure diagram of graphene/Si heterojunction photodetector with diamond-like intermediate carbon layer (DLC)[86]; (h) SEM image of graphene/DLC/Si device[86]

    表  1  石墨烯异质结制备方法与器件的性能研究现状

    Table  1.   Current research status of graphene heterojunction preparation methods and device performances

    Preparation type Heterojunction structure Method Application and performance Ref.
    Random transfer Graphene/GaN/PDMS MOCVD Strain-controlled sensor 0.1% compression strain with a gauge factor of 13.48 [49]
    Graphene/MoS2 CVD Optoelectronic device Response time is 2 ps [50]
    Graphene/WS2 Mechanical peeling - - [51]
    Graphene/AlN/Si CVD/ALD Photodetector Rmax=3.96 A·W-1 [52]
    P3HT/Graphene/ PZT CVD Photodetector Rmax=50 A·W-1 [53]
    Controlled transfer Graphene/β-Ga2O3 CVD Photodetector R=12.8 A·W-1 [54]
    MLG/β-Ga2O3 CVD Photodetector D*=5.92×1013 Jones [33]
    Graphene/Si MOCVD Photodetector R=635 mAW-1 [38]
    Ge1-xSnx/Graphene CVD Photodetector R=1968 AW-1
    D*=2.962×1011 Jones
    [55]
    Graphene/Black phosphorus Mechanical peeling Photodetector R=183 mA·W-1
    D*=6.69×108 Jones
    [56]
    Black phosphorus/Graphene/InSe Mechanical peeling Photodetector R=3.02×104 mA·W-1
    D*=3.19×1015 Jones
    [57]
    Induced grown Bi2Se3/Graphene MBE Topological insulator anoplate - [58]
    Graphene/MoS2
    Grephene/WSe2
    Graphene/h-BN
    CVD - The light response of the device is significantly improved [59]
    Bi2Se3/Graphene MBE - - [60]
    WS2/Graphene CVD - Carrier lifetime increased by an order of magnitude [61]
    Graphene/MoS2
    Grephene/WSe2
    Graphene/h-BN
    CVD Van der Waals (vdWs) hetero-structures Light response is greatly improved [62]
    WS2/Graphene Hydrothermal Photoelectro chemical-type photodetector Light current is 1.4 μA·cm-2 at 0 V bias [63]
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