CN106025070A - Photomultiplier organic light detector with spectral selectivity and preparation method of photomultiplier organic light detector - Google Patents

Photomultiplier organic light detector with spectral selectivity and preparation method of photomultiplier organic light detector Download PDF

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CN106025070A
CN106025070A CN201610348206.2A CN201610348206A CN106025070A CN 106025070 A CN106025070 A CN 106025070A CN 201610348206 A CN201610348206 A CN 201610348206A CN 106025070 A CN106025070 A CN 106025070A
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transparency electrode
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CN106025070B (en
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高米勒
王文斌
苗建利
张福俊
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Beijing Jiaotong University
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    • H10K30/00Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
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Abstract

The invention provides a photomultiplier organic light detector with spectral selectivity. The photomultiplier organic light detector comprises a transparent substrate (1), a transparent electrode (2), a transparent electrode modifying layer (3), an active layer (4) and a metal electrode (5), wherein the transparent electrode (2) is arranged on the transparent substrate (1); the transparent electrode modifying layer (3) is arranged on the transparent electrode (2); the active layer (4) is arranged on the transparent electrode modifying layer (3); the metal electrode (5) is arranged on the active layer (4); the active layer is a blend film of an electron donor material and an electron acceptor material; the thickness of the film is 2.0-5.0 microns; the weight ratio of an electron donor material to the electron acceptor material in the active layer is 100 to 1; the electron donor material is a poly(3-exylthiophene) (P3HT) or perylene polymer (PBDT-TS1); and the electron acceptor material is a fullerene derivative (PCBM, ICBA) or a non-fullerene receptor (ITIC).

Description

具有光谱选择性的光电倍增型有机光探测器及其制备方法Photomultiplier organic photodetector with spectral selectivity and preparation method thereof

技术领域technical field

本发明涉及光探测领域。更具体地,涉及具有光谱选择性的光电倍增型有机光探测器及其制备方法。The invention relates to the field of light detection. More specifically, it relates to a photomultiplier organic photodetector with spectral selectivity and a preparation method thereof.

背景技术Background technique

有机半导体材料由于其消光系数高、成本低、绿色、可制成大面积柔性器件而备受人们的关注。随着有机半导体材料的不断发展,基于有机材料的光电子器件性能也有了大幅度提高,有机光探测器的研究也备受人们的关注。目前文献报道的有机光探测器主要基于有机光伏效应。有机材料捕获太阳光子而产生激子,激子扩散到给受体材料的界面处,解离成自由载流子,载流子被电极收集,从而产生光生电流,实现对光的探测和响应。由于受到材料消光系数、激子解离效率、载流子传输与收集效率的影响,这类光探测器的外量子效率都小于100%,对于弱光或超弱光探测,器件的响应度就受到了限制。因此,在实际应用中该类探测器需要加前置放大器,对微弱的电信号进行采样、放大,从而实现对微弱光的探测,而采用前置放大器则会增大探测系统的成本,同时带来新的噪音。Organic semiconductor materials have attracted much attention because of their high extinction coefficient, low cost, green, and large-area flexible devices. With the continuous development of organic semiconductor materials, the performance of optoelectronic devices based on organic materials has also been greatly improved, and the research on organic photodetectors has also attracted people's attention. The organic photodetectors reported in the literature are mainly based on the organic photovoltaic effect. The organic material captures solar photons to generate excitons. The excitons diffuse to the interface of the acceptor material and dissociate into free carriers. The carriers are collected by the electrodes, thereby generating a photo-generated current and realizing the detection and response to light. Due to the influence of material extinction coefficient, exciton dissociation efficiency, carrier transport and collection efficiency, the external quantum efficiency of this type of photodetector is less than 100%. For weak light or ultra-weak light detection, the responsivity of the device is restricted. Therefore, in practical applications, this type of detector needs to add a preamplifier to sample and amplify the weak electrical signal, so as to realize the detection of weak light, and the use of the preamplifier will increase the cost of the detection system and bring Come new noises.

基于光伏效应的有机光探测器,不可能直接制备出具有光谱选择性的有机光探测器,其有源层为给受体材料按重量比为1:0.8到1:4的比例掺杂,从而实现高效率的激子解离和载流子传输。两种有机半导体材料使得器件的光谱响应范围较宽,制备的有机光探测器不具有光谱选择性,其光谱响应范围一般都大于100nm。具有光谱选择性的有机光探测器在许多领域都有广泛的应用,诸如图像、医学传感、安全系统等,这些领域的共同特点是需要探测特定波长范围的光而忽略背景噪音。为了提高有机光探测器的光谱选择性,通常的做法是将宽光谱响应范围的光探测器与二向色棱镜或者带通光学滤光器耦合在一起。这无疑会增加有机光探测器制造成本及应用的复杂性,也会导致器件性能的降低。此外,商业化的带通光学滤波器并没有覆盖所有应用所需的波段,使得器件的半高全宽(FWHM)大于50nm。Based on the photovoltaic effect, it is impossible to directly prepare an organic photodetector with spectral selectivity. High-efficiency exciton dissociation and carrier transport are realized. The two organic semiconductor materials make the spectral response range of the device wider, and the prepared organic photodetector has no spectral selectivity, and its spectral response range is generally greater than 100nm. Spectrally selective organic photodetectors are widely used in many fields, such as imaging, medical sensing, security systems, etc. The common feature of these fields is the need to detect light in a specific wavelength range while ignoring background noise. In order to improve the spectral selectivity of organic photodetectors, it is common practice to couple a photodetector with a wide spectral response range to a dichroic prism or a bandpass optical filter. This will undoubtedly increase the manufacturing cost of the organic photodetector and the complexity of the application, and will also lead to a decrease in device performance. In addition, commercial bandpass optical filters do not cover all bands required for applications, resulting in devices with full width at half maximum (FWHM) greater than 50nm.

发明内容Contents of the invention

本发明的一个目的在于提供一种具有光谱选择性的光电倍增型有机光探测器,以较低的成本和简单的器件结构,实现光电倍增和光谱选择功能。An object of the present invention is to provide a photomultiplier organic photodetector with spectral selectivity, which realizes photomultiplier and spectral selection functions at a lower cost and with a simple device structure.

本发明的另一个目的在于提供一种具有光谱选择性的光电倍增型有机光探测器的制备方法,以简单的制备方法,实现光电倍增和光谱选择功能。Another object of the present invention is to provide a method for preparing a photomultiplier organic photodetector with spectral selectivity, which realizes photomultiplication and spectral selection functions with a simple preparation method.

为达到上述目的,本发明采用下述技术方案:To achieve the above object, the present invention adopts the following technical solutions:

具有光谱选择性的光电倍增型有机光探测器,包括:Photomultiplier organic photodetectors with spectral selectivity, including:

透明基底(1);transparent base(1);

设置在该透明基底(1)上的透明电极(2);a transparent electrode (2) arranged on the transparent substrate (1);

设置在该透明电极(2)上的透明电极修饰层(3);a transparent electrode modification layer (3) disposed on the transparent electrode (2);

设置在该透明电极修饰层(3)上的有源层(4);以及an active layer (4) disposed on the transparent electrode modification layer (3); and

设置在该有源层(4)上的金属电极(5),a metal electrode (5) disposed on the active layer (4),

其中,所述有源层为电子给体材料与电子受体材料的共混薄膜,所述薄膜厚度为2.0-5.0μm;所述有源层中电子给体和电子受体材料的重量比为100:1;其中,所述电子给体材料为聚(3-己基噻吩)(P3HT)或苝类聚合物(PBDT-TS1),所述电子受体材料为富勒烯衍生物(PCBM、ICBA)或非富勒烯受体(ITIC)。Wherein, the active layer is a blend film of an electron donor material and an electron acceptor material, and the thickness of the film is 2.0-5.0 μm; the weight ratio of the electron donor and the electron acceptor material in the active layer is 100:1; wherein, the electron donor material is poly(3-hexylthiophene) (P3HT) or perylene polymer (PBDT-TS1), and the electron acceptor material is fullerene derivative (PCBM, ICBA ) or non-fullerene acceptors (ITIC).

优选的,所述透明基底为玻璃。Preferably, the transparent substrate is glass.

优选的,所述透明电极为铟锡氧化物(ITO)。Preferably, the transparent electrode is indium tin oxide (ITO).

优选的,所述透明电极修饰层由聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸(PEDOT:PSS)、氧化钼(MoO3)或[9,9-二辛基芴-9,9-双(N,N-二甲基胺丙基)芴](PFN)构成。Preferably, the transparent electrode modification layer is made of poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid (PEDOT:PSS), molybdenum oxide (MoO 3 ) or [9,9-dioctylfluorene- 9,9-bis(N,N-dimethylaminopropyl)fluorene] (PFN).

优选的,所述金属电极为铝或银,厚度为100nm。Preferably, the metal electrode is made of aluminum or silver with a thickness of 100 nm.

优选的,所述有源层的共混薄膜厚度为2.0μm。Preferably, the thickness of the blended film of the active layer is 2.0 μm.

具有光谱选择性的光电倍增型有机光探测器的制备方法,包括以下步骤:A method for preparing a photomultiplier organic photodetector with spectral selectivity, comprising the following steps:

步骤1:将玻璃作为透明基底;Step 1: Use glass as a transparent substrate;

步骤2:在所述透明基底上制备透明电极;Step 2: preparing a transparent electrode on the transparent substrate;

步骤3:在所述透明电极上制备透明电极修饰层;Step 3: preparing a transparent electrode modification layer on the transparent electrode;

步骤4:在所述透明电极修饰层上制备有源层,包括:将聚(3-己基噻吩)(P3HT)或苝类聚合物(PBDT-TS1)作为电子给体材料,将富勒烯衍生物(PCBM、ICBA)或非富勒烯受体(ITIC)作为电子受体材料;所述电子给体材料和所述电子受体材料按照重量比100:1溶于邻二氯苯(o-DCB)中,制备成混合溶液,将所述混合溶液均匀滴涂在制备的透明电极修饰层上,再加热使邻二氯苯(o-DCB)快速挥发,留下厚度为2.0-5.0μm电子给体材料与电子受体材料的共混薄膜作为有源层,其中,所述加热温度为80-120℃;Step 4: Prepare an active layer on the transparent electrode modification layer, including: using poly(3-hexylthiophene) (P3HT) or perylene polymer (PBDT-TS1) as an electron donor material, derivatizing fullerene (PCBM, ICBA) or non-fullerene acceptor (ITIC) as the electron acceptor material; The electron donor material and the electron acceptor material are dissolved in o-dichlorobenzene (o- In DCB), a mixed solution is prepared, and the mixed solution is uniformly drip-coated on the prepared transparent electrode modification layer, and then heated to quickly volatilize o-dichlorobenzene (o-DCB), leaving a thickness of 2.0-5.0μm Electron A blended thin film of a donor material and an electron acceptor material is used as an active layer, wherein the heating temperature is 80-120°C;

步骤5:在所述有源层上制备金属电极。Step 5: preparing metal electrodes on the active layer.

优选的,步骤2进一步包括:将铟锡氧化物(ITO)镀在所述透明基底上,然后分别浸泡于去离子水、无水乙醇中,再用超声波清洗仪清洗;清洗干净后用氮气吹干,再用等离子清洗仪处理1min。Preferably, step 2 further includes: plating indium tin oxide (ITO) on the transparent substrate, then soaking in deionized water and absolute ethanol respectively, and cleaning with an ultrasonic cleaner; blowing with nitrogen after cleaning dry, and then treated with a plasma cleaner for 1 min.

优选的,步骤3进一步包括:在步骤2中制备的透明电极上旋涂聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸(PEDOT:PSS)或[9,9-二辛基芴-9,9-双(N,N-二甲基胺丙基)芴](PFN),其中旋涂速率为5000r/min,旋涂时间40s,聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸(PEDOT:PSS)用量为80μL;旋涂完毕后放在150℃的加热台上退火10min;或在步骤2中制备的透明电极上以0.2nm/s的速率蒸镀一层10nm厚的氧化钼(MoO3)。Preferably, step 3 further includes: spin-coating poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid (PEDOT:PSS) or [9,9-dioctyl] on the transparent electrode prepared in step 2 Fluorene-9,9-bis(N,N-dimethylaminopropyl)fluorene] (PFN), where the spin-coating rate is 5000r/min, the spin-coating time is 40s, poly(3,4-ethylenedioxythiophene) - The amount of polystyrene sulfonic acid (PEDOT:PSS) is 80 μL; after spin coating, put it on a heating platform at 150 ° C for 10 min; or evaporate a Molybdenum oxide (MoO 3 ) layer 10 nm thick.

优选的,步骤5进一步包括:将步骤4中得到的样品放入放置有铝丝的真空室中,所述真空室真空度低于1×10-4Pa;加热铝丝使其蒸发,蒸发速率为0.2nm/s,蒸发厚度为100nm。Preferably, step 5 further includes: putting the sample obtained in step 4 into a vacuum chamber with an aluminum wire, and the vacuum degree of the vacuum chamber is lower than 1×10 -4 Pa; heating the aluminum wire to make it evaporate, and the evaporation rate is It is 0.2nm/s, and the evaporation thickness is 100nm.

本发明的有益效果如下:The beneficial effects of the present invention are as follows:

1、所述有机光探测器法的半高全宽(FWHM)小于30nm,进而具有光谱选择性;1. The full width at half maximum (FWHM) of the organic photodetector method is less than 30nm, and then has spectral selectivity;

2、所述有机光探测器具有大于100%的外量子效率且器件结构简单;2. The organic photodetector has an external quantum efficiency greater than 100% and the device structure is simple;

3、所述有机光探测器制备方法经济且简单。3. The preparation method of the organic photodetector is economical and simple.

附图说明Description of drawings

下面结合附图对本发明的具体实施方式作进一步详细的说明。The specific implementation manners of the present invention will be further described in detail below in conjunction with the accompanying drawings.

图1示出本发明所述有机光探测器结构示意图。Fig. 1 shows a schematic diagram of the structure of the organic photodetector of the present invention.

图2示出本发明所述基于1.0μm厚P3HT:PCBM(100:1)为有源层的有机光探测器在-20V偏压下的外量子效率光谱曲线。FIG. 2 shows the external quantum efficiency spectrum curve of the organic photodetector based on the active layer of 1.0 μm thick P3HT:PCBM (100:1) under the bias voltage of -20V according to the present invention.

图3示出本发明所述基于2.0μm,2.5μm,5.0μm和7.5μm厚P3HT:PCBM(100:1)为有源层的有机光探测器在-20V偏压下的外量子效率光谱曲线。Fig. 3 shows that based on 2.0 μm, 2.5 μm, 5.0 μm and 7.5 μm thick P3HT: PCBM (100:1) is the external quantum efficiency spectral curve of the organic photodetector of active layer under-20V bias .

图4示出本发明所述方法流程图。Fig. 4 shows a flow chart of the method of the present invention.

图5示出本发明所述基于2.0μm厚P3HT:PCBM(100:1)为有源层的有机光探测器在-20V偏压下的外量子效率光谱曲线。FIG. 5 shows the external quantum efficiency spectrum curve of the organic photodetector based on the active layer of 2.0 μm thick P3HT:PCBM (100:1) under the bias voltage of -20V.

图6示出本发明所述基于2.0μm厚P3HT:PCBM(100:1)为有源层的有机光探测器在-20V偏压下的灵敏度曲线。FIG. 6 shows the sensitivity curve of the organic photodetector based on the active layer of 2.0 μm thick P3HT:PCBM (100:1) under the bias voltage of -20V according to the present invention.

具体实施方式detailed description

为了更清楚地说明本发明,下面结合优选实施例和附图对本发明做进一步的说明。附图中相似的部件以相同的附图标记进行表示。本领域技术人员应当理解,下面所具体描述的内容是说明性的而非限制性的,不应以此限制本发明的保护范围。In order to illustrate the present invention more clearly, the present invention will be further described below in conjunction with preferred embodiments and accompanying drawings. Similar parts in the figures are denoted by the same reference numerals. Those skilled in the art should understand that the content specifically described below is illustrative rather than restrictive, and should not limit the protection scope of the present invention.

如图1所示,具有光谱选择性的光电倍增型有机光探测器,包括透明基底1;设置在该透明基底1上的透明电极2;设置在该透明电极2上的透明电极修饰层3;设置在该透明电极修饰层3上的有源层4;以及设置在该有源层(4)上的金属电极5。As shown in Figure 1, a photomultiplier organic photodetector with spectral selectivity includes a transparent substrate 1; a transparent electrode 2 arranged on the transparent substrate 1; a transparent electrode modification layer 3 arranged on the transparent electrode 2; an active layer 4 arranged on the transparent electrode modification layer 3; and a metal electrode 5 arranged on the active layer (4).

所述透明基底1为玻璃,所述透明电极2为铟锡氧化物(ITO),所述透明电极修饰层3为聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸(PEDOT:PSS)、氧化钼(MoO3)或[9,9-二辛基芴-9,9-双(N,N-二甲基胺丙基)芴](PFN)。The transparent substrate 1 is glass, the transparent electrode 2 is indium tin oxide (ITO), and the transparent electrode modification layer 3 is poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid (PEDOT: PSS), molybdenum oxide (MoO 3 ) or [9,9-dioctylfluorene-9,9-bis(N,N-dimethylaminopropyl)fluorene] (PFN).

所述有源层4为电子给体材料与电子受体材料的共混薄膜,在本发明中,共混薄膜厚度选择为2.0-5.0μm。电子给体材料为聚(3-己基噻吩)(P3HT)或苝类聚合物(PBDT-TS1),电子受体材料为富勒烯衍生物(PCBM、ICBA)或非富勒烯受体(ITIC),电子给受体材料按重量比为100:1配比。The active layer 4 is a blended film of an electron donor material and an electron acceptor material. In the present invention, the thickness of the blended film is selected to be 2.0-5.0 μm. The electron donor material is poly(3-hexylthiophene) (P3HT) or perylene polymer (PBDT-TS1), and the electron acceptor material is fullerene derivative (PCBM, ICBA) or non-fullerene acceptor (ITIC ), the electron donor and acceptor materials are in a ratio of 100:1 by weight.

其中,有源层4的电子给受体材料的重量比为100:1,通过使用少量电子受体在器件中的质量比获得了光电倍增响应,器件具有大于100%的外量子效率,同时降低了器件的制备成本;通过调控有源层的厚度,使有机光探测器具有光谱选择性。Wherein, the weight ratio of the electron-donor-acceptor material of the active layer 4 is 100:1, and the photomultiplier response is obtained by using a small amount of electron-acceptor mass ratio in the device, and the device has an external quantum efficiency greater than 100%, while reducing The preparation cost of the device is reduced; by adjusting the thickness of the active layer, the organic photodetector has spectral selectivity.

具体的,所述有源层4吸收一个光子就可以导致很多载流子流过器件,从而获得较大的光电流,其工作机理为:界面附近陷阱中的电子诱导界面能带弯曲,从而降低空穴注入势垒,增强空穴从外电路的隧穿注入,获得较大的光电流。Specifically, the absorption of one photon by the active layer 4 can cause many carriers to flow through the device, thereby obtaining a larger photocurrent. The working mechanism is: electrons in traps near the interface induce interface energy band bending, thereby reducing The hole injection barrier enhances the tunneling injection of holes from the external circuit and obtains a larger photocurrent.

需要说明的是,如果有源层4共混薄膜厚度小于2.0μm,如图2所示,则器件的外量子效率在短波段处也会产生一个外量子效率峰值,器件在全光谱范围内就有两个外量子效率峰值,这就影响了器件的光谱选择性;如图3所示,器件的外量子效率会随着有源层4共混薄膜厚度的增加而减低,如果有源层4共混薄膜厚度在5.0-7.5μm之间,虽然部分厚度范围内外量子效率仍然大于100%,但考虑到实际应用中的误差,为了保证器件仍然具有光电倍增效应,所以共混薄膜应维持在2.0-5.0μm之间。It should be noted that if the thickness of the blended film of the active layer 4 is less than 2.0 μm, as shown in Figure 2, the external quantum efficiency of the device will also produce an external quantum efficiency peak at the short wavelength band, and the device will be stable in the full spectral range. There are two external quantum efficiency peaks, which affect the spectral selectivity of the device; as shown in Figure 3, the external quantum efficiency of the device will decrease with the increase of the thickness of the active layer 4 blended film, if the active layer 4 The thickness of the blended film is between 5.0-7.5 μm. Although the quantum efficiency inside and outside the partial thickness range is still greater than 100%, considering the error in practical applications, in order to ensure that the device still has a photoelectric multiplication effect, the blended film should be maintained at 2.0 Between -5.0μm.

进一步讲,2.0μm和5.0μm是实际应用中所述有机光探测器保持窄带探测(即光谱选择性)和光电倍增响应的两个临界值。Furthermore, 2.0 μm and 5.0 μm are two critical values for the organic photodetector to maintain narrow-band detection (ie, spectral selectivity) and photomultiplier response in practical applications.

如图4所示,所述有机光探测器制备过程如下:As shown in Figure 4, the preparation process of the organic photodetector is as follows:

步骤1:将玻璃作为透明基底。Step 1: Use glass as a transparent substrate.

步骤2:将铟锡氧化物(ITO)镀在所述透明基底上,然后分别浸泡于去离子水、无水乙醇中,再用超声波清洗仪清洗;清洗干净后用氮气吹干,再用等离子清洗仪处理1min。Step 2: Plating indium tin oxide (ITO) on the transparent substrate, then soaking in deionized water and absolute ethanol respectively, and then cleaning with an ultrasonic cleaner; after cleaning, blow dry with nitrogen, and then use plasma Washing instrument for 1min.

步骤3:在步骤2中铟锡氧化物(ITO)层上旋涂聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸(PEDOT:PSS)或[9,9-二辛基芴-9,9-双(N,N-二甲基胺丙基)芴](PFN),旋涂速率为5000r/min,旋涂时间40s,聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸(PEDOT:PSS)用量为80μL;旋涂完毕后放在150℃的加热台上退火10min;或在步骤2中铟锡氧化物(ITO)层上以0.2nm/s的速率蒸镀一层10nm厚的氧化钼(MoO3)。Step 3: Spin-coat poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid (PEDOT:PSS) or [9,9-dioctylfluorene on the indium tin oxide (ITO) layer in step 2 -9,9-bis(N,N-dimethylaminopropyl)fluorene](PFN), the spin coating speed is 5000r/min, the spin coating time is 40s, poly(3,4-ethylenedioxythiophene)-poly The amount of styrene sulfonic acid (PEDOT:PSS) is 80 μL; after the spin coating is completed, place it on a heating platform at 150 ° C for 10 min; Plating a layer of molybdenum oxide (MoO 3 ) with a thickness of 10nm.

步骤4:将聚(3-己基噻吩)(P3HT)或苝类聚合物(PBDT-TS1)作为电子给体材料,将富勒烯衍生物(PCBM、ICBA)或非富勒烯受体(ITIC)作为电子受体材料;所述电子给体材料和所述电子受体材料按照重量比100:1溶于邻二氯苯(o-DCB)中,制备成混合溶液,将所述混合溶液均匀滴涂在步骤3中聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸(PEDOT:PSS)层上,再加热使邻二氯苯(o-DCB)快速挥发,留下电子给体材料与电子受体材料的共混薄膜,其中,所述加热温度为80-120℃,共混薄膜厚度为2.0-5.0μm。Step 4: Using poly(3-hexylthiophene) (P3HT) or perylene polymer (PBDT-TS1) as the electron donor material, fullerene derivatives (PCBM, ICBA) or non-fullerene acceptors (ITIC ) as an electron acceptor material; the electron donor material and the electron acceptor material are dissolved in o-dichlorobenzene (o-DCB) according to a weight ratio of 100:1 to prepare a mixed solution, and the mixed solution is uniformly Drop-coat on the poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid (PEDOT:PSS) layer in step 3, and then heat to make o-dichlorobenzene (o-DCB) volatilize quickly, leaving electrons for A blended film of a bulk material and an electron acceptor material, wherein the heating temperature is 80-120° C., and the thickness of the blended film is 2.0-5.0 μm.

步骤5:将步骤4中得到的样品放入放置有铝丝的真空室中,所述真空室真空度低于1×10-4Pa;加热铝丝使其蒸发,蒸发速率为0.2nm/s,蒸发厚度为100nm,得到具有光谱选择性的光电倍增型有机光探测器。Step 5: Put the sample obtained in step 4 into a vacuum chamber with an aluminum wire, the vacuum degree of the vacuum chamber is lower than 1×10 -4 Pa; heat the aluminum wire to evaporate it, and the evaporation rate is 0.2nm/s , the evaporation thickness is 100nm, and a photomultiplier organic photodetector with spectral selectivity is obtained.

实施例一Embodiment one

具有光谱选择性的光电倍增型有机光探测器包括:透明基底1、透明电极2、透明电极修饰层3、有源层4以及金属电极5。The photomultiplier organic photodetector with spectral selectivity comprises: a transparent substrate 1 , a transparent electrode 2 , a transparent electrode modification layer 3 , an active layer 4 and a metal electrode 5 .

所述的透明电极2为透明ITO电极;所述透明电极修饰层3为聚(3,4-乙烯二氧噻吩)-聚苯乙烯磺酸(PEDOT:PSS);所述有源层4为聚(3-己基噻吩)P3HT与富勒烯衍生物PCBM的共混薄膜,其中,聚(3-己基噻吩)P3HT和富勒烯衍生物PCBM的质量比为100:1,有源层4厚度为2.0μm;所述金属电极5为铝。The transparent electrode 2 is a transparent ITO electrode; the transparent electrode modification layer 3 is poly(3,4-ethylenedioxythiophene)-polystyrenesulfonic acid (PEDOT:PSS); the active layer 4 is poly The blend film of (3-hexylthiophene) P3HT and fullerene derivative PCBM, wherein, the mass ratio of poly(3-hexylthiophene) P3HT and fullerene derivative PCBM is 100:1, and the thickness of active layer 4 is 2.0 μm; the metal electrode 5 is aluminum.

上述有机光探测器制备方法包括以下步骤:The preparation method of the above-mentioned organic photodetector comprises the following steps:

步骤1:将面积为4cm2玻璃作为透明基底。Step 1 : Use glass with an area of 4cm2 as a transparent substrate.

步骤2:将铟锡氧化物(ITO)镀在所述透明基底上,然后分别浸泡于去离子水、无水乙醇中,用超声波清洗仪清洗;清洗干净后用氮气吹干,将干燥的衬底表面用等离子清洗仪处理1min,提高衬底表面的清洁度及ITO表面的功函数。Step 2: Plating indium tin oxide (ITO) on the transparent substrate, then soaking in deionized water and absolute ethanol respectively, cleaning with an ultrasonic cleaner; blowing dry with nitrogen after cleaning, and drying the dried substrate The bottom surface is treated with a plasma cleaner for 1 min to improve the cleanliness of the substrate surface and the work function of the ITO surface.

步骤3:在步骤2中处理完毕的镀有ITO的玻璃衬底上旋涂PEDOT:PSS,其旋涂速率为5000r/min,容量80μL,旋涂时间40s,然后放在150℃的加热台上退火10min,去除PEDOT:PSS薄膜中的水份。Step 3: Spin-coat PEDOT:PSS on the ITO-coated glass substrate processed in step 2, with a spin-coating rate of 5000r/min, a capacity of 80μL, and a spin-coating time of 40s, and then place it on a heating stage at 150°C Anneal for 10 minutes to remove the moisture in the PEDOT:PSS film.

步骤4:将聚(3-己基噻吩)P3HT和富勒烯衍生物PCBM按照重量比100:1溶于邻二氯苯(o-DCB)中,制备成40mg/ml混合溶液,取50μL的混合溶液均匀滴涂在PEDOT:PSS/ITO衬底上,然后将基片转移到80℃的加热平台上使薄膜内的溶剂快速挥发,制备成2.0μm的混合薄膜。Step 4: Dissolve poly(3-hexylthiophene) P3HT and fullerene derivative PCBM in o-dichlorobenzene (o-DCB) at a weight ratio of 100:1 to prepare a 40 mg/ml mixed solution, and take 50 μL of mixed The solution was uniformly drop-coated on the PEDOT:PSS/ITO substrate, and then the substrate was transferred to a heating platform at 80°C to quickly evaporate the solvent in the film to prepare a 2.0 μm mixed film.

步骤5:将样品放入真空室中,对真空腔抽真空,使真空度达到4×10-5Pa。加热铝丝,使铝丝蒸发,蒸发速率为0.2nm/s,蒸发厚度为100nm,得到具有光谱选择性的光电倍增型有机光探测器。Step 5: put the sample into a vacuum chamber, and evacuate the vacuum chamber to make the vacuum degree reach 4×10 -5 Pa. The aluminum wire is heated to evaporate the aluminum wire with an evaporation rate of 0.2nm/s and an evaporation thickness of 100nm to obtain a photomultiplier organic photodetector with spectral selectivity.

如图5和图6所示,制成的2.0μm有源混合薄膜有机光探测器在-20V偏压下,在645nm处最大的外量子效率达到610%,探测灵敏度为1.71×1014琼斯。As shown in Figures 5 and 6, the fabricated 2.0μm active hybrid thin film organic photodetector has a maximum external quantum efficiency of 610% at 645nm and a detection sensitivity of 1.71×10 14 Jones under a bias voltage of -20V.

有源层4的电子给体材料聚(3-己基噻吩)(P3HT)与电子受体材料富勒烯衍生物(PCBM)按100:1重量比混合制备的共混薄膜通过减少电子受体在器件中的质量比获得光电倍增效果,即该有机光探测器具有大于100%的外量子效率,同时降低了器件的制备成本;通过调控该共混薄膜即有源层的厚度,使所述有机光探测器具有光谱选择性;具体的,设定有源层共混薄膜厚度为2.0μm使得该有机光探测器半高全宽(FWHM)小于30nm,因而具有光谱选择性。The blend film prepared by mixing the electron donor material poly(3-hexylthiophene) (P3HT) and the electron acceptor material fullerene derivative (PCBM) at a weight ratio of 100:1 in the active layer 4 reduces the electron acceptor in The mass ratio in the device obtains a photoelectric multiplication effect, that is, the organic photodetector has an external quantum efficiency greater than 100%, and at the same time reduces the preparation cost of the device; by regulating the thickness of the blend film, that is, the active layer, the organic The photodetector has spectral selectivity; specifically, setting the thickness of the active layer blend film to 2.0 μm makes the full width at half maximum (FWHM) of the organic photodetector less than 30 nm, thus having spectral selectivity.

实施例二Embodiment two

将实施例一中的有源层4共混薄膜厚度分别设置为2.5μm和5.0μm,如图3所示,两种情况下的有机光探测器外量子效率均大于100%,半高全宽(FWHM)均小于30nm,进而均具有光谱选择性。The active layer 4 blend film thickness in embodiment one is respectively set to 2.5 μm and 5.0 μm, as shown in Figure 3, the organic photodetector external quantum efficiency of two kinds of situations is all greater than 100%, full width at half maximum (FWHM ) are less than 30nm, and then all have spectral selectivity.

显然,本发明的上述实施例仅仅是为清楚地说明本发明所作的举例,而并非是对本发明的实施方式的限定,对于所属领域的普通技术人员来说,在上述说明的基础上还可以做出其它不同形式的变化或变动,例如有源层的制备可以有多种选择,电子给体材料可以为聚(3-己基噻吩)(P3HT)和苝类聚合物(PBDT-TS1)中任意一种,电子受体材料可以为富勒烯衍生物(PCBM、ICBA)或非富勒烯受体(ITIC)中任意一种,这里无法对所有的实施方式予以穷举,凡是属于本发明的技术方案所引伸出的显而易见的变化或变动仍处于本发明的保护范围之列。Apparently, the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. Those of ordinary skill in the art can also make There are other different forms of changes or changes, such as the preparation of the active layer, there are many options, and the electron donor material can be any one of poly(3-hexylthiophene) (P3HT) and perylene polymer (PBDT-TS1) The electron acceptor material can be any one of fullerene derivatives (PCBM, ICBA) or non-fullerene acceptors (ITIC), and it is impossible to exhaustively enumerate all the implementation modes here, and those belonging to the technology of the present invention Obvious changes or variations derived from the scheme are still within the protection scope of the present invention.

Claims (10)

1. there is the photomultiplier transit type organic photodetector of spectral selection, including:
Transparent substrates (1);
The transparency electrode (2) being arranged in this transparent substrates (1);
The transparency electrode decorative layer (3) being arranged in this transparency electrode (2);
It is arranged on the active layer (4) on this transparency electrode decorative layer (3);And
The metal electrode (5) being arranged on this active layer (4);
It is characterized in that, described active layer is the blend film of electron donor material and electron acceptor material, Described film thickness is 2.0-5.0 μm;Electron donor and the weight ratio of electron acceptor material in described active layer For 100:1;Wherein, described electron donor material is poly-(3-hexyl thiophene) (P3HT) or birds of the same feather flock together Compound (PBDT-TS1), described electron acceptor material be fullerene derivate (PCBM, ICBA) or Non-fullerene acceptor (ITIC).
Organic photodetector the most according to claim 1, it is characterised in that described transparent substrates is Glass.
Organic photodetector the most according to claim 1, it is characterised in that described transparency electrode is Indium tin oxide (ITO).
Organic photodetector the most according to claim 1, it is characterised in that described transparency electrode is repaiied Decorations layer is by poly-(3,4-ethene dioxythiophene)-polystyrolsulfon acid (PEDOT:PSS), molybdenum oxide (MoO3) Or [double (N, the N-DimethylAminopropyl) fluorenes of 9,9-dioctyl fluorene-9,9-] (PFN) is constituted.
Organic photodetector the most according to claim 1, it is characterised in that described metal electrode is Aluminum or silver, thickness is 100nm.
Organic photodetector the most according to claim 1, it is characterised in that being total to of described active layer Mixed film thickness is 2.0 μm.
7. there is the preparation method of the photomultiplier transit type organic photodetector of spectral selection, it is characterised in that Said method comprising the steps of:
Step 1: using glass as transparent substrates;
Step 2: prepare transparency electrode in described transparent substrates;
Step 3: prepare transparency electrode decorative layer in described transparency electrode;
Step 4: prepare active layer on described transparency electrode decorative layer, including: by poly-(3-hexyl thiophene) Or base polymer (PBDT-TS1) is as electron donor material, by fullerene derivate (P3HT) (PCBM, ICBA) or non-fullerene acceptor (ITIC) are as electron acceptor material;Described electronics is given Body material and described electron acceptor material are dissolved in o-dichlorohenzene (o-DCB) according to weight ratio 100:1, system Standby one-tenth mixed solution, by uniform for described mixed solution drop coating on the transparency electrode decorative layer of preparation, then adds Heat makes o-dichlorohenzene (o-DCB) quickly volatilize, and leaving thickness is 2.0-5.0 μm electron donor material and electricity The blend film of sub-acceptor material is as active layer, and wherein, described heating-up temperature is 80-120 DEG C;
Step 5: prepare metal electrode on described active layer.
Method the most according to claim 7, it is characterised in that step 2 farther includes: by indium Tin-oxide (ITO) is plated in described transparent substrates, is soaked in deionized water, dehydrated alcohol the most respectively In, then clean with ultrasonic washing instrument;Dry up with nitrogen after cleaning up, then with at plasma cleaning instrument Reason 1min.
Method the most according to claim 7, it is characterised in that step 3 farther includes: in step Spin coating poly-(3,4-ethene dioxythiophene)-polystyrolsulfon acid in the transparency electrode of preparation in rapid 2 (PEDOT:PSS) or [9,9-dioctyl fluorene-9,9-double (N, N-DimethylAminopropyl) fluorenes] (PFN), wherein Spin coating speed is 5000r/min, spin-coating time 40s, poly-(3,4-rthylene dioxythiophene)-polystyrene sulphur Acid (PEDOT:PSS) consumption is 80 μ L;Annealing 10min it is placed on the warm table of 150 DEG C after spin coating; Or it is deposited with the thick molybdenum oxide of one layer of 10nm with the speed of 0.2nm/s in the transparency electrode prepared in step 2 (MoO3)。
Method the most according to claim 7, it is characterised in that step 5 farther includes: will The sample obtained in step 4 is put in the vacuum chamber being placed with aluminium wire, and described vacuum degree in vacuum chamber is less than 1 ×10-4Pa;Heating aluminium wire makes it evaporate, and evaporation rate is 0.2nm/s, and evaporation thickness is 100nm.
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JP2023043171A (en) * 2021-09-15 2023-03-28 レイナジー テック インコーポレイション Structure of photodiode
JP7470752B2 (en) 2021-09-15 2024-04-18 レイナジー テック インコーポレイション Photodiode structure that self-filters light of a specific wavelength
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