Organic photodetector based on all-fused-ring small-molecule electron acceptor and use thereof

Abstract

The present invention provides an organic photodetector based on an all-fused-ring small-molecule electron acceptor and a use thereof. The structure of the all-fused-ring small-molecule compound is as shown in following formula (I). The organic photodetector provided by the present invention may mitigate corrosion by water and oxygen and photoaging degradation in an environment due to the use of highly stable all-fused-ring acceptor materials, thereby enhancing device stability, and may reduce the trap density of an active layer thin film and suppress the noise current of the device, thereby enabling the device to have high sensitivity. The organic photodetector provided by the present invention has near-infrared / short-wave infrared light detection capability, and implements the use in the fields of infrared imaging, biological recognition technology, medical monitoring, etc.

Description

Organic photodetectors based on fully fused-ring small molecule electron acceptors and their applications Technical Field

[0001] The present invention belongs to the field of organic optoelectronic materials and devices. Specifically, the present invention provides an organic photodetector based on a fully condensed-ring small molecule electron acceptor and its application. Background Art

[0002] The invention belongs to the field of organic optoelectronic materials and devices, and solves the technical problem of insufficient stability of organic photoelectric detection devices in the prior art.

[0003] Organic photodetectors, with their characteristics of solution processing, large-area flexibility, and compatibility with various readout circuits, have broad applications in optical communications, imaging, flexible wearable electronics, and bio-health monitoring. Diode-type organic photodetectors typically consist of an active layer composed of a blend of electron donors and electron acceptors sandwiched between two electrodes. They achieve low dark current and high response speed, thus holding great promise for future applications.

[0004] Currently, stability is a key issue affecting the development and application of organic photodetectors, and improving stability is crucial for their practical application. Active layer donor and acceptor materials are the core limiting factors in the stability of organic photodetector devices. Compared to donor materials, acceptor materials have a greater impact on device stability. In the early development of organic photodetectors, fullerenes and their derivatives were used as electron acceptors. However, fullerene-based acceptor systems suffer from insufficient morphological stability and are prone to clustering, resulting in insufficient device stability. Subsequently, mainstream small molecule acceptor materials have been non-fullerene materials with ADA or A-DA'DA configurations, where A and A' are electron-withdrawing units and D is an electron-donating unit. In these molecules, the central core and terminal groups are connected by single bonds, and an exocyclic ethylene double bond exists at the junction, making the material susceptible to photooxidative and chemical degradation, thereby reducing the device's lifespan. Therefore, how to address the stability issues facing existing organic photodetectors through the development of active layer acceptor materials and develop highly sensitive and stable organic photodetector devices has become a pressing issue for many researchers in the field. Summary of the Invention

[0005] One purpose of the present invention is to solve the technical problem of insufficient stability of organic photodetection devices in the prior art and to provide an application of a fully condensed ring small molecule compound;

[0006] Another object of the present invention is to provide an organic photodetector;

[0007] Another object of the present invention is to provide applications of the organic photodetector.

[0008] To achieve the above objectives, on the one hand, the present invention provides an application of a fully fused-ring small molecule compound in the preparation of an organic photodetector, wherein the compound structure is shown in the following formula (I):

[0009] R1 is -C m1 H 2m1+1 or -(CH2) n1 C(C x1 H 2x1+1 )(C y1 H 2y1+1 ),

[0010] m1 is an integer from 1 to 36, n1 is an integer from 0 to 10, and x1 and y1 are each independently an integer from 1 to 40;

[0011] Ar1 is a substituted or unsubstituted 4- to 14-membered heteroaryl or 4- to 8-membered heterocycloalkyl; when substituted, the heteroaryl or heterocycloalkyl is substituted by 1, 2, 3 or 4 substituents selected from F, Cl, Br, I, ═O or R2; the heteroaryl contains 1, 2 or 3 heteroatoms selected from N, S, O or Se;

[0012] R2 is selected from -C m2 H 2m2+1 or -(CH2) n2 C(C x2 H 2x2+1 )(C y2 H 2y2+1 ),

[0013] m2 is an integer from 1 to 36, n2 is an integer from 0 to 10, and x2 and y2 are each independently an integer from 1 to 40;

[0014] Ar2 is a substituted or unsubstituted 5- to 14-membered monocyclic or condensed-ring heteroaryl group, which, when substituted, is substituted by 1, 2 or 3 substituents selected from F, Cl, Br, I or R3; the heteroaryl group contains 1, 2, 3, 4 or 5 heteroatoms selected from N, S or O;

[0015] R3 is selected from -C m3 H 2m3+1 or -(CH2) n3 C(C x3 H 2x3+1 )(C y3 H 2y3+1 ),

[0016] m3 is an integer from 1 to 36, n3 is an integer from 0 to 10, and x3 and y3 are each independently an integer from 1 to 40;

[0017] A is selected from one of the following structures:

[0018] Z is H, F, Cl, Br or CN; R4 is selected from -C m4 H 2m4+1 ,m4 is an integer from 1 to 16;

[0019] X and Y are each independently selected from H, F, Cl, Br or CN;

[0020] * is the connection site.

[0021] According to some specific embodiments of the present invention, wherein R1 is -C m1 H 2m1+1 or -(CH2) n1 C(C x1 H 2x1+1 )(C y1 H 2y1+1 ),

[0022] m1 is an integer of 1 to 10, n1 is an integer of 1 to 5, and x1 and y1 are each independently an integer of 1 to 5.

[0023] According to some specific embodiments of the present invention, wherein R1 is -(CH2) n1 C(C x1 H 2x1+1 )(C y1 H 2y1+1 ),

[0024] n1 is an integer of 1 to 3, and x1 and y1 are each independently an integer of 1, 2, 3, 4 or 5.

[0025] According to some specific embodiments of the present invention, Ar1 is a substituted or unsubstituted 4-membered, 5-membered or 6-membered monocyclic heteroaryl, a 4-membered, 5-membered or 6-membered monocyclic heterocycloalkyl, or a 10-membered to 14-membered fused ring heteroaryl.

[0026] According to some specific embodiments of the present invention, Ar1 is a substituted or unsubstituted 4-membered, 5-membered or 6-membered monocyclic heteroaryl, a 4-membered, 5-membered or 6-membered monocyclic heterocycloalkyl, or a 10-membered to 14-membered fused-ring heteroaryl; the fused-ring heteroaryl consists of 2 or 3 6-membered rings.

[0027] According to some specific embodiments of the present invention, the heteroatoms of the monocyclic heteroaryl group are 1, 2 or 3 heteroatoms selected from N, O, S or Se; the heteroatoms of the monocyclic heterocycloalkyl group or the fused-ring heteroaryl group are 1, 2 or 3 heteroatoms selected from N, O or S.

[0028] According to some specific embodiments of the present invention, when the above-mentioned heteroaryl or heterocycloalkyl is substituted, it is substituted by 1, 2, 3 or 4 substituents selected from =O or R2.

[0029] According to some specific embodiments of the present invention, wherein R2 is selected from -C m2 H 2m2+1 or -(CH2) n2 C(C x2 H 2x2+1 )(C y2 H 2y2+1 ),

[0030] m2 is an integer of 1 to 10, n2 is an integer of 1 to 5, and x2 and y2 are each independently an integer of 2 to 10.

[0031] According to some specific embodiments of the present invention, wherein R2 is selected from -(CH2) n2 C(C x2 H 2x2+1 )(C y2 H 2y2+1 ), n2 is an integer from 1 to 3, and x2 and y2 are each independently an integer from 4 to 6.

[0032] According to some specific embodiments of the present invention, Ar2 is a substituted or unsubstituted 5-membered or 6-membered monocyclic heteroaryl or an 8-membered to 14-membered condensed ring heteroaryl.

[0033] According to some specific embodiments of the present invention, Ar2 is a substituted or unsubstituted 5-membered monocyclic heteroaryl group or an 8- to 14-membered condensed-ring heteroaryl group.

[0034] According to some specific embodiments of the present invention, Ar2 is a substituted or unsubstituted 5-membered monocyclic heteroaryl group or an 8- to 14-membered fused-ring heteroaryl group; the fused-ring heteroaryl group consists of 2, 3 or 4 5-membered rings.

[0035] According to some specific embodiments of the present invention, Ar2 is a substituted or unsubstituted 5-membered monocyclic heteroaryl group or an 8- to 14-membered fused-ring heteroaryl group; the fused-ring heteroaryl group consists of 2, 3 or 4 5-membered heteroaryl rings.

[0036] According to some specific embodiments of the present invention, when the heteroaryl group is substituted, it is substituted by 1 or 2 R3.

[0037] According to some specific embodiments of the present invention, wherein R3 is selected from -C m3 H 2m3+1 or -(CH2) n3 C(C x3 H 2x3+1 )(C y3 H 2y3+1),

[0038] m3 is an integer of 1 to 5, n3 is an integer of 1 to 3, and x3 and y3 are each independently an integer of 1 to 5.

[0039] According to some specific embodiments of the present invention, R3 is selected from methyl, ethyl or propyl.

[0040] According to some specific embodiments of the present invention, wherein Ar1 is selected from one of the following structures:

[0041] According to some specific embodiments of the present invention, wherein Ar2 is selected from one of the following structures:

[0042] According to some specific embodiments of the present invention,

[0043] m1 is an integer from 5 to 10, n1 is an integer of 1, 2 or 3, and x1 and y1 are each independently an integer of 1, 2, 3, 4 or 5;

[0044] Ar1 is a substituted or unsubstituted 4-membered, 5-membered or 6-membered heteroaryl; when substituted, the heteroaryl is substituted by =O or R2;

[0045] R2 is selected from -C m2 H 2m2+1 or -(CH2) n2 C(C x2 H 2x2+1 )(C y2 H 2y2+1 ),

[0046] m2 is an integer from 5 to 10, n2 is an integer from 1, 2 or 3, and x2 and y2 are each independently an integer from 3 to 10;

[0047] Ar2 is a substituted or unsubstituted 8-, 9-, 10-, 11-, 12-, 13-, or 14-membered fused ring heteroaryl group, and when substituted, the heteroaryl group is substituted by 1, 2, or 3 R3 groups;

[0048] R3 is selected from -C m3 H 2m3+1 or -(CH2) n3 C(C x3 H 2x3+1 )(C y3 H 2y3+1 ),

[0049] m3 is an integer of 1, 2, 3, 4 or 5, n3 is an integer of 0 to 3, and x3 and y3 are each independently an integer of 1 to 5;

[0050] A is selected from

[0051] Z is H, F, Cl, Br or CN; R4 is selected from -C m4 H 2m4+1 ,m4 is an integer from 1 to 16;

[0052] X and Y are each independently selected from H, F, Cl or Br;

[0053] * is the connection site.

[0054] According to some specific embodiments of the present invention,

[0055] Ar1 is a substituted or unsubstituted, 4-membered, 5-membered or 6-membered monocyclic heteroaryl; when substituted, the heteroaryl is replaced by R2;

[0056] R2 is selected from -C m2 H 2m2+1 or -(CH2) n2 C(C x2 H 2x2+1 )(C y2 H 2y2+1 ),

[0057] m2 is an integer from 5 to 10, n2 is an integer from 1, 2 or 3, and x2 and y2 are each independently an integer from 3 to 10;

[0058] Ar2 is a substituted or unsubstituted 8-, 9-, 10-, 11-, 12-, 13-, or 14-membered fused ring heteroaryl; when substituted, the heteroaryl is substituted by 1, 2, or 3 R3;

[0059] R3 is selected from -C m3 H 2m3+1 or -(CH2) n3 C(C x3 H 2x3+1 )(C y3 H 2y3+1 ),

[0060] m3 is an integer of 1, 2, 3, 4 or 5, n3 is an integer of 0 to 3, and x3 and y3 are each independently an integer of 1 to 5.

[0061] According to some specific embodiments of the present invention,

[0062] R1 is -(CH2) n1 C(C x1 H 2x1+1 )(C y1 H 2y1+1 ),

[0063] n1 is an integer from 1 to 3, and x1 and y1 are each independently an integer of 1, 2, 3, 4 or 5;

[0064] Ar1 is a substituted or unsubstituted, 5-membered or 6-membered monocyclic heteroaryl; when substituted, the heteroaryl is replaced by R2;

[0065] R2 is selected from -(CH2) n2 C(C x2 H 2x2+1 )(C y2 H 2y2+1 ),

[0066] n2 is an integer of 1, 2 or 3, and x2 and y2 are each independently an integer of 3 to 8;

[0067] Ar2 is a substituted or unsubstituted 8-, 11- or 14-membered fused heteroaryl group; the fused heteroaryl group is composed of 2, 3 or 4 5-membered heteroaryl rings; when substituted, the heteroaryl group is substituted by 1 or 2 R3;

[0068] R3 is selected from -C m3 H 2m3+1 ,

[0069] m3 is an integer of 1, 2 or 3;

[0070] R4 is selected from -C m4 H 2m4+1 ,m4 is 2.

[0071] According to some specific embodiments of the present invention, the compound is preferably selected from one of the following structures:

[0072] On the other hand, the present invention also provides an organic photodetector, which is prepared using the fully condensed-ring small molecule compound of the present invention as an electron acceptor.

[0073] On the other hand, the present invention also provides applications of the organic photodetector in optical communications, infrared imaging, flexible wearable electronic products, biological health testing, or biomedical monitoring.

[0074] According to some specific embodiments of the present invention, the infrared imaging is achieved by detecting near-infrared / short-wave infrared light.

[0075] In summary, the present invention provides an organic photodetector based on a fully fused-ring small molecule electron acceptor and its applications. The present invention has the following advantages:

[0076] 1) The photodetector of the present invention can alleviate the corrosion and photo-aging degradation of water and oxygen in the environment due to the use of highly stable fully fused ring receptor materials, thereby improving the stability of the device;

[0077] 2) The fully fused ring small molecule of the photodetector of the present invention reduces the trap density of the active layer film due to its fixed conformation, suppresses the noise current of the device, and thus makes the device have high sensitivity;

[0078] 3) The photodetector of the present invention regulates the intramolecular charge transfer properties of the fully condensed ring molecule and adjusts the energy gap of the molecule, so that the organic photodetector based on the fully condensed ring molecule has the ability to detect near-infrared / short-wave infrared light, realizing applications in infrared imaging, biometric technology, medical monitoring and other fields.

[0079] The experimental results show that organic photodetectors based on fully condensed ring small molecule electron acceptors have a low -10 A cm -2 The dark current density and more than 10 13 Jones's specific detection rate, and the device exhibits excellent light stability and moisture stability, and can be used for near-infrared / short-wave infrared light detection in actual environments, proving the practical application prospects of the organic photodetector provided by the present invention. BRIEF DESCRIPTION OF THE DRAWINGS

[0080] FIG1 is a hydrogen spectrum of compound 1-2 of Example 1;

[0081] FIG2 is a hydrogen spectrum of compound 1-3 of Example 1;

[0082] FIG3 is a hydrogen spectrum of compound 1-4 of Example 1;

[0083] FIG4 is a hydrogen spectrum of compound 1-5 of Example 1;

[0084] FIG5 is a hydrogen spectrum of compound 1-6 of Example 1;

[0085] FIG6 is a dark state current-voltage characteristic curve of the organic photodetector of Example 1;

[0086] FIG7 is a responsivity-wavelength characteristic curve of the organic photodetector of Example 1;

[0087] FIG8 is a dark state current-voltage characteristic curve of the organic photodetector of Example 2;

[0088] FIG9 is a noise current density-frequency characteristic curve of the organic photodetector of Example 3;

[0089] FIG10 is a responsivity-wavelength characteristic curve of the organic photodetector of Example 3;

[0090] FIG11 is a curve showing the specific detectivity-wavelength characteristic of the organic photodetector of Example 3;

[0091] FIG12 is a noise current density-frequency characteristic curve of the organic photodetector of Example 4;

[0092] FIG13 is a responsivity-wavelength characteristic curve of the organic photodetector of Example 5;

[0093] FIG14 is a dark-state current-voltage characteristic curve of the organic photodetector of Example 6;

[0094] FIG15 is a dark-state current-voltage characteristic curve of the organic photodetector of Example 7;

[0095] FIG16 is a normalized responsivity-time curve of the decay of the organic photodetector with dark state storage of Example 9;

[0096] FIG17 is a normalized responsivity-time curve of the attenuation of the organic photodetector in an indoor lighting environment of 600 lux according to Example 10;

[0097] FIG18 is a schematic diagram of the test environment of Example 11;

[0098] FIG19 is a normalized responsivity-time curve of the attenuation of the organic photodetector at a relative humidity of 75% according to Example 11;

[0099] FIG20 is a noise current density-frequency characteristic curve of the organic photodetector of Example 12;

[0100] FIG21 is a noise current density-frequency characteristic curve of the organic photodetector of Example 13;

[0101] FIG22 is a responsivity-wavelength characteristic curve of the flexible organic photodetector of Example 14;

[0102] FIG23 is a noise current density-frequency characteristic curve of the flexible organic photodetector of Example 14;

[0103] FIG24 is a curve showing the specific detectivity-wavelength characteristic of the flexible organic photodetector of Example 14;

[0104] FIG25 is an output voltage-time characteristic curve of the flexible organic photodetector of Example 15 under 808 nm LED irradiation;

[0105] FIG26 is a normalized responsivity-time curve of the attenuation of the flexible organic photodetector of Example 16 in an indoor white light LED illumination environment of 600 lux;

[0106] FIG27 is a dark-state current-voltage characteristic curve of the organic photodetector of Example 17;

[0107] FIG28 is a dark-state current-voltage characteristic curve of the organic photodetector of Example 18;

[0108] FIG29 is a dark-state current-voltage characteristic curve of the organic photodetector of Example 19;

[0109] FIG30 is a noise current density-frequency characteristic curve of the organic photodetector of Example 20;

[0110] FIG31 is a noise current density-frequency characteristic curve of the organic photodetector of Example 21;

[0111] FIG32 is a dark-state current-voltage characteristic curve of the organic photodetector of Example 22;

[0112] FIG33 is a responsivity-wavelength characteristic curve of the organic photodetector of Example 22;

[0113] FIG34 is a dark-state current-voltage characteristic curve of the organic photodetector of Example 23;

[0114] FIG35 is a responsivity-wavelength characteristic curve of the organic photodetector of Example 24;

[0115] FIG36 is a noise current density-frequency characteristic curve of the organic photodetector of Example 25;

[0116] FIG37 is a dark-state current-voltage characteristic curve of the organic photodetector of Example 26;

[0117] FIG38 is a schematic diagram of the device structure of the flexible organic photodetector of Example 26;

[0118] FIG39 is a dark-state current-voltage characteristic curve of the organic photodetector of Example 27;

[0119] FIG40 is a responsivity-wavelength characteristic curve of the organic photodetector of Example 28;

[0120] FIG41 is a dark-state current-voltage characteristic curve of the organic photodetector of Example 29;

[0121] FIG42 is a dark-state current-voltage characteristic curve of the organic photodetector of Example 30;

[0122] FIG43 is a dark-state current-voltage characteristic curve of the organic photodetector of Example 31;

[0123] FIG44 is a noise current density-frequency characteristic curve of the organic photodetector of Example 32

[0124] FIG45 is a schematic diagram of the device structure of the rigid organic photodetector of Example 1. DETAILED DESCRIPTION

[0125] The following describes in detail the implementation process of the present invention and the beneficial effects produced by specific embodiments, which is intended to help readers better understand the essence and characteristics of the present invention and is not intended to limit the scope of implementation of this case.

[0126] Example 1

[0127] Synthesis of fully fused-ring small molecule 1 and preparation of organic photodetector devices.

[0128] 1. Synthesis of fully fused ring small molecule 1 (Compound 1-6):

[0129] The synthetic route of the above-mentioned ADA'DA type fully fused ring small molecule 1 is as follows:

[0130] Compound 1-2: Under argon, a three-necked flask was charged with compound 1-1 (5.00 g, 9.34 mmol), (thieno[3,2-B]thiophen-2-yl)tributyltin (11.10 g, 22.87 mmol), Pd(PPh3)4 (0.35 g, 0.30 mmol), and CuI (0.11 g, 0.60 mmol). The mixture was evacuated three times, and toluene (100.0 mL) was added. The mixture was refluxed at 110°C with stirring overnight. After cooling to room temperature, a large amount of orange solid precipitated. The solid was filtered, and the filter cake was rinsed three times with methanol. Purification by column chromatography afforded compound 1-2 as an orange-red solid (6.44 g, 91% yield). The H NMR spectrum of compound 1-2 is shown in Figure 1.

[0131] NMR analysis: 1 H NMR (500MHz, CDCl3): δ (ppm) 7.78 (s, 2H), 7.48 (d, J = 5.2Hz, 2H), 7.33 (d, J = 5.2Hz, 2H), 4. 80(d,J=6.7Hz,2H),2.33-2.28(m,1H),1.44-1.23(m,16H),0.89(dt,J=13.0,6.9Hz,6H).

[0132] Compound 1-3: Under argon, compound 1-2 (1.00 g, 2.06 mmol) and triethyl phosphite (17.0 mL) were added to a three-necked flask. The mixture was evacuated three times, and o-dichlorobenzene (17.0 mL) was added. The mixture was refluxed and stirred at 180°C overnight. After cooling to room temperature, the solvent was removed under reduced pressure and the mixture was directly used for the next reaction. Under argon, potassium iodide (0.34 g, 2.06 mmol), potassium carbonate (2.90 g, 20.60 mmol), and isooctane bromide (1.5 mL) were added. Anhydrous DMF (26.0 mL) was added, and the mixture was heated and stirred at 80°C for 24 h. The reaction was quenched with water, and the reaction solution was extracted three times with dichloromethane. The organic phases were combined, dried over anhydrous sodium sulfate, and concentrated. Purification by column chromatography afforded compound 3 (0.50 g, 38.4% yield) as a yellow oil. The H NMR spectrum of compound 1-3 is shown in Figure 2.

[0133] NMR analysis: 1 H NMR (400MHz, Benzene-d6) δ6.79(d,J=5.2Hz,1H),6.75(d,J=5.2Hz,1H),4.87(d,J=5.0Hz,2H),4.58(d,J=7.0Hz,1H),2.34(s,1H),2.18 (s,1H),1.46(s,2H),1.19(d,J=23.7Hz,39H),1.04(s,6H),0.89(d,J=18.3Hz,20H),0.78(q,J=7.1Hz,5H),0.64(dt,J=14.5,7.2Hz,5H).

[0134] Compound 1-4: Under argon, 2-iodo-4,5-dichlorobenzoyl chloride (0.32 g, 1.23 mmol) and aluminum chloride (0.16 g, 1.23 mmol) were added to a solution of compound 1-3 (0.25 g, 0.31 mmol) in anhydrous dichloromethane (8.0 mL). The mixture was stirred at room temperature for 24 hours. The reaction was then quenched with water, and the reaction solution was extracted three times with dichloromethane. The organic phases were combined, dried over anhydrous sodium sulfate, and concentrated. Purification by column chromatography (petroleum ether / dichloromethane = 1.5:1.0, v / v) afforded compound 1-4 as an orange solid (0.28 g, 74% yield). The H NMR spectrum of compound 1-4 is shown in Figure 3.

[0135] NMR analysis: 1H NMR(500MHz,Chloroform-d)δ7.69(s,2H),7.62–7.53(m,2H),7.46–7.39(m,2H),4.72(d,J=7.1Hz,2H),4.65( d,J=7.7Hz,4H),2.38(s,1H),2.00–1.90(m,2H),1.42–1.23(m,16H),1.04–0.74(m,20H),0.72–0.50(m,12H).

[0136] Compound 1-5: Under argon, Herrmann's catalyst (3.0 mg, 0.003 mmol), P(o-MeOPh)3 (2.0 mg, 0.006 mmol), pivalic acid (17.0 mg, 0.17 mmol), and Cs2CO3 (0.16 g, 0.50 mmol) were added to a 7.0 mL toluene solution of compound 1-4 (0.21 g, 0.17 mmol). The mixture was heated to 120°C and stirred for 32 hours. The solvent was then removed under reduced pressure, and the mixture was purified by column chromatography (petroleum ether / dichloromethane = 1.0:1.5, v / v) to obtain compound 1-5 as a purple-black solid (188 mg, 90% yield). The H NMR spectrum of compound 1-5 is shown in Figure 4.

[0137] NMR analysis: 1 H NMR(500MHz,Chloroform-d)δ7.43–7.37(m,2H),7.18–7.13(m,2H),4.76(d,J=7.0Hz,2H),4.72(d,J=7.1Hz,2H),4 .65(d,J=7.7Hz,4H),2.38(s,1H),2.00–1.90(m,2H),1.42–1.23(m,16H),1.04–0.74(m,22H),0.72–0.50(m,12H).

[0138] Fully fused ring small molecule 1 (Compound 1-6): Compound 1-5 (0.17 g, 0.15 mmol) and malononitrile (50.0 mg, 0.76 mmol) were added to a single-necked flask. 20.0 mL of chlorobenzene, 0.2 mL of pyridine, and 0.2 mL of TiCl₄ were then added sequentially. The mixture was heated to 50°C and stirred for 4 hours. The mixture was cooled to room temperature and extracted with dichloromethane. The organic layer was washed sequentially with water and saturated brine, dried over Na₂SO₄, and the solvent was removed. The mixture was purified by column chromatography (petroleum ether / dichloromethane = 1.0:1.5, v / v) to afford compound FM7 as a black solid (0.14 g, 78% yield). The H NMR spectrum of compound 1-6 is shown in Figure 5.

[0139] NMR analysis: 1H NMR(500MHz,Chloroform-d)δ8.11–8.05(m,2H),7.25–7.23(m,2H),4.75(d,J=7.0Hz,2H),4.61(d,J=7 .7Hz,4H),2.38(s,1H),2.00-1.90(m,2H),1.42-1.23(m,16H),1.04–0.74(m,20H),0.72–0.50(m,12H).

[0140] 2. Preparation of organic photodetector devices based on fully fused ring small molecule 1:

[0141] (1) Pretreatment of the substrate: The patterned glass-indium tin oxide electrode substrate was ultrasonically cleaned in distilled water, isopropyl alcohol, and acetone for 10 minutes, transferred to a 100°C oven and dried for 15 minutes. It was then treated with UV-ozone for 10 minutes before use and placed aside.

[0142] (2) Preparation of zinc oxide cathode interface layer, active layer and electrode deposition: Weigh 0.28 g of ethanolamine and 1 g of zinc acetate, measure 10 mL of methoxyethanol, add them to a 25 mL round-bottom flask and stir at room temperature overnight, filter with a syringe filter, spin-coat at 5000 rpm in air environment to form a film, heat-treat at 160°C for 1 h, store for future use, and use an optical profilometer to test that the thickness of the zinc oxide cathode interface layer is 25 nm.

[0143] To a 1.5mL vial, 7mg of compound PBDB-T, 8.4mg of fully fused-ring small molecule 1, and 1mL of chloroform (dry solvent) were added. The mixture was stirred at 55°C at 500 rpm for 1.5h. After cooling to room temperature, 15µL of chloronaphthalene was added and stirring continued for 0.5h. Using a pipette, 45µL of the blend solution was dropped onto a substrate and spin-coated at 2500 rpm to form a film. The wet film was thermally annealed at 110°C for 10 min. An optical profilometer was used to measure the thickness of the functional layer, which was 195nm. As a control, 8mg of compound PBDB-T, 8mg of small molecule ITIC, and 1mL of chlorobenzene (CB) (dry solvent) were added to vial #2. The mixture was stirred at 55°C at 500 rpm for 1.5h. After cooling to room temperature, 12.5µL of 1,8-diiodooctane was added and stirring continued for 0.5h. 35 μL of the blend solution was pipetted onto a substrate and spin-coated at 1700 rpm to form a film. The wet film was thermally annealed at 90°C for 10 minutes. An optical profilometer was used to measure the thickness of the functional layer, which was 180 nm. To sample vial No. 3, 8 mg of compound PBDB-T, 12.8 mg of small molecule Y6, and 1 mL of chloroform (CF) drying solvent were added. The mixed solution was stirred at 500 rpm for 1 hour at 55°C. After cooling to room temperature, 7 μL of 1-chloronaphthalene was added and stirring continued for 0.5 hour. 40 μL of the blend solution was pipetted onto a substrate and spin-coated at 2500 rpm to form a film. The wet film was thermally annealed at 110°C for 10 minutes. An optical profilometer was used to measure the thickness of the functional layer, which was 210 nm.

[0144] Place the substrate on the metal mask and transfer it to the vacuum coating machine. Evacuate the chamber until the pressure is lower than 2×10 -4 Pa, using thermal evaporation at speeds of 0.3 nm / s and 1 nm / s to deposit 15 nm MoO3 and 100 nm Ag electrodes, respectively, yielded organic photodetector devices based on PBDB-T: fully fused ring small molecule 1, PBDB-T:ITIC, and PBDB-T:Y6. The rigid OPD device structures are shown in Figure 45.

[0145] 3. Characterization of the light detection performance of organic photodetectors based on PBDB-T: fully condensed-ring small molecule 1.

[0146] The PBDB-T:ITIC device was used as a control device. The Keithley 2635B digital source meter was used to measure the current-voltage (JV) characteristic curves of the PBDB-T: fully fused ring small molecule 1 and the PBDB-T:ITIC photodetector devices in the dark state. The dark state JV characteristic curves of the devices are shown in Figure 6. Secondly, the external quantum efficiency of the device in the UV-vis-NIR range was measured using the QE quantum efficiency test system, and the responsivity curve of the corresponding band was calculated. The responsivity-wavelength characteristic curve of the device is shown in Figure 7. Assuming that shot noise is the main source of detector noise, the device's specific detectivity D can be estimated based on the dark state JV curve and the responsivity characteristic curve. sh *, the shot noise limited specific detectivity D of the device sh *Can be calculated from the device's dark current and responsivity level. Detailed parameters are listed in Table 1.

[0147] Table 1

[0148] The results are as follows: Under 0V bias, the photodetector based on PBDB-T: fully condensed ring small molecule 1 is in self-powered mode, and the device dark current J d Up to 1.52×10 -10 A cm -2 , which is significantly lower than 4.84×10 -9 A cm -2 PBDB-T: The response R of the fully condensed ring small molecule 1 reaches a maximum value of 0.45 AW at 920 nm. -1 , significantly higher than PBDB-T:ITIC's 0.35AW at 700nm -1 PBDB-T: The peak ratio detectivity of the fully condensed ring small molecule 1 is 6.46×10 13 Jones, achieved over 10 13 Jones’s specific detection rate is significantly better than PBDB-T:ITIC’s 8.88×10 12 Jones. In summary, the fully fused-ring small molecule 1 has obvious advantages over the non-fully fused-ring ITIC in the preparation of highly sensitive infrared OPDs.

[0149] Example 2

[0150] A similar synthetic route was used to obtain the fully fused ring small molecule 2. The preparation method of small molecule 2 was the same as that of the compound in Example 1, except that the raw material 2-iodo-4,5-dichlorobenzoyl chloride was replaced with 2-bromo-3,4,5,6-tetrafluorobenzoyl chloride in the synthesis of compound 1-4.

[0151] Elemental analysis structure (C 70 H 67 F8N9S4), theoretical values: C, 63.96; H, 5.14; F, 11.56; N, 9.59; S, 9.76, measured values: C, 63.90; H, 5.24; F, 11.52; N, 9.61; S, 9.73. MALDI-TOF analysis, theoretical value: 1314.60, found value: 1314.6.

[0152] The preparation process of the photodetector device is similar to that of Example 1. The photodetection performance of the OPD device of PBDB-T: fully fused ring small molecule 2 was characterized. The current-voltage (JV) characteristic curves of the PBDB-T: small molecule 2 and PBDB-T: ITIC photodetector devices in the dark state were measured using a Keithley 2635B digital source meter. The dark state JV characteristic curves of the devices are shown in Figure 8. Under 0V bias, the photodetector based on PBDB-T: small molecule 2 is in self-powered mode, and the device dark current J d Up to 1.27×10 -9 A cm -2 , which is lower than 4.84×10 of PBDB-T:ITIC -9 A cm -2 Compared with non-fully fused-ring ITIC, the fully fused-ring small molecule 2 has certain advantages in the preparation of highly sensitive infrared OPD.

[0153] Example 3

[0154] A similar synthetic route was used to obtain the fully fused ring small molecule 3. The preparation method of small molecule 3 was the same as that of the compound in Example 1, except that the raw material malononitrile was replaced with 3-ethylrhodanine in the synthesis of the final product.

[0155] Elemental analysis structure C 82 H 97 Cl4N7O2S8), theoretical: C, 61.14; H, 6.07; Cl, ​​8.80; N, 6.09; S, 15.92, found: C, 66.02; H, 6.11; N, 6.13; S, 15.84. MALDI-TOF analysis, theoretical: 1607.42, found: 1607.4.

[0156] The preparation process of the photodetector device is similar to that of Example 1. The photodetection performance of the OPD device of PBDB-T: fully fused ring small molecule 3 was characterized. In order to avoid overestimation of the performance of the photodetector, the noise of the photodetector at different frequencies was quantitatively measured using ProPlus 9812D. The S nThe frequency characteristic curve is shown in Figure 9. The device's responsivity-wavelength characteristic curve is shown in Figure 10. Based on the device's normal operating frequency, we selected the device's noise current density at 1kHz and calculated the device's true specific detectivity D*. The device's D*-wavelength characteristic curve is shown in Figure 11. The results are as follows: Under 0V bias, the photodetector based on PBDB-T: fully fused ring small molecule 3 has a noise current of 1.27×10 at 1kHz. -14 A Hz -1 / 2 , which is significantly lower than 6.73×10 -14 A Hz -1 / 2 PBDB-T: The peak specific detectivity of the fully condensed ring small molecule 3 device reached 6.46×10 at 920nm. 13 Jones, also achieved more than 10 13 Jones's specific detectivity. The specific detectivity of the OPD device based on PBDB-T:ITIC is 8.88×10 12 Jones, which is only about 1 / 7 of the OPD device of PBDB-T: fully condensed ring small molecule 3. In summary, fully condensed ring small molecule 3 has obvious advantages over non-fully condensed ring ITIC in the preparation of highly sensitive infrared OPD.

[0157] Example 4

[0158] A similar synthetic route was used to obtain the fully fused ring small molecule 4. The preparation method of molecule 4 was the same as that of the compound in Example 1, except that in the synthesis of compound 1-4, the raw material 2-iodo-4,5-dichlorobenzoyl chloride was replaced with 2-bromo-4,5-difluorobenzoyl chloride; and in the synthesis of the final product, the raw material malononitrile was replaced with 6-cyano-3-(dicyanomethylidene)indone.

[0159] Elemental analysis structure C 94 H 85 F4N 11 O2S4), theoretical value: C, 70.34; H, 5.34; F, 4.73; N, 9.60; O, 1.99; S, 7.99, found value: C, 70.36; H, 5.34; F, 4.71; N, 9.58; O, 1.98; S, 7.96. MALDI-TOF analysis, theoretical value: 1605.02, found value: 1605.0.

[0160] The preparation process of the photodetector device is similar to that of Example 1. The noise level of the OPD device based on PBDB-T: fully condensed ring small molecule 4 is characterized, and the results are shown in Figure 12. Under 0V bias, the noise current of the photodetector based on PBDB-T: fully condensed ring small molecule 4 at 1kHz is 3.42×10 -14 A Hz-1 / 2 , which is significantly lower than 6.73×10 -14 A Hz -1 / 2 ; This shows that the fully fused ring small molecule 4 can be used to prepare highly sensitive OPD.

[0161] Example 5

[0162] A similar synthetic route was used to obtain the fully fused ring small molecule 5. The preparation method of molecule 5 was the same as that of the compound in Example 1, except that in the synthesis of compound 1-4, the raw material 2-iodo-4,5-dichlorobenzoyl chloride was replaced with 2-bromobenzoyl chloride; and in the synthesis of the final product, the raw material malononitrile was replaced with dicyanorhodamine.

[0163] Elemental analysis structure (C 84 H 93 N 11 S8), theoretical value: C, 66.67; H, 6.19; N, 10.18; S, 16.95, found value: C, 66.45; H, 6.26; N, 10.19; S, 16.86. MALDI-TOF analysis, theoretical value: 1511.54, found value: 1511.5.

[0164] The preparation process of the photodetector device is similar to that of Example 1. The responsivity-wavelength characteristic curve of the OPD device of PBDB-T: fully condensed ring small molecule 5 is shown in Figure 13 (measured using a QE quantum efficiency test system). Under a bias of 0V, the photodetector based on PBDB-T: fully condensed ring small molecule 1 is in self-powered mode, and the device responsivity R reaches a maximum value of 0.34A W-1 at 900nm. The responsivity value is close to 0.35A W-1 of the PBDB-T: ITIC device, but the device peak responsivity red-shifts by about 200nm. This shows that the fully condensed ring small molecule 5 can be used to prepare near-infrared OPD.

[0165] Example 6

[0166] A similar synthetic route was used to obtain the fully fused ring small molecule 6. The preparation method of molecule 6 was the same as that of the compound in Example 1, except that in the synthesis of compound 1-4, the raw material 2-iodo-4,5-dichlorobenzoyl chloride was replaced with 2-bromo-3,4,5,6-tetrafluorobenzoyl chloride; and in the synthesis of the final product, the raw material malononitrile was replaced with 5,6-difluoro-3-(dicyanomethylidene)indone.

[0167] Elemental analysis structure (C 92 H 79 F 12N9O2S4), theoretical: C, 65.04; H, 4.69; F, 13.42; N, 7.42; O, 1.88; S, 7.55, found: C, 65.10; H, 4.67; F, 13.40; N, 7.47; O, 1.89; S, 7.52. MALDI-TOF analysis, theoretical: 1698.93, found: 1698.9.

[0168] The preparation process of the photodetector device is similar to that of Example 1. The optical detection performance of the OPD device of PBDB-T: all-condensed ring small molecule 6 was characterized (measured using a Keithley 2400 digital source meter). The results are shown in Figure 14. Under 0V bias, the photodetector based on PBDB-T: all-condensed ring small molecule 6 is in self-powered mode, and the device dark current J d Up to 4.40×10 -10 A cm -2 , which is about 1 / 10 of PBDB-T:ITIC, indicating that the fully condensed-ring small molecule 6 has advantages in preparing highly sensitive infrared OPD.

[0169] Example 7

[0170] A similar synthetic route was used to obtain the fully fused ring small molecule 7. The preparation method of molecule 7 was the same as that of the compound in Example 1, except that in the synthesis of compound 1-4, the raw material 2-iodo-4,5-dichlorobenzoyl chloride was replaced with 2-bromo-3,4,5,6-tetrafluorobenzoyl chloride; and in the synthesis of the final product, the raw material malononitrile was replaced with 6-cyano-3-(dicyanomethylidene)indone.

[0171] Elemental analysis structure (C 94 H 81 F8N 11 O2S4), theoretical value: C, 67.33; H, 4.87; F, 9.06; N, 9.19; O, 1.91; S, 7.65, found: C, 67.43; H, 4.83; F, 9.04; N, 9.15; O, 1.90; S, 7.63. MALDI-TOF analysis, theoretical value: 1676.98, found: 1677.0.

[0172] The preparation process of the photodetector device is similar to that of Example 1. The photodetection performance of the OPD device of PBDB-T: fully condensed ring small molecule 7 was characterized (measured using a Keithley 2400 digital source meter). The results are shown in Figure 15. Under 0V bias, the dark current J of the device based on PBDB-T: fully condensed ring small molecule 7 is d Up to 1.95×10 -9 A cm -2, which is about 1 / 2 of PBDB-T:ITIC, indicating that the fully fused-ring small molecule 7 can be used to prepare highly sensitive OPD.

[0173] Example 8

[0174] A similar synthetic route was used to obtain the fully fused ring small molecule 8. The preparation method of molecule 8 was the same as that of the compound in Example 1, except that in the synthesis of compound 1-2, the raw material was replaced by (thieno[3,2-b]thiophen-2-yl)tributyltin instead of (dithieno[3,2-b:2',3'-d]thiophene)tributyltin; and in the synthesis of compound 1-4, the raw material 2-iodo-4,5-dichlorobenzoyl chloride was replaced by 2-iodo-4,5-dicyanobenzoyl chloride.

[0175] Elemental analysis structure (C 82 H 79 N 13 S6), theoretical value: C, 68.44; H, 5.53; N, 12.65; S, 13.37, found value: C, 68.54; H, 5.51; N, 12.62; S, 13.34. MALDI-TOF analysis, theoretical value: 1438.99, found value: 1439.0.

[0176] Linear dynamic range, response time, and cutoff frequency are often used to comprehensively evaluate the application value of photodetectors. A comprehensive performance test and characterization of an organic photodetector based on PBDB-T: fully condensed ring small molecule 8 was conducted using the CEL-PD291 photodetection system. The linear dynamic range of the photodetector based on PBDB-T: fully condensed ring small molecule 8 reached 158dB, which can meet the performance requirements of photodetectors in a variety of application scenarios. This is significantly better than the 66dB of inorganic InGaAs detectors and comparable to the 160dB of inorganic Si detectors. The response time (t rise / t fall ) reach 26us / 12us respectively, which can achieve a fast response to infrared light; the -3dB cutoff frequency of the OPD device can reach 40kHz, enabling it to work efficiently in a wide range.

[0177] Example 9

[0178] A similar synthetic route was used to obtain the fully fused ring small molecule 9. The preparation method of molecule 9 was the same as that of the compound in Example 1, except that in the synthesis of compound 1-2, the raw material (thieno[3,2-b]thiophen-2-yl)tributyltin was replaced with a (dithieno[3,2-b:2',3'-d]thiophene)tributyltin compound; in the synthesis of compound 1-4, the raw material 2-iodo-4,5-dichlorobenzoyl chloride was replaced with 2-bromo-4,5-difluorobenzoyl chloride; and in the synthesis of the final product, the raw material malononitrile was replaced with 5,6-difluoro-3-(dicyanomethylidene)indone.

[0179] Elemental analysis structure (C 96 H 83 F8N9O2S6), theoretical: C, 66.30; H, 4.81; F, 8.74; N, 7.25; O, 1.84; S, 11.06, found: C, 66.39; H, 4.80; F, 8.72; N, 7.22; O, 1.86; S, 11.09. MALDI-TOF analysis, theoretical: 1739.13, found: 1739.1.

[0180] The photodetector device preparation process was similar to that in Example 1, and the dark-state storage stability of the OPD device based on PBDB-T: all-condensed ring small molecule 9 was characterized. To test the stability of organic photodetectors based on all-condensed ring small molecule electron acceptors, the prepared high-sensitivity organic photodetector based on PBDB-T: all-condensed ring small molecule 9 was stored in air in a dark environment, and the device responsivity stability was tested.

[0181] The prepared 12 PBDB-T: all-condensed ring small molecule 9 and PBDB-T: ITIC unpackaged organic photodetectors were placed in the air for dark storage. The room temperature was about 16-20 ° C and the relative humidity was 15-25%. The responsivity curves of all devices were tested at regular intervals, and the responsivity at 920nm and 700nm was taken for data statistics. The normalized responsivity-time curve that can describe the device attenuation was drawn, as shown in Figure 16. The results show that after 1500 hours of dark storage in air, the peak responsivity of the PBDB-T: all-condensed ring small molecule 9 device only dropped from 0.453AW -1 Down to 0.414AW -1 , only dropped by 8.7% of the initial value, while the peak responsivity of the PBDB-T:ITIC device dropped by 21.3%. Organic photodetectors based on fully fused-ring small molecule electron acceptors have excellent dark storage stability.

[0182] Example 10

[0183] A similar synthetic route was used to obtain the fully fused ring small molecule 10. The preparation method of molecule 10 was the same as that of the compound in Example 1, except that in the synthesis of compound 1-2, the starting material was replaced from (thieno[3,2-b]thiophen-2-yl)tributyltin to (dithieno[3,2-b:2',3'-d]thiophene)tributyltin; in the synthesis of compound 1-4, the starting material 2-iodo-4,5-dichlorobenzoyl chloride was replaced with 2-bromo-3,4,5,6-tetrafluorobenzoyl chloride; and in the synthesis of the final product, the starting material malononitrile was replaced with 5,6-difluoro-3-(dicyanomethylidene)indone.

[0184] Elemental analysis structure (C 96 H 79 F 12 N₁₂O₂S₂, theoretical: C, 63.67; H, 4.40; F, 12.59; N, 6.96; O, 1.77; S, 10.62, found: C, 63.57; H, 4.41; F, 12.60; N, 6.97; O, 1.78; S, 10.63. MALDI-TOF analysis, theoretical: 1811.09, found: 1811.1.

[0185] The photodetector device preparation process was similar to that in Example 1, and the storage stability of the PBDB-T: all-condensed ring small molecule 10 OPD device was characterized. To test the stability of organic photodetectors based on all-condensed ring small molecule electron acceptors, the prepared high-sensitivity organic photodetector based on PBDB-T: all-condensed ring small molecule 10 was stored in air under 600 lux indoor lighting, and the device responsivity stability was tested.

[0186] The prepared 8 PBDB-T: fully fused ring small molecule 10 and PBDB-T: ITIC unpackaged organic photodetectors were placed in air and stored under 600 lux indoor light. The light intensity was calibrated by a lux meter. The indoor temperature was about 16-20°C and the relative humidity was 15-25%. The responsivity curve of the device was tested at regular intervals, and the highest responsivity value at 920nm was taken for data statistics. The normalized responsivity-time curve that can describe the device attenuation was drawn, as shown in Figure 17. The results show that after 1200 hours of dark storage in air, the peak responsivity of the device only dropped from 0.450 AW to 0.61 AW. -1 Down to 0.405AW -1 , T of unpackaged devices 90 It can reach 1200h. In comparison, the T 90 It can be as short as 480h, proving that the organic photodetector based on fully condensed-ring small molecule electron acceptor has excellent light storage stability.

[0187] Example 11

[0188] A similar synthetic route was used to obtain the fully fused ring small molecule 11. The preparation method of molecule 11 was the same as that of the compound in Example 1, except that in the synthesis of compound 1-2, the raw material was replaced from (thieno[3,2-b]thiophen-2-yl)tributyltin to 4-methyl-2-(triisopropylsilyl)-5-(trimethylstannyl)-4H-thieno[3,2-b]pyrrole; and in the synthesis of compound 1-4, 2-iodo-4,5-dichlorobenzoyl chloride was replaced with 2-iodo-4,5-dicyanobenzoyl chloride.

[0189] Elemental analysis structure (C 94 H 81 F8N 11 O2S4), theoretical value: C, 67.33; H, 4.87; F, 9.06; N, 9.19; O, 1.91; S, 7.65, found: C, 67.43; H, 4.83; F, 9.04; N, 9.15; O, 1.90; S, 7.63. MALDI-TOF analysis, theoretical value: 1676.98, found: 1677.0.

[0190] The photodetector device preparation process was similar to that in Example 1. The photodetection performance and humidity storage stability of the OPD device based on PBDB-T: fully condensed ring small molecule 16 were characterized. To test the stability of organic photodetectors based on fully condensed ring small molecule electron acceptors, different test environments were constructed, including high humidity, illumination, and dark storage. A schematic diagram of the test environment is shown in Figure 18. The prepared highly sensitive organic photodetector device based on PBDB-T: fully condensed ring small molecule 11 was stored in the dark in air at a relative humidity of 75%, and the device response stability was tested.

[0191] The prepared 12 PBDB-T: all-condensed ring small molecule 11 unpackaged organic photodetectors were placed in a sealed box with a relative humidity of 75% for dark storage. The air humidity was calibrated by a hygrometer and calibrated by a humidifier every 6 hours. The indoor temperature was about 16-20°C. The responsivity curve of the device was tested at regular intervals, and the highest responsivity value at 920nm was taken for data statistics. The normalized responsivity-time curve that can describe the attenuation of the device was drawn, as shown in Figure 19. The results show that after 500 hours of dark storage in air, the peak responsivity of the device only dropped from 0.443AW to 0.543AW. -1 Down to 0.398AW -1 , T of unpackaged devices 90It can reach 500h, which is significantly better than the 240h of PBDB-T:ITIC device, proving that the organic photodetector based on fully condensed-ring small molecule electron acceptors has excellent humidity storage stability.

[0192] Example 12

[0193] A similar synthetic route was used to obtain the fully fused ring small molecule 12. The preparation method of molecule 12 was the same as that of the compound in Example 1, except that in the synthesis of compound 1-2, (thieno[3,2-b]thiophen-2-yl)tributyltin was replaced with 4-methyl-2-(triisopropylsilyl)-5-(trimethylstannyl)-4H-thieno[3,2-b]pyrrole; and in the synthesis of compound 1-4, 2-iodo-4,5-dichlorobenzoyl chloride was replaced with 2-bromo-3,4,5,6-tetrafluorobenzoyl chloride.

[0194] Elemental analysis structure (C 76 H 81 F8N 11 S2), theoretical value: C, 66.89; H, 5.98; F, 11.14; N, 11.29; S, 4.70, measured value: C, 66.99; H, 5.98; F, 11.12; N, 11.25; S, 4.71. MALDI-TOF analysis, theoretical value: 1364.67, found value: 1364.7.

[0195] The preparation process of the photodetector device is similar to that of Example 1. The photodetection performance of the OPD device of PBDB-T: fully condensed ring small molecule 12 is characterized by quantitatively measuring the noise of the PBDB-T: fully condensed ring small molecule 12 photodetector at different frequencies using ProPlus 9812D. n The frequency characteristic curve is shown in Figure 20. Under a bias voltage of -0.5V, the noise current of the photodetector based on PBDB-T: fully condensed ring small molecule 12 at 1kHz reaches 3.12×10 -14 A Hz -1 / 2 , which is significantly lower than 1.35×10 -13 A Hz -1 / 2 ; In summary, the fully fused-ring small molecule 12 has potential in the preparation of highly sensitive OPD.

[0196] Example 13

[0197] A similar synthetic route was used to obtain the fully fused ring small molecule 13. The preparation method of molecule 13 was the same as that of the compound in Example 1, except that in the synthesis of compound 1-2, (thieno[3,2-b]thiophen-2-yl)tributyltin was replaced with 4-methyl-2-(triisopropylsilyl)-5-(trimethylstannyl)-4H-thieno[3,2-b]pyrrole; and in the synthesis of compound 1-4, the 2-iodo-4,5-dichlorobenzoyl chloride in the raw material was replaced with 2-bromo-4,5-difluorobenzoyl chloride.

[0198] Elemental analysis structure (C 76 H 85 F4N 11 S2), theoretical value: C, 70.61; H, 6.63; F, 5.88; N, 11.92; S, 4.96, measured value: C, 70.55; H, 6.65; F, 5.89; N, 11.93; S, 4.97. MALDI-TOF analysis, theoretical value: 1291.64, found value: 1291.6.

[0199] The preparation process of the photodetector device is similar to that of Example 1, and the photodetection performance of the OPD device of PBDB-T: fully condensed ring small molecule 13 is characterized. n The frequency characteristic curve is shown in Figure 21 (measured using ProPlus 9812D). Under a bias voltage of -1 V, the noise current of the photodetector based on PBDB-T: fully fused ring small molecule 13 at 1 kHz reaches 9.15×10 -14 A Hz -1 / 2 , which is significantly lower than 2.03×10 of PBDB-T:ITIC -13 A Hz -1 / 2 .

[0200] Example 14

[0201] A similar synthetic route was used to obtain the fully fused ring small molecule 14. The preparation method of molecule 14 was the same as that of the compound in Example 1, except that in the synthesis of compound 1-2, the raw material (thieno[3,2-b]thiophen-2-yl)tributyltin was replaced with 4-methyl-2-(triisopropylsilyl)-5-(trimethylstannyl)-4H-thieno[3,2-b]pyrrole; in the synthesis of compound 1-4, the raw material 2-iodo-4,5-dichlorobenzoyl chloride was replaced with 2-bromo-4,5-difluorobenzoyl chloride; and in the synthesis of the final product, the raw material malononitrile was replaced with dicyanorhodamine.

[0202] Elemental analysis structure (C 86 H 95 F4N 13S6), theoretical value: C, 65.41; H, 6.06; F, 4.81; N, 11.53; S, 12.18, measured value: C, 65.23; H, 6.12; F, 4.74; N, 11.61; S, 12.25. MALDI-TOF analysis, theoretical value: 1577.61, found value: 1577.6.

[0203] PBDB-T: Preparation and characterization of the light detection performance of flexible organic photodetectors based on the fully fused ring small molecule 14:

[0204] First, a flexible organic photodetector device was fabricated based on the PBDB-T: fully fused ring small molecule 14 and PBDB-T:Y6. The fabrication process was as follows: a PET-ITO substrate was patterned using a laser etching machine, with a substrate size of 1.5 cm × 1.5 cm. The treated substrate was ultrasonically cleaned in distilled water, isopropyl alcohol, and acetone for 10 minutes, then dried in a 100°C oven for 15 minutes. Prior to use, it was etched using oxygen plasma for 10 minutes and then stored for later use.

[0205] The PEDOT Al 4083 aqueous solution was filtered using a syringe filter, 40uL of the solution was dropped onto the substrate, and a film was formed by spin coating at a speed of 3500 rpm, heat treated at 110°C for 15 minutes, and stored under a nitrogen atmosphere. The thickness of the functional layer was characterized by an optical profilometer to be 40nm. The photoactive layer was formed by spin coating at a speed of 2500 rpm using the same solution concentration as in Example 1. The wet film was heat annealed at 110°C for 8 minutes, and the thickness of the functional layer was characterized by an optical profilometer to be 180-200nm. The substrate was placed on a metal mask and transferred to a vacuum coating machine, and the vacuum was evacuated to a box pressure of less than 2×10 -4 Pa, a flexible near-infrared organic photodetector device was obtained by depositing 0.5nm LiF and 100nm Ag electrodes at speeds of 0.05nm / s and 1nm / s, respectively.

[0206] Second, the device's responsivity-wavelength characteristic curve was measured using the CEL-PD291 photodetector test system, as shown in Figure 22. The device's noise current density Sn at different frequencies was measured using the ProPlus 9812D, as shown in Figure 23. The device's true specific detectivity D*-wavelength characteristic curve was then calculated, as shown in Figure 24. The results are as follows: In self-powered mode, the photodetector based on the PBDB-T: fully fused ring small molecule 14 has a response range of 1300nm, and the device's responsivity R reaches a maximum of 0.07AW at 1070nm. -1 The response range of the device based on the fully condensed ring molecule is significantly red-shifted by about 300 nm compared to the non-fully condensed ring molecule Y6; the noise current of the PBDB-T: fully condensed ring small molecule 14 device at 1 kHz reaches 3.90×10-14 A Hz -1 / 2 significantly lower than the 1.01×10 -13 A Hz -1 / 2 PBDB-T: The peak specific detectivity of the fully condensed ring small molecule 14 device reached 5.08×10 at 1070nm. 11 Jones. In summary, compared with the non-fully fused ring molecule Y6, the fully fused ring small molecule 14 achieves excellent light detection performance in the near-infrared region II.

[0207] Example 15

[0208] The preparation method of molecule 15 is the same as the preparation method of the compound in Example 1, except that in the synthesis of compound 1-2, (thieno[3,2-b]thien-2-yl)tributyltin is replaced by 7-methyl-2-(triisopropylsilyl)-6-(trimethylstannyl)-7H-thieno[2',3':4,5]thieno[3,2-b]pyrrole; in the synthesis of compound 1-4, 2-iodo-4,5-dichlorobenzoyl chloride is replaced by 2-bromo-4,5-difluorobenzoyl chloride.

[0209] Elemental analysis structure (C 80 H 85 F4N 11 S4), theoretical values: C, 68.40; H, 6.10; F, 5.41; N, 10.97; S, 9.13, measured values: C, 68.45; H, 6.11; F, 5.40; N, 10.95; S, 9.10. MALDI-TOF analysis, theoretical value: 1404.87, found value: 1404.9.

[0210] The preparation process of the photodetector device is similar to that of Example 14. The flexible OPD device of PBDB-T: fully condensed ring small molecule 15 is used to demonstrate flexible biosensing applications: using a Keithley 2000 digital source meter, a Puyuan oscilloscope and an 808nm laser emitter, a human finger is placed between the light source and the detector, and the device output current-time curve is measured, as shown in Figure 25. The human pulse waveform can be clearly observed by photoplethysmography (PPG), and the real-time heart rate of the subject can be read as 72 beats / min. In summary, compared to inorganic photodetectors that can only be integrated on rigid substrates, based on the fully condensed ring small molecule 15, we can prepare organic photodetection devices on flexible substrates and realize real-time monitoring of human heart rate.

[0211] Example 16

[0212] The preparation method of the fully fused ring small molecule 16 is the same as the preparation method of the compound in Example 1, except that in the synthesis of compound 1-2, the raw material is replaced by (thieno[3,2-B]thien-2-yl)tributyltin to 7-methyl-2-(triisopropylsilyl)-6-(trimethylstannyl)-7H-thieno[2',3':4,5]thieno[3,2-b]pyrrole; in the synthesis of compound 1-4, the 2-iodo-4,5-dichlorobenzoyl chloride in the raw material is replaced by 2-bromo-3,4,5,6-tetrafluorobenzoyl chloride.

[0213] Elemental analysis structure (C 80 H 81 F8N 11 S4), theoretical values: C, 65.06; H, 5.53; F, 10.29; N, 10.43; S, 8.68, measured values: C, 65.01; H, 5.53; F, 10.30; N, 10.45; S, 8.69. MALDI-TOF analysis, theoretical value: 1476.83, found value: 1476.8.

[0214] The preparation process of the photodetector device is similar to that of Example 1. The photodetection performance and photostorage stability of the OPD device of PBDB-T: fully condensed ring small molecule 16 are characterized: the prepared 6 PBDB-T: fully condensed ring small molecule 16 and 6 PBDB-T:Y6 unpackaged organic photodetectors are placed in the air and stored with 600lux indoor light. The light intensity is calibrated by a lux meter. The indoor temperature is about 18-23℃ and the relative humidity is 15-30%. The response curve of the device is tested at regular intervals, and the peak response at 810nm and 840nm is taken for data statistics. The normalized response-time curve that can describe the attenuation of the device is drawn, as shown in Figure 26. The results show that after 1350 hours of light storage in the air, the peak response of the PBDB-T: fully condensed ring small molecule 16 device only changes from 0.39AW -1 Down to 0.352AW -1 , T of unpackaged devices 90 It can reach 1350h. In contrast, the peak responsivity of PBDB-T:Y6 device is from 0.424AW -1 Down to 0.347AW -1 , T of unpackaged devices 90 In summary, the organic photodetector based on the fully condensed-ring small molecule electron acceptor 16 has good light storage stability.

[0215] Example 17

[0216] A fully fused ring small molecule 17 was obtained through a similar synthetic route. The preparation method of molecule 17 is the same as that of the compound in Example 1, except that in the synthesis of compound 1-2, (thieno[3,2-B]thien-2-yl)tributyltin is replaced with 7-methyl-2-(triisopropylsilyl)-6-(trimethylstannyl)-7H-thieno[2',3':4,5]thieno[3,2-b]pyrrole; in the synthesis of compound 1-4, 2-iodo-4,5-dichlorobenzoyl chloride in the raw material is replaced with 2-bromo-4,5-difluorobenzoyl chloride; and in the synthesis of the final product, malononitrile is replaced with 5,6-difluoro-3-(dicyanomethylidene)indone.

[0217] Elemental analysis structure (C 98 H 89 F8N 11 O2S4), theoretical: C, 67.92; H, 5.18; F, 8.77; N, 8.89; O, 1.85; S, 7.40. Measured: C, 67.98; H, 5.18; F, 8.76; N, 8.87; O, 1.83; S, 7.41. MALDI-TOF analysis, theoretical: 1731.60, found: 1731.6.

[0218] The preparation process of the photodetector device is similar to that of Example 1. The light detection performance of the OPD device of PBDB-T: fully condensed ring small molecule 17 is characterized. The results are shown in Figure 27 (measured using a Keithley 2635B digital source meter). Under a bias voltage of -0.5V, the dark current J d 5.37×10 -6 A cm -2 In contrast, at a bias voltage of -0.5 V, the dark current J d Only 3.34×10 -9 A cm -2 , which is about 1 / 1607 of PBDB-T:ITIC. The fully condensed ring small molecule 17 has advantages in the preparation of flexible and highly sensitive OPD.

[0219] Example 18

[0220] A similar synthetic route was used to obtain the fully fused ring small molecule 18. The preparation method of molecule 18 was the same as that of the compound in Example 1, except that in the synthesis of compound 1-2, (thieno[3,2-B]thien-2-yl)tributyltin was replaced with 7-methyl-2-(triisopropylsilyl)-6-(trimethylstannyl)-7H-thieno[2',3':4,5]thieno[3,2-b]pyrrole; in the synthesis of compound 1-4, 2-iodo-4,5-dichlorobenzoyl chloride was replaced with 2-bromo-3,4,5,6-tetrafluorobenzoyl chloride; and in the synthesis of the final product, malononitrile was replaced with 5,6-dichloro-3-(dicyanomethylidene)indone.

[0221] Elemental analysis structure (C 98 H 85 Cl4F8N 11 O2S4), theoretical value: C, 62.92; H, 4.58; Cl, ​​7.58; F, 8.12; N, 8.24; O, 1.71; S, 6.85, measured value: C, 62.86; H, 4.58; Cl, ​​7.59; F, 8.14; N, 8.25; O, 1.70; S, 6.86. MALDI-TOF analysis, theoretical value: 1867.44, found value: 1867.4.

[0222] The preparation process of the photodetector device is similar to that of Example 1. The light detection performance of the OPD device of PBDB-T: fully condensed ring small molecule 18 is characterized and shown in Figure 28 (measured using a Keithley 2635B digital source meter). In the self-powered mode, the dark current J of the organic photodetector device based on PBDB-T:Y6 is d 6.34×10 -10 A cm -2 In contrast, the dark current J of the photodetector device of PBDB-T: fully fused ring small molecule 18 is d Only 2.81×10 -10 A cm -2 , which is about 1 / 2 of PBDB-T:ITIC. The fully fused-ring small molecule 18 can be used to prepare highly sensitive OPD.

[0223] Example 19

[0224] A similar synthetic route was used to obtain the fully fused ring small molecule 19. The preparation method of molecule 19 was the same as that of the compound in Example 1, except that in the synthesis of compound 1-2, (thieno[3,2-B]thien-2-yl)tributyltin was replaced with 7-methyl-2-(triisopropylsilyl)-6-(trimethylstannyl)-7H-thieno[2',3':4,5]thieno[3,2-b]pyrrole; in the synthesis of compound 1-4, 2-iodo-4,5-dichlorobenzoyl chloride was replaced with 2-bromo-4,5-difluorobenzoyl chloride; and in the synthesis of the final product, malononitrile was replaced with 6-cyano-3-(dicyanomethylidene)indone.

[0225] Elemental analysis structure (C 100 H 91 F4N 13 O2S4), theoretical: C, 70.19; H, 5.36; F, 4.44; N, 10.64; O, 1.87; S, 7.49, found: C, 70.27; H, 5.36; F, 4.45; N, 10.67; O, 1.88; S, 7.50. MALDI-TOF analysis, theoretical: 1709.62, found: 1709.6.

[0226] The preparation process of the photodetector device is similar to that of Example 1. The optical detection performance of the OPD device of PBDB-T: fully fused ring small molecule 19 was characterized (measured using a Keithley 2400 digital source meter). The results are shown in Figure 29. Under a reverse bias voltage of -0.1V, the dark current J of the organic photodetector device based on PBDB-T:Y6 is d 9.35×10 -7 A cm -2 In contrast, the dark current J of the photodetector device of PBDB-T: fully fused ring small molecule 19 is d 6.66×10 -9 A cm -2 , which is only 1 / 140 of PBDB-T:ITIC. The fully condensed-ring small molecule 19 has advantages in the preparation of highly sensitive near-infrared OPD.

[0227] Example 20

[0228] A similar synthetic route was used to obtain the fully fused ring small molecule 20. The preparation method of molecule 20 was the same as that of the compound in Example 1, except that in the synthesis of compound 1-2, (thieno[3,2-B]thien-2-yl)tributyltin was replaced with 7-methyl-2-(triisopropylsilyl)-6-(trimethylstannyl)-7H-thieno[2',3':4,5]thieno[3,2-b]pyrrole; in the synthesis of compound 1-4, 2-iodo-4,5-dichlorobenzoyl chloride was replaced with 2-bromo-3,4,5,6-tetrafluorobenzoyl chloride; and in the synthesis of the final product, malononitrile was replaced with 5,6-difluoro-3-(dicyanomethylidene)indone.

[0229] Elemental analysis structure (C 98 H 85 F 12 N 11 O2S4), theoretical: C, 65.21; H, 4.75; F, 12.63; N, 8.54; O, 1.77; S, 7.10. Measured: C, 65.30; H, 4.74; F, 12.62; N, 8.55; O, 1.76; S, 7.11. MALDI-TOF analysis, theoretical: 1803.56, found: 1803.6.

[0230] The photodetector device preparation process was similar to that of Example 1. The photodetection performance of the OPD device based on PBDB-T: fully condensed ring small molecule 20 was characterized. The results are shown in Figure 30 (measured using a ProPlus 9812D). Under a bias voltage of -0.5 V, the noise current of the photodetector based on PBDB-T: fully condensed ring small molecule 20 at 1 kHz reached 3.96×10 -14 A Hz -1 / 2 , which is significantly lower than 1.79×10 -13 A Hz -1 / 2 , which is about 1 / 3 of the PBDB-T:Y6 device, indicating that the fully condensed ring small molecule 20 can be used to prepare highly sensitive near-infrared OPD.

[0231] Example 21

[0232] A fully fused ring small molecule 21 was obtained by a similar synthetic route. The preparation method of molecule 21 is the same as that of the compound in Example 1, except that in the synthesis of compound 1-2, 4,7-dibromo-2-(2-butyl)-5,6-dinitro-2H-benzo[d][1,2,3]triazole was replaced with 4,7-dibromo-5,6-dinitrobenzo[c][1,2,5]thiadiazole; (thieno[3,2-b]thiophen-2-yl)tributyltin was replaced with 4-methyl-2-(triisopropylsilyl)-5-(trimethylstannyl)-4H-thieno[3,2-b]pyrrole; and in the synthesis of compound 1-4, 2-iodo-4,5-dichlorobenzoyl chloride was replaced with 2-bromo-3,4,5,6-tetrafluorobenzoyl chloride.

[0233] Elemental analysis structure (C 72 H 72 F8N 10 S3), theoretical value: C, 65.24; H, 5.47; F, 11.47; N, 10.57; S, 7.26, measured value: C, 65.34; H, 5.46; F, 11.46; N, 10.56; S, 7.24. MALDI-TOF analysis, theoretical value: 1325.61, actual value: 1325.6.

[0234] The preparation process of the photodetector device is similar to that of Example 1. The photodetection performance of the OPD device of PBDB-T: fully condensed ring small molecule 21 is characterized. The S n The frequency characteristic curve is shown in Figure 31 (measured using ProPlus 9812D). Under a bias voltage of -0.5V, the noise current of the photodetector based on PBDB-T: fully fused ring small molecule 21 at 1kHz reaches 6.83×10 -14 A Hz -1 / 2 , which is lower than the 1.79×10 -13 A Hz -1 / 2 In summary, the fully fused-ring small molecule 21 has certain advantages over the non-fully fused-ring ITIC in the preparation of highly sensitive OPDs.

[0235] Example 22

[0236] A similar synthetic route was used to obtain the fully fused ring small molecule 22. The preparation method of molecule 22 was the same as that of the compound in Example 1, except that in the synthesis of compound 1-2, the raw material was replaced by 4,7-dibromo-2-(2-butyl)-5,6-dinitro-2H-benzo[d][1,2,3]triazole instead of 4,7-dibromo-5,6-dinitrobenzo[c][1,2,5]thiadiazole; in the synthesis of compound 1-4, the raw material 2-iodo-4,5-dichlorobenzoyl chloride was replaced by 2-bromo-3,4,5,6-tetrafluorobenzoyl chloride; and in the synthesis of the final product, the raw material malononitrile was replaced by 5,6-difluoro-3-(dicyanomethylidene)indone.

[0237] Elemental analysis structure (C 68 H 46 F4N8O2S3), theoretical: C, 69.25; H, 3.93; F, 6.44; N, 9.50; O, 2.71; S, 8.16, found: C, 69.61; H, 3.84; N, 9.57; S, 8.30. MALDI-TOF analysis, theoretical: 1178.28, found: 1178.3.

[0238] The preparation process of the interface layer and the electrode is the same as that in Example 1. During the preparation of the photosensitive layer, 8 mg of compound PM6, 12 mg of fully condensed ring small molecule 22 and 1 mL of CB drying solvent were first added to a 1.5 mL sample bottle, and the mixed solution was stirred at 400 rpm at 90 ° C for 2 h. After cooling to room temperature, 18 uL of chloronaphthalene was added and the stirring was continued for 0.5 h for standby use. 35 uL of the blended solution was dropped onto the substrate using a pipette, and the film was spin-coated at 2100 rpm. The wet film was thermally annealed at 100 ° C for 8 min, and the thickness of the functional layer was tested using an optical profilometer to be 215 nm. As a control, 10 mg of compound PM6 and 10 mg of small molecule PC were added to another sample bottle. 71 BM and 1 mL of CB dry solvent were stirred at 55°C at 400 rpm for 2 hours. After cooling to room temperature, 15 μL of 1,8-diiodooctane was added and stirring continued for 0.5 hours. Using a pipette, 35 μL of the blended solution was dropped onto a substrate and spin-coated at 1900 rpm to form a film. The wet film was thermally annealed at 90°C for 10 minutes. An optical profilometer was used to measure the thickness of the functional layer, which was 200 nm.

[0239] The light detection performance of the PM6: fully condensed ring small molecule 22 OPD device was characterized. The dark state JV characteristic curve of the device is shown in Figure 32 (measured using a Keithley 2635B digital source meter), and the responsivity-wavelength characteristic curve of the device is shown in Figure 33 (measured using a CEL-PD291 quantum efficiency test system). In the self-powered mode, the dark current J of the OPD device based on PM6: fully condensed ring small molecule 22 is d 3.35×10 -10 A cm -2 In contrast, PM6:PC 71 BM photodetector device dark current J d 1.63×10 -9 A cm -2 , which is about 5 times that of PM6: all-condensed ring small molecule 22. The peak responsivity of the OPD device of PM6: all-condensed ring small molecule 22 is 0.349AW at 870nm. -1 , and PM6:PC 71 The peak responsivity of BM is 0.313AW at 640nm -1 By comparison, it can be seen that the OPD device based on the fully condensed ring small molecule 22 can achieve higher responsiveness in a more red-shifted spectral range.

[0240] Example 23

[0241] A fully fused ring small molecule 23 was obtained through a similar synthetic route. The preparation method of molecule 23 is the same as that of the compound in Example 1, except that in the synthesis of compound 1-2, 4,7-dibromo-2-(2-butyl)-5,6-dinitro-2H-benzo[d][1,2,3]triazole was replaced with 4,7-dibromo-5,6-dinitrobenzo[c][1,2,5]thiadiazole; (thieno[3,2-b]thiophen-2-yl)tributyltin was replaced with 4-methyl-2-(triisopropylsilyl)-5-(trimethylstannyl)-4H-thieno[3,2-b]pyrrole; and in the synthesis of the final product, malononitrile was replaced with 5,6-difluoro-3-(dicyanomethylidene)indone.

[0242] Elemental analysis structure (C 90 H 80 Cl4F4N 10 O2S3), theoretical value: C, 65.61; H, 4.89; Cl, ​​8.61; F, 4.61; N, 8.50; O, 1.94; S, 5.84, measured value: C, 65.50; H, 4.90; Cl, ​​8.62; F, 4.62; N, 8.50; O, 1.95; S, 5.84. MALDI-TOF analysis, theoretical value: 1647.67, found value: 1647.7.

[0243] The preparation process of the photodetector device is similar to that of Example 22. The light detection performance of the OPD device of PM6: fully condensed ring small molecule 23 is characterized. The dark state JV characteristic curve of the device is shown in Figure 34 (measured using Keithley 2635B digital source meter, probe station and electromagnetic shielding box). The schematic diagram of the flexible OPD device structure is shown in Figure 38. In the self-powered mode, the dark current J of the OPD device based on PM6: fully condensed ring small molecule 23 is 0.13 V. d 3.79×10 -10 A cm -2 In contrast, PM6:PC 71 BM photodetector device dark current J d 1.63×10 -9 A cm -2 , which is about 5 times that of PM6: fully fused ring small molecule 23. In summary, fully fused ring small molecule 23 is better than fullerene electron acceptor PC 71 BM has certain advantages in preparing highly sensitive OPD.

[0244] Example 24

[0245] A similar synthetic route was used to obtain the fully fused ring small molecule 24. The preparation method of molecule 24 was the same as that of the compound in Example 1, except that in the synthesis of compound 1-2, the starting material was replaced by 4,7-dibromo-2-(2-butyl)-5,6-dinitro-2H-benzo[d][1,2,3]triazole instead of 4,7-dibromo-5,6-dinitrobenzo[c][1,2,5]thiadiazole; in the synthesis of compound 1-4, the starting material 2-iodo-4,5-dichlorobenzoyl chloride was replaced by 2-bromo-4,5-tetrafluorobenzoyl chloride; and in the synthesis of the final product, the starting material malononitrile was replaced by 2-ethylrhodanine.

[0246] Elemental analysis structure (C 74 H 80 F4N6O2S9), theoretical: C, 61.30; H, 5.56; F, 5.24; N, 5.80; O, 2.21; S, 19.90, found: C, 61.21; H, 5.43; N, 5.86; S, 19.79. MALDI-TOF analysis, theoretical: 1448.38, found: 1448.4.

[0247] The preparation process of the photodetector device is similar to that of Example 22. The device responsivity-wavelength characteristic curve is shown in Figure 35 (measured using a CEL-PD291 quantum efficiency test system). In the self-powered mode, the peak responsivity of the OPD device based on PM6: fully condensed ring small molecule 24 is 0.267 AW at 900 nm.-1 , and PM6:PC 71 The peak responsivity of BM is 0.313AW at 640nm -1 , the comparison shows that the OPD device based on the fully condensed ring small molecule 24 can realize light detection in a more red-shifted spectral range. Comprehensive analysis shows that the fully condensed ring small molecule 24 is better than the fullerene receptor PC 71 BM is more suitable for infrared light detection.

[0248] Example 25

[0249] A similar synthetic route was used to obtain the fully fused ring small molecule 25. The preparation method of molecule 25 was the same as that of the compound in Example 1, except that in the synthesis of compound 1-2, 4,7-dibromo-2-(2-butyl)-5,6-dinitro-2H-benzo[d][1,2,3]triazole was replaced with 4,7-dibromo-5,6-dinitrobenzo[c][1,2,5]thiadiazole; (thieno[3,2-b]thiophen-2-yl)tributyltin was replaced with (dithieno[3,2-b:2',3'-d]thiophene)tributyltin; in the synthesis of compound 1-4, 2-iodo-4,5-dichlorobenzoyl chloride was replaced with 2-bromo-4,5-difluorobenzoyl chloride; and in the synthesis of the final product, malononitrile was replaced with 5,6-difluoro-3-(dicyanomethylidene)indone.

[0250] Elemental analysis structure (C 92 H 74 F8N8O2S7), theoretical: C, 65.00; H, 4.39; F, 8.94; N, 6.59; O, 1.88; S, 13.20, found: C, 65.04; H, 4.38; F, 8.95; N, 6.58; O, 1.88; S, 13.23. MALDI TOF analysis, theoretical: 1700.07, found: 1700.1.

[0251] The preparation process of the photodetector device is similar to that of Example 22. The photodetection performance of the OPD device of PM6: fully condensed ring small molecule 25 is characterized. The S n The frequency characteristic curve is shown in Figure 36 (measured using ProPlus 9812D). Under a bias voltage of -0.5V, the noise current of the photodetector based on PM6: fully fused ring small molecule 25 at 1kHz reaches 8.63×10 -14 A Hz -1 / 2 , lower than PM6:PC 71 BM device 3.57×10 -13 A Hz -1 / 2 .

[0252] Example 26

[0253] A similar synthetic route was used to obtain the fully fused-ring small molecule 26. The preparation method of molecule 26 is the same as the preparation method of the compound in Example 1, except that in the synthesis of compound 1-2, 4,7-dibromo-2-(2-butyl)-5,6-dinitro-2H-benzo[d][1,2,3]triazole is replaced with 4,7-dibromo-5,6-dinitrobenzo[c][1,2,5]thiadiazole; (thieno[3,2-b]thieno[2,3-d]thieno-2-yl)tributyltin is replaced with (thieno[2',3':4,5]thieno[3,2-b]thieno[2,3-d]thieno-2-yl)tributyltin; in the synthesis of compound 1-4, 2-iodo-4,5-dichlorobenzoyl chloride is replaced with 2-bromo-3,4,5,6-tetrafluorobenzoyl chloride; and in the synthesis of the final product, malononitrile is replaced with 6-cyano-3-(dicyanomethyl)indone.

[0254] Elemental analysis structure (C 98 H 72 F8N 10 O2S9), theoretical: C, 63.21; H, 3.90; F, 8.16; N, 7.52; O, 1.72; S, 15.49, found: C, 63.30; H, 3.89; F, 8.15; N, 7.51; O, 1.73; S, 15.47. MALDI TOF analysis, theoretical: 1862.25, found: 1862.3.

[0255] The preparation process of the flexible photodetector device is similar to that of Example 14. The light detection performance of the PM6: fully condensed ring small molecule 26 OPD flexible device was characterized (measured using a Keithley 2400 digital source meter). The dark state JV characteristic curve of the device is shown in Figure 37, and the structure of the flexible OPD device is shown in Figure 38. In the self-powered mode, the dark current J of the OPD device based on PM6: fully condensed ring small molecule 26 is 0.13 V. d 1.39×10 -10 A cm -2 In contrast, PM6:PC 71 BM photodetector device dark current J d 1.63×10 -9 A cm -2 , which is about 10 times that of PM6: fully condensed ring small molecule 26. This indicates that fully condensed ring small molecule 26 has potential in the preparation of highly sensitive self-powered OPDs.

[0256] Example 27

[0257] A similar synthetic route was used to obtain the fully fused-ring small molecule 27. The preparation method of molecule 27 is the same as the preparation method of the compound in Example 1, except that in the synthesis of compound 1-2, 4,7-dibromo-2-(2-butyl)-5,6-dinitro-2H-benzo[d][1,2,3]triazole is replaced with 4,7-dibromo-5,6-dinitrobenzo[c][1,2,5]thiadiazole; (thieno[3,2-b]thieno[2,3-d]thieno-2-yl)tributyltin is replaced with (thieno[2',3':4,5]thieno[3,2-b]thieno[2,3-d]thieno-2-yl)tributyltin; in the synthesis of compound 1-4, 2-iodo-4,5-dichlorobenzoyl chloride is replaced with 2-bromo-3,4,5,6-tetrafluorobenzoyl chloride; and in the synthesis of the final product, malononitrile is replaced with 5,6-difluoro-3-(dicyanomethyl)indone.

[0258] Elemental analysis structure (C 89 H 56 F 12 N8O2S9), theoretical: C, 59.85; H, 3.16; F, 12.76; N, 6.27; O, 1.79; S, 16.16. Measured: C, 59.77; H, 3.17; F, 12.77; N, 6.29; O, 1.78; S, 16.17. MALDI TOF analysis, theoretical: 1786.00, found: 1786.0.

[0259] The preparation process of the flexible photodetector device is similar to that of Example 14. The light detection performance of the PM6: fully condensed ring small molecule 27 OPD flexible device was characterized (measured using a Keithley 2400 digital source meter). The dark state JV characteristic curve of the device is shown in Figure 39. Under a bias voltage of -0.1V, the dark current J of the OPD device based on PM6: fully condensed ring small molecule 27 is d 1.80×10 -10 A cm -2 In contrast, PM6:PC 71 BM photodetector device dark current J d 2.63×10 -8 A cm -2 , which is about 146 times that of PM6: fully condensed ring small molecule 27. This shows that fully condensed ring small molecule 27 is better than PC 71 BM has obvious advantages in preparing highly sensitive OPD.

[0260] Example 28

[0261] A similar synthetic route was used to obtain the fully fused-ring small molecule 28. The preparation method of molecule 28 is the same as the preparation method of the compound in Example 1, except that in the synthesis of compound 1-2, 4,7-dibromo-2-(2-butyl)-5,6-dinitro-2H-benzo[d][1,2,3]triazole is replaced with 4,7-dibromo-5,6-dinitrobenzo[c][1,2,5]thiadiazole; (thieno[3,2-b]thiophen-2-yl)tributyltin is replaced with 8-methyl-6-(tributyltin)-2-(triisopropylsilyl)-8H-thiopheno[2',3':4,5]thiopheno[3,2-b]thiopheno[2,3-d]pyrrole; in the synthesis of compound 1-4, 2-iodo-4,5-dichlorobenzoyl chloride is replaced with 2-bromobenzoyl chloride; in the synthesis of compound 1-6, malononitrile is replaced with dicyanorhodamine.

[0262] Elemental analysis structure (C 88 H 84 N 10 S 13 ), theoretical value: C, 62.23; H, 4.99; N, 8.25; S, 24.54, measured value: C, 62.48; H, 5.03; N, 8.41; S, 24.61. MALDI TOF analysis, theoretical value: 1696.32, found value: 1696.3.

[0263] The photodetector device preparation process is similar to that of Example 22. The device responsivity-wavelength characteristic curve is shown in Figure 40 (measured using a CEL-PD291 quantum efficiency test system). In the self-powered mode, the peak responsivity of the OPD device based on PM6: fully condensed ring small molecule 28 is 0.087 AW at 1090 nm. -1 , and PM6:PC 71 The peak responsivity of BM is 0.313AW at 640nm -1 By comparison, it can be seen that the OPD device based on the fully condensed ring small molecule 28 can achieve light detection in the NIR-II spectral range. This shows that the fully condensed ring small molecule 28 is suitable for NIR-II infrared light detection.

[0264] Example 29

[0265] The fully fused ring small molecule 29 was obtained by a similar synthetic route. The preparation method of molecule 29 is the same as that of the compound in Example 1, except that in the synthesis of compound 1-2, the raw material was replaced by 4,7-dibromo-2-(2-butyl)-5,6-dinitro-2H-benzo[d][1,2,3]triazole instead of 4,7-dibromo-5,6-dinitrobenzo[c][1,2,5]thiadiazole; (thieno[3,2-B]thiophen-2-yl)tributyltin was replaced by 8 -methyl-6-(tributyltin)-2-(triisopropylsilyl)-8H-thiopheno[2',3':4,5]thiopheno[3,2-b]thiopheno[2,3-d]pyrrole; in the synthesis of compound 1-4, the 2-iodo-4,5-dichlorobenzoyl chloride in the raw material was replaced with 2-bromo-4,5-difluorobenzoyl chloride; in the synthesis of the final product, the malononitrile in the raw material was replaced with 5,6-difluoro-3-(dicyanomethylidene)indone.

[0266] Elemental analysis structure (C 100 H 78 F8N 12 O2S7), theoretical: C, 64.71; H, 4.24; F, 8.19; N, 9.06; O, 1.72; S, 12.09, found: C, 64.65; H, 4.25; F, 8.18; N, 9.07; O, 1.73; S, 12.10. MALDI TOF analysis, theoretical: 1856.21, found: 1856.2.

[0267] The preparation process of the photodetector device is similar to that of Example 22. The light detection performance of the OPD device of PM6: fully condensed ring small molecule 29 is characterized. The dark state JV characteristic curve of the device is shown in Figure 41 (measured using a Keithley 2635B digital source meter, a probe station and an electromagnetic shielding box). In the self-powered mode, the dark current J of the OPD device based on PM6: fully condensed ring small molecule 29 is d 1.00×10 -10 A cm -2 In contrast, PM6:PC 71 BM photodetector device dark current J d Significantly higher, at 1.63×10 -9 A cm -2 In summary, the fully fused ring small molecule 29 is better than the fullerene electron acceptor PC 71 BM has obvious advantages in preparing highly sensitive OPD.

[0268] Example 30

[0269] A similar synthetic route was used to obtain the fully fused-ring small molecule 30. The preparation method of molecule 30 is the same as the preparation method of the compound in Example 1, except that in the synthesis of compound 1-2, 4,7-dibromo-2-(2-butyl)-5,6-dinitro-2H-benzo[d][1,2,3]triazole is replaced with 4,7-dibromo-5,6-dinitrobenzo[c][1,2,5]thiadiazole; (thieno[3,2-b]thieno[2,3-d]thieno-2-yl)tributyltin is replaced with (thieno[2',3':4,5]thieno[3,2-b]thieno[2,3-d]thieno-2-yl)tributyltin; in the synthesis of compound 1-4, 2-iodo-4,5-dichlorobenzoyl chloride is replaced with 2-iodo-3,4,5,6-tetrachlorobenzoyl chloride; in the synthesis of the final product, malononitrile is replaced with 6-cyano-3-(dicyanomethyl)indone.

[0270] Elemental analysis structure (C 98 H 72 Cl8N 10 O2S9), theoretical: C, 59.04; H, 3.64; Cl, ​​14.22; N, 7.03; O, 1.60; S, 14.47, found: C, 59.08; H, 3.63; Cl, ​​14.21; N, 7.02; O, 1.59; S, 14.46. MALDI TOF analysis, theoretical: 1993.86, found: 1993.9.

[0271] The photodetector device fabrication process was similar to that of Example 22, except that the anode interface layer used inorganic copper thiocyanate (CuSCN). 15 mg of CuSCN and 1 mL of CB drying solvent were added to a 1.5 mL sample vial. The mixed solution was stirred at 500 rpm at room temperature for 3 h. Using a pipette, 35 μL of the blended solution was dropped onto a substrate and spin-coated at 3000 rpm to form a film. The wet film was thermally annealed at 120°C for 10 min. An optical profilometer was used to measure the thickness of the functional layer, which was 25 nm. Subsequently, an active layer composed of a PM6: fully fused ring small molecule 30 blend was applied to the anode interface layer. Organic PFN-Br was used as the cathode interface layer. 0.5 mg of PFN-Br and 1 mL of methanol drying solvent were added to a 1.5 mL sample bottle. The mixed solution was stirred at 500 rpm for 6 h at room temperature. 60 uL of the mixed solution was dropped onto the substrate using a pipette and spin-coated at 3000 rpm to form a film. The thickness of the functional layer was tested using an optical profilometer and was found to be 8 nm.

[0272] The light detection performance of the PM6: all-condensed ring small molecule 30 OPD device was characterized, and the dark state JV characteristic curve of the device is shown in Figure 42 (measured using a Keithley 2635B digital source meter, a probe station and an electromagnetic shielding box). In the self-powered mode, the dark current J of the OPD device based on PM6: all-condensed ring small molecule 30 is d 9.61×10 -11 A cm -2 In contrast, PM6:PC 71 BM photodetector device dark current J d Significantly higher, at 1.63×10 -9 A cm -2 In summary, the fully fused ring small molecule 30 is better than the fullerene electron acceptor PC 71 BM has obvious advantages in preparing highly sensitive OPD.

[0273] Example 31

[0274] A similar synthetic route was used to obtain the fully fused ring small molecule 31. The preparation method of molecule 31 was the same as that of the compound in Example 1, except that in the synthesis of compound 1-2, the raw material was replaced by 5,8-dibromo-2,3-dibutyl-6,7-dinitroquinoxaline instead of 4,7-dibromo-2-(2-butyl)-5,6-dinitro-2H-benzo[d][1,2,3]triazole; and in the synthesis of compound 1-4, the raw material 2-iodo-4,5-dichlorobenzoyl chloride was replaced by 2-bromo-4,5-difluorobenzoyl chloride.

[0275] The preparation process of the photodetector device is similar to that of Example 30, wherein organic PDINO is used for the cathode interface layer. 1.1 mg of PDINO and 1 mL of methanol drying solvent are added to a 1.5 mL sample bottle, and the mixed solution is stirred at 500 rpm at room temperature for 6 h. 65 uL of the blended solution is dropped onto the substrate using a pipette, and the film is spin-coated at 3000 rpm. The thickness of the functional layer is tested using an optical profilometer and is found to be 15 nm.

[0276] The light detection performance of the PM6: fully condensed ring small molecule 31 OPD device was characterized, and the dark state JV characteristic curve of the device is shown in Figure 43 (measured using a Keithley 2635B digital source meter, a probe station, and an electromagnetic shielding box). In the self-powered mode, the dark current J of the OPD device based on PM6: fully condensed ring small molecule 31 is d 9.85×10 -10 A cm -2 In contrast, PM6:PC 71 BM photodetector device dark current J d Higher, 1.63×10-9 A cm -2 In summary, the fully fused ring small molecule 31 is better than the fullerene electron acceptor PC 71 BM has certain advantages in preparing highly sensitive OPD.

[0277] Example 32

[0278] A similar synthetic route was used to obtain the fully fused ring small molecule 32. The preparation method of molecule 32 was the same as that of the compound in Example 31, except that in the synthesis of compound 1-2, the raw material was replaced by 5,8-dibromo-2,3-dibutyl-6,7-dinitroquinoxaline instead of 4,7-dibromo-2-(2-butyl)-5,6-dinitro-2H-benzo[d][1,2,3]triazole; and by 8-methyl-1,4-dibromo-2,3-dibutyl-6,7-dinitroquinoxaline instead of (thieno[3,2-B]thiophen-2-yl)tributyltin. In the synthesis of compound 1-4, the 2-iodo-4,5-dichlorobenzoyl chloride in the raw material was replaced by 2-bromo-3,4,5,6-tetrafluorobenzoyl chloride; in the synthesis of the final product, the malononitrile in the raw material was replaced by 6-cyano-3-(dicyanomethyl)indone.

[0279] Elemental analysis structure (C 110 H 96 F8N 12 O2S6), theoretical: C, 67.33; H, 4.93; F, 7.74; N, 8.57; O, 1.63; S, 9.80, found: C, 67.38; H, 4.92; F, 7.73; N, 8.56; O, 1.62; S, 9.80. MALDI TOF analysis, theoretical: 1962.41, found: 1962.4.

[0280] The preparation process of the corresponding photodetector device is similar to that of Example 31. The photodetection performance of the OPD device of PM6: fully condensed ring small molecule 32 is characterized. The S n -Frequency characteristic curve is shown in Figure 44 (measured using ProPlus 9812D). Under 0V bias, the dark current J of the device based on PM6: fully condensed ring small molecule 32 is d Up to 1.05×10 -10 A cm -2 , significantly lower than PM6:PC 71 1.50×10 of BM -9 A cm -2 ; In terms of noise current, at 0V, 1kHz, PM6:PC 71 BM's S nReaching 1.55×10 -13 A Hz -1 / 2 , which is significantly higher than the 2.96×10 -9 A Hz -1 / 2 Compared with the fullerene electron acceptor PC, the fully fused ring small molecule acceptor 32 71 BM has obvious advantages in preparing highly sensitive OPD.

[0281] Obviously, the above embodiments are merely examples for clarity of explanation and are not intended to limit the implementation methods. Those skilled in the art will readily appreciate that other variations or modifications based on the above descriptions are possible. It is not necessary and impossible to enumerate all implementation methods here. Obvious variations or modifications arising therefrom remain within the scope of protection of the present invention.

Claims

1. Application of a fully condensed ring small molecule compound in the preparation of an organic photodetector, wherein: The structure of the fully fused ring small molecule compound is shown in the following formula (I): R1 is -C m1 H 2m1+1 or -(CH2) n1 C(C x1 H 2x1+1 )(C y1 H 2y1+1 ), m1 is an integer from 1 to 36, n1 is an integer from 0 to 10, and x1 and y1 are each independently an integer from 1 to 40; Ar1 is a substituted or unsubstituted 4- to 14-membered heteroaryl or 4- to 8-membered heterocycloalkyl; when substituted, the heteroaryl or heterocycloalkyl is substituted by 1, 2, 3 or 4 substituents selected from F, Cl, Br, I, ═O or R2; the heteroaryl contains 1, 2 or 3 heteroatoms selected from N, S, O or Se; R2 is selected from -C m2 H 2m2+1 or -(CH2) n2 C(C x2 H 2x2+1 )(C y2 H 2y2+1 ), m2 is an integer from 1 to 36, n2 is an integer from 0 to 10, and x2 and y2 are each independently an integer from 1 to 40; Ar2 is a substituted or unsubstituted 5- to 14-membered monocyclic or condensed-ring heteroaryl group, which, when substituted, is substituted by 1, 2 or 3 substituents selected from F, Cl, Br, I or R3; the heteroaryl group contains 1, 2, 3, 4 or 5 heteroatoms selected from N, S or O; R3 is selected from -C m3 H 2m3+1 or -(CH2) n3 C(C x3 H 2x3+1 )(C y3 H 2y3+1 ), m3 is an integer from 1 to 36, n3 is an integer from 0 to 10, and x3 and y3 are each independently an integer from 1 to 40; A is selected from one of the following structures: Z is H, F, Cl, Br or CN; R4 is selected from -C m4 H 2m4+1 ,m4 is an integer from 1 to 16; X and Y are each independently selected from H, F, Cl, Br or CN; * is the connection site.

2. The use according to claim 1, wherein Ar2 is a substituted or unsubstituted 5-membered monocyclic heteroaryl group or an 8- to 14-membered condensed-ring heteroaryl group.

3. The use according to claim 1, wherein: Ar1 is a substituted or unsubstituted 4-, 5- or 6-membered monocyclic heteroaryl, a 4-, 5- or 6-membered monocyclic heterocycloalkyl, or a 10- to 14-membered fused heteroaryl; Ar2 is a substituted or unsubstituted 5- or 6-membered monocyclic heteroaryl or an 8- to 14-membered fused heteroaryl.

4. The use according to any one of claims 1 to 3, wherein: Ar1 is selected from one of the following structures:

5. The use according to any one of claims 1 to 4, wherein: Ar2 is selected from one of the following structures:

6. The use according to claim 1, wherein: m1 is an integer from 5 to 10, n1 is an integer from 1, 2 or 3, and x1 and y1 are each independently an integer from 1, 2, 3, 4 or 5; Ar1 is a substituted or unsubstituted 4-membered, 5-membered or 6-membered heteroaryl group; when substituted, the heteroaryl group is substituted by R2; the heteroatoms of the heteroaryl group are 2 or 3 nitrogen atoms; R2 is selected from -C m2 H 2m2+1 or -(CH2) n2 C(C x2 H 2x2+1 )(C y2 H 2y2+1 ), m2 is an integer from 5 to 10, n2 is an integer from 1, 2 or 3, and x2 and y2 are each independently an integer from 3 to 10; Ar2 is a substituted or unsubstituted 8-, 9-, 10-, 11-, 12-, 13-, or 14-membered fused ring heteroaryl group, and when substituted, the heteroaryl group is substituted by 1, 2, or 3 R3 groups; R3 is selected from -C m3 H 2m3+1 or -(CH2) n3 C(C x3 H 2x3+1 )(C y3 H 2y3+1 ), m3 is an integer of 1, 2, 3, 4 or 5, n3 is an integer of 0 to 3, and x3 and y3 are each independently an integer of 1 to 5; A is selected from Z is H, F, Cl, Br or CN; R4 is selected from -C m4 H 2m4+1 , m4 is an integer from 1 to 16; X and Y are each independently selected from H, F, Cl or Br.

7. The use according to claim 1, wherein: The compound is selected from one of the following structures:

8. An organic photodetector, prepared by using the fully condensed-ring small molecule compound according to any one of claims 1 to 7 as an electron acceptor.

9. Use of the organic photodetector according to claim 8 in optical communications, infrared imaging, flexible wearable electronics, biological health testing, or biomedical monitoring.

10. The use according to claim 9, wherein: The infrared imaging is achieved by detecting near-infrared / short-wave infrared light.

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