Method for preparing short-wave-infrared-responsive deuterated quinone terminal group end-capped n-type organic molecule, method for preparing deuterated quinone terminal group, and use of short-wave-infrared-responsive deuterated quinone terminal group end-capped n-type organic molecule

Abstract

The present invention relates to the field of photoelectric materials. Disclosed are a method for preparing a short-wave-infrared-responsive deuterated quinone terminal group end-capped N-type organic molecule, a method for preparing a deuterated quinone terminal group, and a use of the short-wave-infrared-responsive deuterated quinone terminal group end-capped N-type organic molecule. The short-wave-infrared-responsive deuterated quinone end-capped N-type organic molecule has the following structural formula. The deuterated quinone terminal group end-capped N-type organic molecular material of the present invention has excellent solubility, is beneficial to processing and film formation, and has an extremely narrow optical band gap and an appropriate electron energy level. Compared with a non-deuterated quinone terminal group end-capped N-type organic molecule material, an optical detector prepared from the deuterated quinone terminal group end-capped N-type organic molecule material has a higher specific detection rate in a short-wave infrared region, thereby greatly improving the capability of the optical detector detecting short-wave infrared light. The prepared optical detector has more balanced carrier mobility, lower dark current, higher EQE response, and prolonged service life.

Description

A short-wave infrared responsive deuterated quinone-type end-capped N-type organic molecule and a preparation method and application of the deuterated quinone-type end group Technical Field

[0001] The present invention relates to the field of photoelectric materials, and in particular to an N-type organic molecule terminated with a deuterated quinone-type end group whose infrared response reaches the short-wave infrared region, and a preparation method and application of the deuterated quinone-type end group. Background Art

[0002] A photodetector is a device that can convert light signals into electrical signals. It can be used to detect light intensity, frequency, phase and other characteristics, and can convert this information into electrical signal output.

[0003] Organic photodetectors (OPDs) are a key component of photodetectors. They are optoelectronic devices constructed from organic semiconductor materials, primarily used to convert incident light signals into electrical signals and perform signal amplification and processing. Compared to inorganic photodetectors, which suffer from disadvantages such as expensive materials, brittleness, large weight and volume, strong temperature dependence, and high manufacturing difficulty, OPDs, at their core, are bulk heterojunction organic semiconductor materials. These materials possess key advantages such as high absorption coefficient, tunable energy levels and absorption spectra, flexibility, lightweight, and large-area solution processing. These advantages enable large-scale, low-cost fabrication of OPDs, along with their tunable spectral response range, fast response time, flexible and wearable design, and environmental friendliness. OPDs have become a research hotspot and are promising candidates for next-generation photodetectors, with great commercial potential. With the advancement of organic semiconductor materials, OPDs have demonstrated excellent light detection performance in the ultraviolet-visible (UV-Vis) and near-infrared (NIR) wavelengths, comparable to commercial photodetectors. However, in the SWIR band, the development and application of high-performance OPDs that can respond to short-wave infrared are still greatly restricted due to the limitations of the number and types of organic semiconductor materials and their material properties. In addition, due to the inherent characteristics of organic semiconductor materials, they are limited by the energy gap law, wavelength red shift, non-radiative transition enhancement, external quantum efficiency (EQE) and dark current (J d ) will be greatly affected. In addition, since organic semiconductor materials are composed of elements such as carbon, hydrogen, oxygen, and nitrogen, they are more susceptible to the effects of water, oxygen, high temperature, and light in the environment, resulting in poor chemical stability, which also limits the commercial application of OPDs.

[0004] Based on the above problems, the present invention adopts a deuteration strategy to design and synthesize a series of N-type organic semiconductor materials capped with deuterated quinone end groups that can respond to short-wave infrared. By deuterating the end groups of organic semiconductor materials, the specific detection rate of OPDs in the short-wave infrared region is greatly improved, and the detection ability of photodetectors for short-wave infrared light is greatly improved. The prepared photodetectors have more balanced carrier mobility, lower dark current and higher EQE response, and longer photodetector life, which has greatly promoted the development and commercial application of short-wave infrared OPDs. Summary of the Invention

[0005] The present invention relates to the field of optoelectronic materials, and in particular to an N-type organic molecule capped with a deuterated quinone-type end group having an infrared response reaching the short-wave infrared region, and a preparation method and application of the deuterated quinone-type end group. The N-type organic molecular material capped with a deuterated quinone-type end group has excellent solubility, is easy to process into a film, has an extremely narrow optical band gap, and has a suitable electronic energy level. Compared with the N-type organic molecular material capped with a non-deuterated quinone-type end group, the prepared photodetector has a higher specific detection rate in the short-wave infrared region, greatly improving the photodetector's detection capability for short-wave infrared light. The prepared photodetector has a more balanced carrier mobility, a lower dark current, a higher EQE response, and a longer photodetector life.

[0006] The term "bulk heterojunction" in the present invention refers to an interpenetrating network structure with nanoscale phase separation formed by blending donor and acceptor materials.

[0007] The term "donor material" in the present invention refers to a P-type semiconductor material.

[0008] The term "acceptor material" in the present invention refers to an N-type semiconductor material.

[0009] The term "band gap" in the present invention refers to the optical band gap of a semiconductor material, and its value is obtained by dividing 1240 by the cut-off wavelength of the absorption edge of the semiconductor material.

[0010] The term "spectral response region" in the present invention refers to the effective operating optical band of the photodiode and its array, and is defined as the wavelength range where the external quantum efficiency is greater than zero efficiency.

[0011] The term "active layer" in the present invention refers to a thin film layer in a device structure that is responsible for absorbing photons and generating free electrons and holes.

[0012] The term "aromatic group" as used herein refers to an aromatic ring system containing a conjugated structure, which may be partially or fully conjugated. Aromatic groups may be independently connected to adjacent units by bonding or fusion. They may contain carbon atoms, or some of their carbon atoms, independently substituted with heteroatoms such as N, O, S, or Se; the N and S atoms may be independently oxidized; and the nitrogen atoms may be independently substituted or unsubstituted, and may be independently quaternized.

[0013] To achieve the purpose of the present invention, a short-wave infrared responsive N-type organic molecule capped with a deuterated quinone end group is provided.

[0014] It has the following structural formula (I)

[0015] wherein n is independently selected from 0 or a positive integer; each E is independently selected from a substituted or unsubstituted aromatic group or cycloalkyl group, or is absent; each K is independently selected from a substituted or unsubstituted aromatic group or cycloalkyl group, or is absent; each R1 is independently selected from one or more of a hydrogen atom, an ester group, a hydroxyl group, a nitro group, a halogen, a cyano group, an alkyl group, an alkyl derivative, an alkoxy group, an alkoxy derivative, an alkylthio group, an alkylthio derivative, an alkylene group, an alkylene derivative, an aralkyl group, and an aralkyl derivative; and one or more carbon atoms on the alkyl derivative, alkoxy derivative, alkylthio derivative, alkylene derivative, or aralkyl derivative are independently substituted with one or more of an oxygen atom, an amino group, a sulfone group, a carbonyl group, an aryl group, an alkene group, an alkynyl group, an ester group, a cyano group, and a nitro group;

[0016] and / or

[0017] One or more hydrogen atoms on the alkyl derivative, alkylthio derivative, alkoxy derivative, alkylene derivative or aralkyl derivative are independently substituted by one or more of halogen, hydroxyl, amino, carboxyl, cyano, nitro, aryl, alkene or alkyne groups; each X and X' are independently selected from R1-C-R1, S, O, Se, N-R1 or R1-Si-R1;

[0018] Each Y is independently selected from R1-C-R1, S, O, Se, N-R1 or R1-Si-R1; each group Ar is independently selected from one of the groups shown in the following formula:

[0019] wherein each Z is independently selected from R1-C-R1, S, O, Se, N-R1 or R1-Si-R1;

[0020] Each R2 is independently selected from hydrogen, fluorine, chlorine, bromine, trifluoromethyl, substituted or unsubstituted alkyl, substituted or unsubstituted aromatic, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylthio, substituted or unsubstituted silyl or substituted or unsubstituted ester;

[0021] Any one or more hydrogen atoms in the structural formula (I) are not substituted by other atoms and / or groups, or are independently substituted by protium, deuterium or tritium atoms.

[0022] The term "alkyl" in the present invention refers to a branched or straight-chain saturated aliphatic hydrocarbon group having a specified number of carbon atoms. Examples of alkyl groups include straight-chain or branched alkyl groups, and straight-chain alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, n-heneicosyl, n-docosyl, n-tricosyl, and n-tetracosyl; branched-chain alkyl groups include, but are not limited to, isopropyl, isobutyl, tert-butyl, isopentyl, 1-Hexyl, 1-Hexyl, 1-Hexyl, 1-Hexyldecyl, 2-Hexyldecyl, 3-Hexylundecyl, 2-octyldecyl, 2-octyldodecyl, 3-octyltridecyl, 2-decyldodecyl, 2-decyltetradecyl, 3-decylpentadecyl, 2-dodecylhexadecyl, 4-octyltetradecyl, 4-decylhexadecyl, 4-hexyldecyl, 4-octyldodecyl, 4-decyltetradecyl, 4-dodecylhexadecyl and the like.

[0023] The term "alkoxy" as used herein refers to -O-alkyl, wherein the definition of alkyl is consistent with the definition of alkyl described above. Examples of alkoxy include, but are not limited to, methoxy, ethoxy, propoxy, n-butoxy, n-pentoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, n-undecyloxy, n-dodecyloxy, 2-ethylhexyloxy, 2-ethyloctyloxy, 2-butylhexyloxy, 2-hexyloctyloxy, 4-hexyldecyloxy, 3-hexylundecyloxy, 2-octyldecyloxy, 2-octyldodecyloxy, 3-octyltridecyloxy, 2-decyldodecyloxy, 2-decyltetradecyloxy, 3-decylpentadecyloxy, 2-dodecylhexadecyloxy, 4-octyltetradecyloxy, 4-decylhexadecyloxy, 4-hexyldecyloxy, 4-octyldodecyloxy, 4-decyltetradecyloxy, 4-dodecylhexadecyloxy, and the like;

[0024] The term "alkylthio" herein refers to -S-alkyl, wherein the definition of alkyl is the same as that of alkyl above. Examples of alkylthio groups include, but are not limited to, methylthio, ethylthio, propylthio, n-butylthio, n-pentylthio, n-hexylthio, n-heptylthio, n-octylthio, n-nonylthio, n-decylthio, n-undecylthio, n-dodecylthio, 2-ethylhexylthio, 2-ethyloctylthio, 2-butylhexylthio, 2-hexyloctylthio, 4-hexyldecylthio, 3-hexylundecylthio, 2-octyldecylthio, 2-octyldodecylthio, 3-octyltridecylthio, 2-decyldodecylthio, 2-decyltetradecylthio, 3-decylpentadecylthio, 2-dodecylhexadecylthio, 4-octyltetradecylthio, 4-decylhexadecylthio, 4-hexyldecylthio, 4-octyldodecylthio, 4-decyltetradecylthio, 4-dodecylhexadecylthio, and the like;

[0025] The term "silyl" in the present invention refers to -Si-alkyl, wherein the definition of alkyl conforms to the definition of alkyl described above. Examples of silyl include, but are not limited to, methylsilane, ethylsilane, propylsilane, n-butylsilane, n-pentylsilane, n-hexylsilane, n-heptylsilane, n-octylsilane, n-nonylsilane, n-decylsilane, n-undecylsilane, n-dodecylsilane, trimethylhexylsilane, trimethylheptylsilane, trimethyloctylsilane, trimethylnonylsilane, trimethyldecylsilane, trimethylhexylsilane, hexylmethylbis(trimethylsiloxy)silane, heptylmethylbis(trimethylsiloxy)silane, octylmethylbis(trimethylsiloxy)silane, nonylmethylbis(trimethylsiloxy)silane, decylmethylbis(trimethylsiloxy)silane, undecylmethylbis(trimethylsiloxy)silane, and dodecylmethylbis(trimethylsiloxy)silane.

[0026] The second aspect of the present invention provides a deuterated quinone-type end group as shown in the following figure,

[0027] Wherein, each Z is independently selected from R1-C-R1, S, O, Se, N-R1 or R1-Si-R1; each R2 is independently selected from hydrogen, fluorine, chlorine, bromine, trifluoromethyl, substituted or unsubstituted alkyl, substituted or unsubstituted aromatic, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylthio, substituted or unsubstituted silanyl or substituted or unsubstituted ester.

[0028] The third aspect of the present invention provides a method for preparing a deuterated quinone-type end group, comprising the following steps:

[0029] 1) N-bromosuccinimide is dissolved in a mixed solution of acetic acid and water, and an acetic acid solution of any one of the compounds shown in the formula is added dropwise at a temperature of 25 to 100° C., followed by reaction at 25 to 100° C. for 0.5 to 5 hours. After the reaction is completed, the mixture is cooled to room temperature, and an aqueous solution of sodium bisulfite is added to the reaction mixture, followed by extraction, concentration under reduced pressure, and purification by silica gel column chromatography using petroleum ether and dichloromethane as eluents to obtain the corresponding product shown in the following formula in a yield of 30% to 80%.

[0030] 2) Any one of the compounds shown in the above formula is dissolved in a 1,2-dichloroethane solution, malononitrile is added, a catalyst is added, and the reaction is carried out at 0-100° C. After the reaction is completed, the temperature is returned to room temperature, deionized water is added to the reactant, extracted, concentrated under reduced pressure, and purified by silica gel column chromatography using petroleum ether and dichloromethane as eluents to obtain the deuterated quinone-type end group corresponding to the following formula with a yield of 20% to 70%.

[0031] The fourth aspect of the present invention provides a method for preparing a short-wave infrared region deuterated quinone-terminated N-type organic molecule represented by structural formula (I), comprising the following steps:

[0032] In the presence of a palladium catalyst, the compound represented by structural formula (II) and the deuterated quinone-type end group of claim 3 are subjected to a Stille coupling reaction in an organic solvent to obtain an N-type organic molecule capped with a deuterated quinone-type end group represented by structural formula (I);

[0033] wherein n is independently selected from 0 or a positive integer; each E is independently selected from a substituted or unsubstituted aromatic group or cycloalkyl group, or is absent; each K is independently selected from a substituted or unsubstituted aromatic group or cycloalkyl group, or is absent; each R1 is independently selected from one or more of a hydrogen atom, an ester group, a hydroxyl group, a nitro group, a halogen, a cyano group, an alkyl group, an alkyl derivative, an alkoxy group, an alkoxy derivative, an alkylthio group, an alkylthio derivative, an alkylene group, an alkylene derivative, an aralkyl group, and an aralkyl derivative; and one or more carbon atoms on the alkyl derivative, alkoxy derivative, alkylthio derivative, alkylene derivative, or aralkyl derivative are independently substituted with one or more of an oxygen atom, an amino group, a sulfone group, a carbonyl group, an aryl group, an alkene group, an alkynyl group, an ester group, a cyano group, and a nitro group;

[0034] and / or

[0035] One or more hydrogen atoms on the alkyl derivative, alkylthio derivative, alkoxy derivative, alkylene derivative or aralkyl derivative are independently replaced by one or more of halogen, hydroxyl, amino, carboxyl, cyano, nitro, aryl, alkene or alkyne groups; each X and X' is independently selected from R1-C-R1, S, O, Se, N-R1 or R1-Si-R1; each Y is independently selected from R1-C-R1, S, O, Se, N-R1 or R1-Si-R1.

[0036] In the above preparation method, the molar ratio of the compound represented by structural formula (II) to the deuterated quinone end group is 1:2 to 20;

[0037] The palladium catalyst is tetrakistriphenylphosphine palladium, bis(dibenzylideneacetone) palladium, 1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride; the molar ratio of the palladium catalyst to the compound represented by formula (II) is 0.015 to 0.15:1;

[0038] The organic solvent is toluene, tetrahydrofuran or chlorobenzene, and the volume ratio of the compound represented by structural formula (II) to the organic solvent is 1 mmol: 25-250 ml; the reaction temperature is 25-150° C.; and the reaction time is 30 min-12 h.

[0039] The volume ratio of the eluent petroleum ether and dichloromethane is petroleum ether:dichloromethane=1-5:1.

[0040] Specifically, the present invention uses a quinoid end group substituted with a deuterium atom to replace a quinoid end group substituted with a non-deuterium atom for capping to obtain an N-type organic molecule with short-wave infrared response. The substitution of deuterium atoms further lowers the energy level of the obtained N-type organic molecule, makes the molecular stacking method more reasonable, improves the carrier transport capacity, and further red-shifts the film absorption, which is conducive to the construction of a non-fullerene small molecule receptor with a wider spectral response.

[0041] In addition, by modifying the deuterium-substituted quinone end groups with different substituents and substituent atoms, the solubility, energy level distribution, absorption range and stacking mode of the molecules can be further affected, thereby achieving different photoelectric properties.

[0042] The short-wave infrared responsive N-type organic molecule terminated with a deuterated quinone-type end group described in the invention can be used as a part of the copolymerization unit in the polymer structure and applied to the polymer receptor, so that the polymer receptor contains the molecular structure of the short-wave infrared responsive N-type organic molecule terminated with a deuterated quinone-type end group.

[0043] Another object of the present invention is to provide the use of the above-mentioned deuterated quinone-terminated short-wave infrared responsive N-type organic molecule in an organic optoelectronic device.

[0044] Compared with the prior art, the present invention has the following beneficial effects:

[0045] 1. The end group of the present invention is a quinone-type end group substituted with a deuterium atom. Compared with the quinone-type end group without a deuterium atom, after being connected to a nucleus with electron donating ability, a significant DA structure is formed. The obtained N-type conjugated material can promote the prepared photodetector to have a higher specific detectivity in the short-wave infrared region while ensuring good solubility, an extremely narrow band gap, and a suitable energy level. It can greatly broaden the detection range of the photodetector for short-wave infrared light and greatly enhance the detection capability of the photodetector for short-wave infrared light. The bulk heterojunction of the prepared photodetector has a more balanced carrier mobility, effectively prolongs the life of the photodetector, and improves the responsivity and detection capability in the short-wave infrared region.

[0046] 2. By modifying the deuterated quinone end groups with different substituents and substituted atoms, the molecular solubility, energy level distribution, absorption range, and stacking pattern of short-wave infrared-responsive N-type organic molecules with deuterated quinone end groups can be further optimized. Precise control of the deuterated quinone end groups can further alter the absorption spectrum and achieve different optoelectronic properties.

[0047] 3. The deuterated quinone-terminated N-type organic molecules of the present invention are applied to optoelectronic devices, especially organic short-wave infrared detectors, and have excellent specific detectivity, reaching the optimal level of short-wave infrared organic light detection wavelength reported so far based on non-fullerene small molecule receptors.

[0048] Contents of attached figure

[0049] FIG1 shows the chemical structural formula of the polymer donor PTB7-Th;

[0050] FIG2 shows a schematic structural diagram of the prepared OPDs device;

[0051] FIG3 shows the UV-visible absorption spectra of Examples D1-D4 and Comparative Examples H1-H4;

[0052] FIG4 shows device EQE diagrams of Examples D1, D4, and Comparative Examples H1, H4;

[0053] FIG5 shows dark current diagrams of devices of Examples D1 and D4 and Comparative Examples H1 and H4;

[0054] FIG6 shows device responsivity diagrams of Examples D1, D4, and Comparative Examples H1, H4;

[0055] FIG7 shows a graph of device specific detectivity of Examples D1, D4, and Comparative Examples H1, H4;

[0056] FIG8 shows a graph of device temporal stability of Examples D1 and D4 and Comparative Examples H1 and H4. DETAILED DESCRIPTION

[0057] To more clearly illustrate the technical solutions of the present invention, the following examples are provided. Unless otherwise specified, the raw materials and reagents mentioned in the examples are commercially available. The reactions and post-processing methods used are, unless otherwise specified, well-known to those skilled in the art. The following examples illustrate the preparation of short-wavelength infrared-responsive N-type organic molecules terminated with deuterated quinone-type end groups according to the present invention.

[0058] Example 1

[0059] This example is used to illustrate the preparation method of the compound of formula 2 below.

[0060] Among them, the intermediate core X is selected from a sulfur atom, Y is selected from a nitrogen atom, and E is selected from n is selected from a positive integer 0, and R1 is independently selected from 2-butyloctyl.

[0061] As shown in the above reaction formula, under an inert gas atmosphere, the compound shown in Formula 1 (108.3 mg, 0.1 mmol) and tetrahydrofuran (15 mL) were added to a reaction vessel, and at a temperature of -78 ° C, lithium diisopropylamide (0.99 mL, 0.8 mmol, 0.8 M) was slowly added dropwise, and stirred at -78 ° C for 1.5 h. Trimethyltin chloride (0.5 mL, 0.5 mmol, 1 M) was added, and then the reaction solution was slowly returned to room temperature and stirred overnight. A saturated aqueous solution of potassium fluoride (5 mL) was then added to quench the mixture, washed with saturated brine, extracted with dichloromethane, dried over anhydrous sodium sulfate, and distilled under reduced pressure to remove the solvent. The concentrated product was dissolved in a small amount of dichloromethane and added dropwise to 80 mL of methanol. It was filtered to obtain an orange-red solid (126 mg, 90% yield), which is the compound shown in Formula 2. Compound 2 was directly processed into the next step.

[0062] Example 2

[0063] This example is used to illustrate the preparation method of the compound of formula 5 below.

[0064] Among them, the intermediate core X is selected from a sulfur atom, Y is selected from a nitrogen atom, and E is selected from n is selected from a positive integer 1, X' is selected from a sulfur atom, and R1 is independently selected from 2-ethylhexyl or 2-butyloctyl.

[0065] As shown in the above reaction formula, under an inert gas atmosphere, the compound represented by Formula 2 (1.41 g, 1 mmol), the compound represented by Formula 3 (875 mg, 3 mmol), 1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium (14.5 mg, 0.02 mmol) and tetrahydrofuran (150 mL) were added to a reaction vessel, the temperature was raised to 80°C, and the reaction was refluxed for 18 hours. Subsequently, after cooling to room temperature, water (100 ml) was added, the mixture was washed with saturated brine, extracted with dichloromethane, dried over anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure. The concentrated product was separated by column chromatography using a silica gel column (200-300 mesh silica gel, eluent: pure petroleum ether) to obtain an orange-yellow liquid (649 mg, yield: 43%), which is the compound represented by Formula 4. 1H NMR(400MHz,Chloroform-d)δ7.18(d,J=5.3Hz,2H),6.74(d,J=5.4Hz,2H),4.65(d,J=8.0Hz,4H),3.99-3.87(d,4H),3.08(t,J=8.1Hz ,4H),2.17–2.07(m,2H),2.03–1.91(m,4H),1.77–1.64(m,2H),1.56–0.85(m,84H),0.79–0.60(m,26H).MS(MALDI-TOF): m / z=1504.34.

[0066] As shown in the above reaction formula, under an inert gas atmosphere, the compound shown in Formula 4 (300 mg, 0.2 mmol) and tetrahydrofuran (20 mL) were added to a reaction vessel, and at a temperature of -78 ° C, lithium diisopropylamide (0.6 mL, 0.6 mmol, 1 M) was slowly added dropwise, and stirred at -78 ° C for 1.5 h. Trimethyltin chloride (0.6 mL, 0.6 mmol, 1 M) was added, and then the reaction solution was slowly returned to room temperature and stirred overnight. A saturated aqueous solution of potassium fluoride (12 mL) was then added to quench the mixture, washed with saturated brine, extracted with dichloromethane, dried over anhydrous sodium sulfate, and distilled under reduced pressure to remove the solvent. The concentrated product was dissolved in a small amount of dichloromethane and added dropwise to 100 mL of methanol. It was filtered to obtain an orange-yellow liquid (304 mg, 83% yield), which is the compound shown in Formula 5. Compound 5 was directly processed to the next step.

[0067] Example 3

[0068] This example is to illustrate the preparation method of the following formula 7.

[0069] As shown in the above reaction formula, under an inert gas atmosphere, liquid bromine (2.10 g, 13.1 mmol) was dissolved in a mixed solution of acetic acid (25 ml) and water (50 ml). At 60° C., the compound represented by Formula 6 (1.20 g, 6.6 mg) was dissolved in acetic acid (25 ml) and then added dropwise to the reaction system. The mixture was stirred at 60° C. for three hours, and then returned to room temperature. Deionized water (50 ml) was added, and the mixture was washed with a saturated aqueous sodium bisulfite solution, extracted with dichloromethane, dried over anhydrous sodium sulfate, and distilled under reduced pressure to remove the solvent. The concentrated product was separated by column chromatography using a silica gel column (200-300 mesh silica gel, eluent: petroleum ether: dichloromethane (volume ratio) = 3:1) to obtain a yellow solid (874 mg, yield 48%), which is the compound represented by Formula 7. 1H NMR (500MHz, Chloroform-d) δ7.54 (s, 1H). LC-MS: m / z=274.8.

[0070] Example 4

[0071] This example is to illustrate the preparation method of the following formula 8.

[0072] As shown in the above reaction formula, under an inert gas atmosphere, the compound represented by Formula 7 (1.20 g, 4.4 mmol), malononitrile (348 mg, 5.3 mmol), and 1.2-dichloroethane (20 mL) were added to a reaction vessel. Subsequently, titanium tetrachloride (5.3 mL, 5.3 mmol, 1 M) was slowly added and stirred at 0°C for 1 hour. Triethylamine (0.9 mL, 6.6 mmol) was slowly added and stirred at 0°C for 1 hour. Deionized water (30 mL) was added and stirred for 10 minutes. The mixture was washed with saturated brine, extracted with dichloromethane, dried over anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure. The concentrated product was separated by column chromatography using a silica gel column (200-300 mesh silica gel, eluent: petroleum ether: dichloromethane (volume ratio) = 2:1) to obtain a bright yellow solid (560 mg, yield 39%), which is the compound represented by Formula 8. 1H NMR (500MHz, Chloroform-d) δ8.35 (s, 1H). LC-MS: m / z=323.1.

[0073] Example 5

[0074] A deuterated quinone-terminated short-wave infrared responsive N-type organon D1, whose molecular structure is shown in the figure below:

[0075] The preparation method of the above-mentioned N-type organic molecule D1 is shown in the figure below:

[0076] As shown in the above reaction formula, under an inert gas atmosphere, the compound represented by Formula 2 obtained in Example 1 (141 mg, 0.1 mmol), the compound represented by Formula 8 obtained in Example 4 (64 mg, 0.2 mmol), 1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium (3.6 mg, 0.06 mmol) and tetrahydrofuran (50 mL) were added to a reaction vessel, heated to 80°C, and refluxed for 8 hours. Subsequently, after cooling to room temperature, water (30 ml) was added, washed with saturated brine, extracted with dichloromethane, dried over anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure. The concentrated product was separated by column chromatography using a silica gel column (200-300 mesh silica gel, eluent: petroleum ether: dichloromethane (volume ratio) = 1:1) to obtain a deuterated quinone-terminated short-wave infrared-responsive N-type organon D1 (78 mg, yield 50%). 1H NMR(400MHz,Chloroform-d)δ8.03(s,2H),4.66(d,J=8.1Hz,4H),3.10(t,J=8.2Hz,4H),2.15–2.06(m,2H),2 .05–1.93(m,4H),1.45–1.23(m,32H),1.14–0.82(m,36H),0.70–0.59(m,14H).MS(MALDI-TOF): m / z=1568.02.

[0077] Example 6

[0078] A short-wave infrared-responsive N-type organon D2 terminated with a deuterated quinone-type end group, the molecular structure of which is shown in the figure below:

[0079] The preparation method of the above-mentioned N-type organic molecule D2 is shown in the figure below:

[0080] As shown in the above reaction formula, under an inert gas atmosphere, the compound represented by Formula 5 obtained in Example 2 (183 mg, 0.1 mmol), the compound represented by Formula 8 obtained in Example 4 (65 mg, 0.2 mmol), 1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium (4.4 mg, 0.06 mmol) and tetrahydrofuran (50 mL) were added to a reaction vessel, heated to 80°C, and refluxed for 8 hours. Subsequently, after cooling to room temperature, water (30 ml) was added, washed with saturated brine, extracted with dichloromethane, dried over anhydrous sodium sulfate, and the solvent was removed by distillation under reduced pressure. The concentrated product was separated by column chromatography using a silica gel column (200-300 mesh silica gel, eluent: petroleum ether: dichloromethane (volume ratio) = 2:1) to obtain a deuterated quinone-terminated short-wave infrared-responsive N-type organon D2 (79 mg, yield 39%). 1H NMR(400MHz,Chloroform-d)δ8.04(s,2H),6.75(d,J=5.4Hz,2H),4.66(d,J=8.0Hz,4H),3.99-3.85(d,4H),3.08(t,J=8.1Hz,4H) ,2.17–2.07(m,2H),2.03–1.91(m,4H),1.77–1.64(m,2H),1.56–0.85(m,84H),0.79–0.60(m,26H).MS(MALDI-TOF): m / z=1988.47.

[0081] Other embodiments

[0082] The following lists a series of N-type organic molecules terminated with deuterated quinone groups, and their structures are shown in Table 1. The preparation methods are the same as those in the above examples, except that the relevant monomers are replaced. Therefore, the preparation methods are all known technologies and are not listed here one by one.

[0083] The total yield is calculated by taking the initial raw material as the basis, calculating it as 100%, and then synthesizing several intermediate products until the yield of the final product.

[0084] The total yield is the product of the yield of the intermediate product / final product in each step of the process, starting from the reaction of the initial raw materials.

[0085] Table 1 Molecular structure and total yield of monomers related to the examples

[0086] Comparative Example

[0087] Based on the preparation methods of the Examples, a set of comparative examples was prepared. The raw materials and preparation methods of the comparative examples were the same as those of the Examples, with the only difference being that the quinone-type end groups were not deuterated. The results are shown in Table 2.

[0088] Table 2 Comparative Examples Related Monomer Molecular Structure and Total Yield

[0089] Test Case

[0090] The photophysical and electrochemical performance tests were conducted on the above Examples D1-D4 and Comparative Examples H1-H4, and OPD devices were prepared and basic performance characterization was performed on the relevant materials. The tested performances include:

[0091] (1) Testing of material absorption spectrum; (2) Testing of material electrochemical energy level; (3) Testing of device dark current; (4) Testing of device EQE; (5) Calculation of device responsivity; (6) Calculation of device specific detectivity; (7) Testing of device carrier mobility; (8) Testing of device stability.

[0092] The above test methods are all well known to those skilled in the art.

[0093] Among them, the preparation of the OPDs device adopts an inverted device structure, namely ITO / zinc oxide / active layer / molybdenum trioxide / silver, wherein the active layer is obtained by blending the polymer donor PTB7-Th with the short-wave infrared responsive small molecule receptor of the above-mentioned comparative example or embodiment.

[0094] The specific preparation method is to use ITO-coated glass as a substrate and clean it by continuous ultrasonic treatment in isopropanol, detergent, deionized water and isopropanol. Then, the substrate was dried in an oven at 60°C for 5h. 0.4g of zinc acetate was dissolved in 4mL of 2-methoxyethanol and 110μL of ethanolamine and stirred at 50°C for 12h to prepare sol-gel zinc oxide (ZnO). A 30nm thick ZnO film was spin-coated onto the ITO-coated glass and thermally annealed on a hot plate at 150°C for 30min. The polymer donor PTB7-Th and the small molecule acceptor of the embodiment or comparative example that can respond to the near infrared were mixed in a certain weight ratio and dissolved in chlorobenzene containing 2% 1-chloronaphthalene. The active layer was then spin-coated on the ZnO layer and then thermally annealed at 80°C for 10 minutes in a nitrogen glove box. At 9×10 -7 A 10 nm MoO3 (molybdenum oxide) film and a 100 nm Ag (silver) layer were sequentially deposited by thermal evaporation under a vacuum of 100 nm. The device area was 0.0516 cm2 and was defined by a shadow mask with four devices per substrate.

[0095] The EQE and dark current of the above OPDs were measured at 0V bias and the corresponding responsivity R and detectivity D* were calculated. Responsivity R refers to the ratio of the photocurrent of the photodetector to the incident light intensity, with the unit of A / W. The calculation formula for R is as follows:

[0096] Among them, J ph EQE refers to the photogenerated current density of the detector, where q is the elementary charge, π is the wavelength of the incident light, P1 is the incident light power density, h is Planck's constant, and c is the speed of light. EQE is directly proportional to R, and both reflect the efficiency of converting photons into electrons.

[0097] Detection rate D* is an indicator that measures the detector's ability to detect the minimum incident light signal. The unit is Jones. Its calculation formula is as follows:

[0098] Where R is the responsivity, q is the charge, and J d is the dark current.

[0099] The test results are shown in Tables 3 and 4.

[0100] Please refer to Figures 3-8 for the relevant characterization images of small molecule receptors related to the above Examples D1-D4 and Comparative Examples H1-H4.

[0101] Table 3. Absorption, energy levels of Examples D1-D4 and Comparative Examples H1-H4

[0102] Table 4. Dark current, EQE, responsivity, specific detectivity, and ratio of electron to hole mobility at 1200 nm for OPDs with PTB7-Th as the active layer in Examples D1, D4 and Comparative Examples H1, H4 Note: 1) μ e / μ h It refers to the ratio of electron and hole mobility in OPDs prepared with this material;

[0103] The present invention discloses a deuterated quinone-terminated N-type organic molecule with an infrared response reaching the short-wave infrared region, which has the following structural formula (I):

[0104] The present invention also includes a preparation method, performance testing, and application of the material in a photodetector. Photodetectors fabricated based on this short-wave infrared-responsive deuterated quinone-terminated N-type organic molecular material exhibit extremely high responsivity in the short-wave infrared region, significantly enhancing the photodetector's ability to detect weak infrared light. Furthermore, photodetectors fabricated using deuterium-substituted quinone-terminated N-type organic molecular material exhibit more balanced carrier mobility, effectively extending the photodetector's lifespan and improving both the device's responsivity and detection capability in the short-wave infrared region.

Claims

1. A deuterated quinone-terminated N-type organic molecule with an infrared response reaching the short-wave infrared region, characterized in that: The short-wave infrared responsive deuterated quinone-terminated N-type organic molecule has the following structural formula (I): wherein each n is independently selected from 0, 1, 2, 3 to 10; each E is independently selected from substituted or unsubstituted aromatic or cycloalkyl, or is absent; each K is independently selected from substituted or unsubstituted aromatic or cycloalkyl, or is absent; Each R1 is independently selected from one or more of a hydrogen atom, an ester group, a hydroxyl group, a nitro group, a halogen group, a cyano group, an alkyl group, an alkyl derivative, an alkoxy group, an alkoxy derivative, an alkylthio group, an alkylthio derivative, an alkylene group, an alkylene derivative, an aralkyl group, and an aralkyl derivative; One or more carbon atoms on the alkyl derivative, alkoxy derivative, alkylthio derivative, alkylene derivative or aralkyl derivative are independently substituted by one or more oxygen atoms, amino groups, sulfone groups, carbonyl groups, aryl groups, alkene groups, alkyne groups, ester groups, cyano groups or nitro groups; and / or One or more hydrogen groups on the alkyl derivative, alkylthio derivative, alkoxy derivative, alkylene derivative or aralkyl derivative are independently substituted by one or more of halogen, hydroxyl, amino, carboxyl, cyano, nitro, aryl, alkene or alkyne groups; Each X, X' is independently selected from R3-C-R3, S, O, Se, N-R3 or R3-Si-R3; Each Y is independently selected from R4-C-R4, S, O, Se, N-R4 or R4-Si-R4; Each group Ar is independently selected from one of the groups shown in the following formula: wherein Z is independently selected from R5-C-R5, S, O, Se, N-R5 or R5-Si-R5; R2 is independently selected from hydrogen, fluorine, chlorine, bromine, cyano, trifluoromethyl, substituted or unsubstituted alkyl, substituted or unsubstituted aromatic, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylthio, substituted or unsubstituted silyl or substituted or unsubstituted ester; R3 are each independently selected from one or more of alkyl, alkyl derivatives, aralkyl, aralkyl derivatives, alkoxy, alkoxy derivatives, alkylthio, alkylthio derivatives, alkylene, and alkylene derivatives; R4 is independently selected from one or more of alkyl, alkyl derivatives, aralkyl, aralkyl derivatives, alkoxy, alkoxy derivatives, alkylthio, alkylthio derivatives, alkylene, and alkylene derivatives; R5 is independently selected from one or more of alkyl, alkyl derivatives, aralkyl, aralkyl derivatives, alkoxy, alkoxy derivatives, alkylthio, alkylthio derivatives, alkylene, and alkylene derivatives; One or more hydrogen groups on the alkyl derivative, alkylthio derivative, alkoxy derivative, alkylene derivative or aralkyl derivative are independently substituted by one or more of halogen, hydroxyl, amino, carboxyl, cyano, nitro, aryl, alkene or alkyne groups; Any one or more hydrogen atoms in the structural formula (I) are not replaced by other atoms and / or groups, or are independently replaced by protium, deuterium or tritium atoms; the aromatic group includes a single aromatic group or a polyvalent aromatic group; the wavelength of the short-wave infrared is 1000nm to 3000nm.

2. The deuterated quinone-terminated N-type organic molecule having an infrared response reaching the short-wave infrared region according to claim 1, characterized in that: The R1 is independently selected from a hydrogen atom, a substituted or unsubstituted C1-C30 straight chain or branched alkyl group, a substituted or unsubstituted C1-C30 straight chain or branched alkoxy group, a substituted or unsubstituted C1-C30 straight chain or branched alkylthio group, and a substituted or unsubstituted C1-C30 straight chain or branched silyl group.

3. The deuterated quinone-terminated N-type organic molecule having an infrared response reaching the short-wave infrared region according to claim 1, characterized in that: The deuterated quinone end groups are each independently selected from one of the following groups: wherein each Z is independently selected from R5-C-R5, S, O, Se, N-R5 or R1-Si-R5; and each R6 is independently selected from hydrogen, fluorine, chlorine, bromine, cyano, trifluoromethyl, substituted or unsubstituted alkyl, substituted or unsubstituted aromatic, substituted or unsubstituted alkoxy, substituted or unsubstituted alkylthio, substituted or unsubstituted silanyl or substituted or unsubstituted ester.

4. The deuterated quinone-terminated N-type organic molecule having an infrared response reaching the short-wave infrared region according to claim 1, characterized in that: The K is selected from one or more of the following structures: wherein R7 and R8 each independently represent a hydrogen atom, an ester group, a hydroxyl group, a nitro group, a halogen group, a cyano group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted silyl group, or a substituted or unsubstituted ester group; X is R9-C-R9, S, O, Se, N-R9, or R9-Si-R9; Y is R 10 -CR 10 、S、O、Se、NR 10 or R 10 -Si-R 10 ; R9 are each independently selected from one or more of alkyl, alkyl derivatives, aralkyl, aralkyl derivatives, alkoxy, alkoxy derivatives, alkylthio, alkylthio derivatives, alkylene, and alkylene derivatives; R 10 Each is independently selected from one or more of alkyl, alkyl derivatives, aralkyl, aralkyl derivatives, alkoxy, alkoxy derivatives, alkylthio, alkylthio derivatives, alkylene, and alkylene derivatives; any one or more hydrogen atoms in the K structure are not replaced by other atoms and / or groups, or are independently replaced by protium, deuterium or tritium atoms.

5. The deuterated quinone-terminated N-type organic molecule having an infrared response reaching the short-wave infrared region according to claim 3, characterized in that: The preparation method of the deuterated quinone-type end group comprises the following steps: 1) N-bromosuccinimide is dissolved in a mixed solution of acetic acid and water, and an acetic acid solution of any one of the compounds shown in the formula is added dropwise at a temperature of 25 to 100° C., followed by reaction at 25 to 100° C. for 0.5 to 5 hours. After the reaction is completed, the mixture is cooled to room temperature, and an aqueous solution of sodium bisulfite is added to the reaction mixture, followed by extraction, concentration under reduced pressure, and purification by silica gel column chromatography using petroleum ether and dichloromethane as eluents to obtain the corresponding product shown in the following formula in a yield of 30% to 80%; 2) dissolving any one of the compounds represented by the above formula in 1,2-dichloroethane solution, adding malononitrile, adding a catalyst, and reacting at 0-100° C. After the reaction is completed, cooling to room temperature, adding deionized water to the reactant, extracting, concentrating under reduced pressure, and purifying by silica gel column chromatography with petroleum ether and dichloromethane as eluents to obtain the deuterated quinone-type end group corresponding to the following formula, with a yield of 20% to 70%; 6. The deuterated quinone-terminated N-type organic molecule having an infrared response reaching the short-wave infrared region according to claim 5, characterized in that: In the deuterated quinone end group synthesis step 1), the volume ratio of acetic acid to water in the acetic acid and water mixed solution is 1:1-4; the volume ratio of the amount of the deuterated reactant to the mixed solvent is 1 mmol:20-50 ml; and the volume ratio of the eluent petroleum ether to dichloromethane is 1-10:

1.

7. The deuterated quinone-terminated N-type organic molecule having an infrared response reaching the short-wave infrared region according to claim 5, characterized in that: In the step 2) of synthesizing the deuterated quinone end group, the molar ratio of the malononitrile to the catalyst is 1:1-20:1-20; the catalyst is titanium tetrachloride and triethylamine; the molar ratio of the catalyst titanium tetrachloride to triethylamine is 1:1-10; the volume ratio of the amount of the deuterated reactant to the mixed solvent is 1 mmol:10-50 ml; and the volume ratio of the eluent petroleum ether to dichloromethane is 1-10:

1.

8. The method for preparing a deuterated quinone-terminated N-type organic molecule in the short-wave infrared region according to any one of claims 1 to 7, characterized in that: The following steps are involved: In the presence of a palladium catalyst and an inert atmosphere, the compound represented by structural formula (II) and the deuterated quinone-type end group according to claim 3 are subjected to a Stille coupling reaction in an organic solvent. After the reaction is completed, the temperature is returned to room temperature, concentrated under reduced pressure, and purified by silica gel chromatography using petroleum ether and dichloromethane as eluents to obtain an N-type organic molecule capped with a deuterated quinone-type end group represented by structural formula (I); wherein n is independently selected from 0, 1, 2, 3 to 10; each E is independently selected from substituted or unsubstituted aromatic or cycloalkyl, or is absent; Each K is independently selected from a substituted or unsubstituted aromatic group or a cycloalkyl group, or is absent; Each R1 is independently selected from one or more of a hydrogen atom, an ester group, a hydroxyl group, a nitro group, a halogen group, a cyano group, an alkyl group, an alkyl derivative, an alkoxy group, an alkoxy derivative, an alkylthio group, an alkylthio derivative, an alkylene group, an alkylene derivative, an aralkyl group, and an aralkyl derivative; One or more carbon atoms on the alkyl derivative, alkoxy derivative, alkylthio derivative, alkylene derivative or aralkyl derivative are independently substituted by one or more oxygen atoms, amino groups, sulfone groups, carbonyl groups, aryl groups, alkene groups, alkyne groups, ester groups, cyano groups or nitro groups; and / or One or more hydrogen groups on the alkyl derivative, alkylthio derivative, alkoxy derivative, alkylene derivative or aralkyl derivative are independently substituted by one or more of halogen, hydroxyl, amino, carboxyl, cyano, nitro, aryl, alkene or alkyne groups; Each X, X' is independently selected from R3-C-R3, S, O, Se, N-R3 or R3-Si-R3; Each Y is independently selected from R4-C-R4, S, O, Se, N-R4 or R4-Si-R4; R3 are each independently selected from one or more of alkyl, alkyl derivatives, aralkyl, aralkyl derivatives, alkoxy, alkoxy derivatives, alkylthio, alkylthio derivatives, alkylene, and alkylene derivatives; R4 is independently selected from one or more of an alkyl group, an alkyl derivative, an aralkyl group, an aralkyl derivative, an alkoxy group, an alkoxy derivative, an alkylthio group, an alkylthio derivative, an alkylene group, and an alkylene derivative.

9. The method for preparing a deuterated quinone-terminated N-type organic molecule in the short-wave infrared region according to claim 8, characterized in that: The molar ratio of the compound represented by structural formula (II) to the deuterated quinone end group is 1:2 to 20; The palladium catalyst is tetrakistriphenylphosphine palladium, bis(dibenzylideneacetone) palladium, 1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride; the molar ratio of the palladium catalyst to the compound represented by formula (II) is 0.015 to 0.15:1; The organic solvent is toluene, tetrahydrofuran or chlorobenzene, and the volume ratio of the compound represented by structural formula (II) to the organic solvent is 1 mmol: 25-250 ml; The reaction temperature is 25 to 150° C. The reaction time is 30min-12h; The volume ratio of the eluent petroleum ether and dichloromethane is petroleum ether:dichloromethane=1-5:

1.

10. A polymer or oligomer material comprising the short-wave infrared responsive N-type organic molecule terminated with a deuterated quinone-type end group as claimed in any one of claims 1 to 7 as a copolymer unit.

11. Use of the short-wave infrared responsive N-type organic molecule terminated with a deuterated quinone-type end group according to any one of claims 1 to 7 in an organic photodetector device.

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