Application of organic compound in photostable field effect transistor, photostable field effect transistor and electronic device

Abstract

The invention relates to an application of an organic compound in a photostable field effect transistor, the photostable field effect transistor and an electronic device, the organic compound has a structure as shown in the following formula 1: in the formula 1, R1 and R2 are the same and are selected from alkyl with a carbon atom number of 5-18 or alkoxy with a carbon atom number of 5-18; x is selected from Pd or Cu. When the organic compound with the structure as shown in the formula 1 is used for preparing the photostable field effect transistor, the photostable field effect transistor has relatively high hole mobility and stability.

Description

Technical Field

[0001] This application relates to the application of an organic compound in a photostable field-effect transistor, a photostable field-effect transistor, and an electronic device. Background Technology

[0002] Extensive research has been conducted on the photoelectric properties of porphyrins and their derivatives in the prior art. However, their excessive sensitivity to light prevents their field-effect transistors from operating stably in light environments, which limits the practical application of this type of organic field-effect transistor and hinders its commercialization. Summary of the Invention

[0003] The purpose of this disclosure is to provide an application of organic compounds in photo-stable field-effect transistors, photo-stable field-effect transistors, and electronic devices. This disclosure uses organic compounds with specific structures to prepare photo-stable field-effect transistors, and the prepared transistors have both high hole mobility and stability.

[0004] To achieve the above objectives, a first aspect of this disclosure provides the application of an organic compound in a photo-stable field-effect transistor, said organic compound having the structure shown in Formula 1:

[0005]

[0006] In Formula 1, R1 and R2 are the same and are selected from alkyl groups with 5-18 carbon atoms or alkoxy groups with 5-18 carbon atoms; X is selected from Pd or Cu.

[0007] Optionally, R1 and R2 are the same and are selected from alkyl groups with 5 carbon atoms, alkyl groups with 12 carbon atoms, alkoxy groups with 5 carbon atoms, and alkoxy groups with 12 carbon atoms.

[0008] Optionally, R1 and R2 are the same and are selected from pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, pentoxy, hexoxy, heptoxy, octoxy, nonoxy, decoxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecanyloxy, or octadecyloxy.

[0009] Optionally, the organic compound is selected from the group consisting of:

[0010]

[0011]

[0012] A second aspect of this disclosure provides a photo-stable field-effect transistor containing an organic compound provided in the first aspect of this disclosure.

[0013] Optionally, the organic field-effect transistor includes a gate electrode, an insulating layer, a modification layer, a semiconductor layer, and source / drain electrodes, wherein the semiconductor layer contains the organic compound.

[0014] Optionally, the semiconductor layer is an organic single crystal layer, and the thickness of the semiconductor layer is 10-50 nm.

[0015] Optionally, the thickness of the gate electrode is 300-500 μm, and the material is nitrogen-doped silicon and / or phosphorus-doped silicon;

[0016] The thickness of the insulating layer is 200-400 nm, and the material is silicon dioxide and / or aluminum oxide;

[0017] The thickness of the modified layer is 5-20 nm, and the material is one or more of octadecyltrichlorosilane, perfluoro(1-butenyl vinyl ether) polymer and polymethyl methacrylate;

[0018] The source and drain electrodes have a thickness of 40-150 nm and are made of gold and / or silver.

[0019] A third aspect of this disclosure provides an electronic device comprising the photo-stable field-effect transistor provided in the second aspect of this disclosure.

[0020] Optionally, the electronic device includes a flexible organic light-emitting diode display and / or logic circuitry.

[0021] Through the above technical solution, this disclosure uses an organic compound with a specific structure to prepare a photo-stable field-effect transistor. The organic compound is tetrabenzoporphyrin as the parent nucleus, and metal ions Pd or Cu are introduced into the parent nucleus. At the same time, alkylphenyl groups or alkoxyphenyl groups are attached to the parent nucleus, which greatly reduces the photosensitivity while improving the hole mobility. This makes the prepared photo-stable field-effect transistor have both high hole mobility and stability.

[0022] Other features and advantages of this disclosure will be described in detail in the following detailed description section. Attached Figure Description

[0023] The accompanying drawings are provided to further illustrate the present disclosure and form part of the specification. They are used together with the following detailed description to explain the present disclosure, but do not constitute a limitation thereof. In the drawings:

[0024] Figure 1This is a schematic diagram of a specific embodiment of the photo-stable field-effect transistor disclosed herein.

[0025] Figure 2a and Figure 2b The solution and thin film absorption spectra of 5,10-pentanylphenyltetrabenzoporphyrin (BP), 5,10-pentanylphenyltetrabenzoporphyrin palladium (II) (PdBP), and 5,10-pentanylphenyltetrabenzoporphyrin copper (II) (CuBP) are shown.

[0026] Figure 3a X-ray diffraction pattern of polycrystalline 5,10-pentanylphenyltetrabenzoporphyrin palladium(II) (PdBP).

[0027] Figure 3b X-ray diffraction pattern of polycrystalline 5,10-pentanylphenyltetrabenzoporphyrin copper(II) (CuBP).

[0028] Figure 4a Optical microscope image of a photostability field-effect transistor based on 5,10-pentanylphenyltetrabenzoporphyrin palladium(II) (PdBP).

[0029] Figure 4b Optical microscope image of a photo-stable field-effect transistor based on 5,10-pentanylphenyltetrabenzoporphyrin copper(II) (CuBP).

[0030] Figure 5a and Figure 5b The transfer and output curves are for a photo-stable field-effect transistor based on 5,10-pentanylphenyltetrabenzoporphyrin palladium(II) (PdBP).

[0031] Figure 6a and Figure 6b Transfer and output curves of a photo-stable field-effect transistor based on 5,10-pentanylphenyltetrabenzoporphyrin copper(II) (CuBP).

[0032] Figure 7a , Figure 7b and Figure 7c The transfer curves of photo-stable field-effect transistors based on BP, PdBP, and CuBP under monochromatic light illumination of different wavelengths are shown.

[0033] Figure 8a , Figure 8b and Figure 8c The photostability field-effect transistors based on PdBP, PdBP, and CuBP were tested in darkness and at 106.6 mW / cm². 2 Output curve under halogen lamp illumination.

[0034] Figure 9a , Figure 9b and Figure 9cThe transfer curves of photostability field-effect transistors based on BP, PdBP, and CuBP under halogen lamp irradiation with different power densities are shown.

[0035] Figure 10 It is 193.2 mW / cm 2 The maximum photosensitivity (P0) of transistor devices based on the photosensitivity effects of BP, PdBP, and CuBP under halogen lamp illumination max ) and threshold voltage change (ΔV th ). Detailed Implementation

[0036] The specific embodiments of this disclosure will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are for illustration and explanation only and are not intended to limit this disclosure.

[0037] The first aspect of this disclosure provides the application of an organic compound in a photo-stable field-effect transistor, said organic compound having the structure shown in Formula 1:

[0038]

[0039] In Formula 1, R1 and R2 are the same and are selected from alkyl groups with 5-18 carbon atoms or alkoxy groups with 5-18 carbon atoms; X is selected from Pd or Cu.

[0040] The inventors of this disclosure have discovered that using an organic compound with the structure of Formula 1 to fabricate a photosensitive field-effect transistor can result in a transistor with both high hole mobility and stability. This is because the organic compound introduces metal ions Pd or Cu into the parent tetrabenzoporphyrin molecule. The metal ion complexation makes the organic molecules more compactly packed, significantly improving the hole mobility of the transistor when the organic compound is used as an organic semiconductor material, while greatly reducing photosensitivity and improving device stability.

[0041] In one specific embodiment of this disclosure, R1 and R2 are identical and selected from alkyl groups with 5 carbon atoms, alkyl groups with 12 carbon atoms, alkoxy groups with 5 carbon atoms, and alkoxy groups with 12 carbon atoms. The organic compound of this embodiment exhibits superior mobility and stability.

[0042] In one specific embodiment of this disclosure, R1 and R2 are the same and are selected from pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, heptadecanyl, octadecyl, pentoxy, hexoxy, heptoxy, octoxy, nonoxy, decoxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecanyloxy, or octadecyloxy.

[0043] In one specific embodiment of this disclosure, the organic compound is selected from the group consisting of:

[0044]

[0045]

[0046] This disclosure does not specifically limit the synthesis methods of organic compounds. Those skilled in the art can determine suitable synthesis methods by referring to the preparation methods provided in the Examples section. In one specific embodiment of this disclosure, a compound in which X in the structure of an organic compound is palladium can be prepared by a method including the following steps:

[0047] (1) Compound 1, Compound 3, trifluoroacetic acid, dichlorodicyanobenzoquinone (DDQ), and the first solvent were mixed and reacted at 20-25°C for 6-10 hours under an inert atmosphere, with monitoring performed by thin-layer chromatography. After the reaction was complete, the product was extracted from the reaction solution with dichloromethane (DCM), adsorbed onto silica gel, and the solvent was evaporated. The crude product was purified by column chromatography, and Compound 2 was collected. Compound 3 was selected from 4-pentylbenzaldehyde, 4-octylbenzaldehyde, 4-dodecylbenzaldehyde, 4-n-octoxybenzaldehyde, 4-n-pentoxybenzaldehyde, 4-n-dodecyloxybenzaldehyde, etc.

[0048]

[0049] (2) Compound 2 is heated to 190-210℃ and reacted for 1-3 hours, then equimolarly aromatized to a purple powder. The purple powder, a palladium-containing metal source, and a second solvent are mixed and reacted under an inert atmosphere at 100-120℃ for 2-5 hours, monitored by thin-layer chromatography. After the reaction is complete, the product is extracted from the reaction solution using DCM, adsorbed onto silica gel, and the solvent is evaporated. The crude product is purified by column chromatography, and the organic compound of this disclosure is obtained by separation and collection. Preferably, the target metal source is PdCl2 or PdSO4.

[0050] According to this disclosure, the inert atmosphere may contain gases such as nitrogen, argon, and helium to make the atmosphere inert.

[0051] According to this disclosure, in step (1), the first solvent is well known to those skilled in the art, such as anhydrous dichloromethane or anhydrous trichloromethane. In a specific embodiment of this disclosure, the molar ratio of compound 1, compound 3, trifluoroacetic acid, and dichlorodicyanobenzoquinone (DDQ) can be 1:(0.9-1.1):(0.1-0.8):(1.0-2.0), preferably 1:1:0.4:1.5.

[0052] According to this disclosure, in step (2), the second solvent is well known to those skilled in the art, such as benzonitrile. In one specific embodiment of this disclosure, the molar ratio of the purple powder to the palladium metal source is 1:(1-2), preferably 1:1.5.

[0053] In another specific embodiment of this disclosure, a compound in which X is copper in the structure of an organic compound can be prepared by a method comprising the following steps: Compound 2, a copper-containing metal source, and a third solvent are mixed and reacted at 20-25°C for 20-30 hours under an inert atmosphere, with monitoring using absorption spectroscopy. After the reaction is complete, the product is extracted from the reaction solution using DCM, and the silica gel is adsorbed and the solvent is evaporated. The crude product is purified by column chromatography, and the solid product is separated and collected. The obtained solid product is heated to 200-220°C and reacted for 1-3 hours, followed by equimolar aromatization to convert it into a purple powder, thus obtaining the organic compound of this disclosure. Preferably, the copper-containing metal source is Cu(CH3COO)2·H2O or CuSO4.

[0054] According to this disclosure, in step (3), the third solvent is well known to those skilled in the art, such as anhydrous dichloromethane, methanol, etc. In one specific embodiment of this disclosure, the molar ratio of compound 2 to the amount of copper-containing metal source is 1:(4-6), preferably 1:(4-5).

[0055] A second aspect of this disclosure provides a photo-stable field-effect transistor containing an organic compound provided in the first aspect of this disclosure.

[0056] Compared with ordinary field-effect transistors, the photo-stable field-effect transistor disclosed herein can operate stably under strong light, wherein the light source can be an instrument such as a monochromator or a halogen lamp.

[0057] In one specific embodiment of this disclosure, the organic field-effect transistor includes a gate electrode, an insulating layer, a modifying layer, a semiconductor layer, and source / drain electrodes, wherein the semiconductor layer contains the organic compound. In this disclosure, source / drain electrodes refer to the source and drain electrodes.

[0058] In one specific embodiment of this disclosure, the semiconductor layer is an organic single crystal layer, and the thickness of the semiconductor layer is 10-50 nm.

[0059] According to this disclosure, the structure of the photo-stable field-effect transistor is well known to those skilled in the art, and the materials of the gate electrode, insulating layer, insulating modification layer, and source / drain electrodes are also well known to those skilled in the art, and their thicknesses can vary within a wide range. In one specific embodiment of this disclosure, the thickness of the gate electrode is 300-500 μm, and the material is nitrogen-doped silicon and / or phosphorus-doped silicon; the thickness of the insulating layer is 200-400 nm, and the material is silicon dioxide and / or aluminum oxide; the thickness of the modification layer is 5-20 nm, and the material is one or more of octadecyltrichlorosilane (OTS), perfluoro(1-butenyl vinyl ether) polymer, and polymethyl methacrylate; the thickness of the source / drain electrodes is 40-150 nm, and the material is gold and / or silver.

[0060] A third aspect of this disclosure provides an electronic device, the electronic device including the phototransistor provided in the second aspect of this disclosure.

[0061] According to this disclosure, the electronic device can be a device employing a photosensitive field-effect transistor that is well known to those skilled in the art. In one specific embodiment, the electronic device includes one or more of a light-emitting device, a driving circuit element device, and an integrated circuit device, such as, but not limited to, flexible organic light-emitting diode (OLED) displays, logic circuits, etc.

[0062] The present disclosure is further illustrated by the following examples, but the disclosure is not limited thereto. Unless otherwise specified, all reagents used in the following examples and comparative examples were commercially available.

[0063] Examples 1-4 are examples of the preparation of organic compounds.

[0064] Example 1

[0065] (1) 1.34 g (3 mmol, 1 eq) of dipyrrolemethane and 2.0 g (12 mmol, 4 eq) of KOH were placed in a 150 mL reaction tube equipped with a magnetic stir bar, purged with nitrogen three times, and dissolved in 35 mL of ethylene glycol. The reaction tube was wrapped with aluminum foil, heated to 175 °C, and reacted in the dark for 1 hour, monitored by TLC. After the reaction was complete, the product was extracted from the reaction solution by DCM. The organic phase was extracted with saturated Na2CO3 solution to remove excess acid and alkali, dried, adsorbed onto silica gel, and the solvent was evaporated. The crude product was rapidly purified by column chromatography (8 cm short column, silica, 1:1 dichloromethane / petroleum ether), separated and collected, and a brown powder was obtained. After NMR confirmation, it was found to be the desired target product, deesterified dipyrrolemethane (0.78 g, yield 86%).

[0066] (2) 0.760 g (2.5 mmol, 1 eq) of deesterified dipyrrolemethane was placed in a 250 mL reaction tube equipped with a magnetic stir bar, purged with nitrogen three times, and dissolved in 90 mL of anhydrous dichloromethane. Under a nitrogen atmosphere, 0.44 g (2.5 mmol, 1 eq) of 4-pentylbenzaldehyde was added dropwise to the solution. After stirring at room temperature for 5 min, 0.026 mL (0.35 mmol, 0.14 eq) of trifluoroacetic acid (TFA) was added. The reaction tube was wrapped with aluminum foil and reacted at room temperature in the dark for 6 hours. Then, 30 mL (0.850 g, 3.75 mmol, 1.5 eq) of a toluene solution of 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) was added to the reaction solution, and the reaction was continued at room temperature in the dark for 2 hours, monitored by TLC. After the reaction, the product was extracted from the reaction solution using DCM. The organic phase was treated with saturated Na₂CO₃ solution to remove excess acid and alkali, followed by extraction, drying, silica gel adsorption, and solvent drying. The crude product was purified by column chromatography (silica, 1:2 dichloromethane / petroleum ether), and the main product was a red powder. This powder was further purified by recrystallization with CH₂Cl₂ / MeOH (10:1) to obtain dark red crystals. NMR confirmed that this was the desired product, 0.435 g of the 5,10-pentanylphenyltetrabenzoporphyrin precursor. Under vacuum, 0.435 g (0.475 mmol, 1 eq) of the 5,10-pentanylphenyltetrabenzoporphyrin precursor was heated to 200 °C for 2 hours to obtain 0.420 g (0.475 mmol, 1 eq) of 5,10-pentanylphenyltetrabenzoporphyrin. The product was placed in a 500 mL reaction tube equipped with a magnetic stirrer, purged with nitrogen three times, and 140 mL of benzonitrile was added as the reaction solvent. The mixture was heated to 100 °C and stirred to dissolve. After increasing the nitrogen flow, 1.277 g (0.712 mmol, 1.5 eq) of palladium dichloride was quickly added. The system was sealed, and the reaction was carried out at 100 °C for 3 hours under a nitrogen atmosphere. The reaction was monitored by absorption spectroscopy (the polarity of the product and the starting material was very similar, but their absorption spectra showed significant differences). After the reaction was completed, the product was extracted using DCM. The organic phase was first treated with saturated Na₂CO₃ solution to remove excess acid and alkali, then extracted, dried, and adsorbed onto silica gel. The solvent was then evaporated. The crude product was purified by column chromatography (silica, 1:2 dichloromethane / petroleum ether), separated and collected, then dissolved in dichloromethane to form a saturated solution. This solution was added dropwise to 200 mL of methanol, and the product was further purified by precipitation. The purple powder was collected by filtration. After NMR confirmation, 5,10-pentanylphenyltetrabenzoporphyrin palladium(II) of formula I was obtained (0.354 g, yield 82.1%).

[0067]

[0068] Structural characterization data of the compound represented by Formula I:

[0069] 1H NMR(400MHz,Chloroform-d)δ10.05(s,2H),8.96(s,8H),7.60-8.08(m,16H),7.5 9(d,4H),7.51(d,4H),3.12(t,4H),2.06(m,4H),1.47-1.73(m,8H),1.04(t,6H);

[0070] MALDI-TOF(m / z)calcd for C 58 H 48 N4Pd907.47,found 906.92[M+H + ].

[0071] As can be seen from the above, the product has the correct structure, which is 5,10-pentanylphenyltetrabenzoporphyrin palladium(II).

[0072] Example 2

[0073] (1) 1.34 g (3 mmol, 1 eq) of dipyrrolemethane and 2.0 g (12 mmol, 4 eq) of KOH were placed in a 150 mL reaction tube equipped with a magnetic stir bar, purged with nitrogen three times, and dissolved in 35 mL of ethylene glycol. The reaction tube was wrapped with aluminum foil, heated to 175 °C, and reacted in the dark for 1 hour, monitored by TLC. After the reaction was complete, the product was extracted from the reaction solution by DCM. The organic phase was extracted with saturated Na2CO3 solution to remove excess acid and alkali, dried, adsorbed onto silica gel, and the solvent was evaporated. The crude product was rapidly purified by column chromatography (8 cm short column, silica, 1:1 dichloromethane / petroleum ether), separated and collected, and a brown powder was obtained. After NMR confirmation, it was found to be the desired target product, deesterified dipyrrolemethane (0.78 g, yield 86%).

[0074] (2) 0.760 g (2.5 mmol, 1 eq) of deesterified dipyrrolemethane was placed in a 250 mL reaction tube equipped with a magnetic stir bar, purged with nitrogen three times, and dissolved in 90 mL of anhydrous dichloromethane. Under a nitrogen atmosphere, 0.44 g (2.5 mmol, 1 eq) of 4-pentylbenzaldehyde was added dropwise to the solution. After stirring at room temperature for 5 min, 0.026 mL (0.35 mmol, 0.14 eq) of trifluoroacetic acid (TFA) was added. The reaction tube was wrapped with aluminum foil and reacted at room temperature in the dark for 6 hours. Then, 30 mL (0.850 g, 3.75 mmol, 1.5 eq) of a toluene solution of 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) was added to the reaction solution, and the reaction was continued at room temperature in the dark for 2 hours, monitored by TLC. After the reaction, the product was extracted from the reaction solution using DCM. The organic phase was treated with saturated Na₂CO₃ solution to remove excess acid and alkali, followed by extraction, drying, silica gel adsorption, and solvent drying. The crude product was purified by column chromatography (silica, 1:2 dichloromethane / petroleum ether), and the main product was a red powder. This powder was further purified by recrystallization with CH₂Cl₂ / MeOH (10:1) to obtain dark red crystals. NMR confirmed that this was the desired product, 0.435 g of the 5,10-pentanylphenyltetrabenzoporphyrin precursor. Under vacuum, 0.435 g (0.475 mmol, 1 eq) of the 5,10-pentanylphenyltetrabenzoporphyrin precursor was placed in a 250 mL reaction tube equipped with a magnetic stir bar, purged with nitrogen three times, and dissolved in 85 mL of anhydrous dichloromethane. In another reaction tube, 0.480 g (2.375 mmol, 5 eq) of copper(II) monohydrate was added, and nitrogen was purged three times. Then, 24 mL of methanol was added and stirred to dissolve the hydrate. 24 mL of a 20 mg / mL copper acetate methanol solution was slowly added dropwise to the reaction tube containing the 5,10-pentanylphenyltetrabenzoporphyrin precursor. The reaction was carried out at room temperature for 24 hours, and the reaction was monitored using absorption spectra (the polarity of the product and the starting material were very similar, but the absorption spectra showed significant differences).

[0075] After the reaction, the product was extracted using DCM. The organic phase was first treated with saturated Na2CO3 solution to remove excess acid and alkali, then extracted, dried, adsorbed onto silica gel, and the solvent was evaporated. The crude product was purified by column chromatography (silica, 1:2 to 1:1 dichloromethane / petroleum ether), and a red powder was collected. The red powder was then heated to 200°C under vacuum and reacted for 2 hours, followed by equimolar aromatization to convert it into a purple powder. After confirmation by NMR and mass spectrometry, 5,10-pentanylphenyltetrabenzoporphyrin copper(II) (0.335 g, yield 81.6%) as shown in Formula I was obtained.

[0076]

[0077] Structural characterization data of the compound represented by Formula II:

[0078] 1 H NMR(400MHz,Chloroform-d)δ12.71(s,2H),10.01(s,4H),7.37-7.87(m,24H),2.96(t,4H),1.92(m,4H),1.27-1.42(m,8H),1.02(t,6H);

[0079] MALDI-TOF(m / z)calcd for C 58 H 48 N4Cu 864.60, found 863.98 [M+H + ].

[0080] As can be seen from the above, the product has the correct structure, which is 5,10-pentanylphenyltetrabenzoporphyrin copper(II).

[0081] Example 3

[0082] Compound 5,10-octylphenyltetrabenzoporphyrin palladium(II) was prepared using a method similar to that in Example 1, except that 0.44 g (2.5 mmol, 1 eq) of 4-pentylbenzaldehyde in step (2) was replaced with 0.55 g (2.5 mmol, 1 eq) of 4-octylbenzaldehyde.

[0083]

[0084] Structural characterization data of the compound represented by Formula III:

[0085] 1 H NMR(400MHz,Chloroform-d)δ10.05(s,2H),8.96(s,8H),7.60-8.08(m,16H),7.5 9(d,4H),7.51(d,4H),3.12(t,4H),2.06(m,4H),1.47-1.73(m,20H),1.04(t,6H);

[0086] MALDI-TOF(m / z)calcd for C 64 H 60 N4Pd 990.39, found 989.88[M+H + ].

[0087] As can be seen from the above, the product has the correct structure, which is 5,10-octylphenyltetrabenzoporphyrin palladium(II) (0.412 g, yield 87.6%).

[0088] Example 4

[0089] Compound 5,10-octylphenyltetrabenzoporphyrin copper(II) was prepared using a method similar to that in Example 2, except that 0.44 g (2.5 mmol, 1 eq) of 4-pentylbenzaldehyde in step (2) was replaced with 0.55 g (2.5 mmol, 1 eq) of 4-octylbenzaldehyde.

[0090]

[0091] Structural characterization data of the compound represented by Formula IV:

[0092] 1 H NMR(400MHz,Chloroform-d)δ12.73(s,2H),10.03(s,4H),7.35-7.87(m,24H),2.97(t,4H),1.92(m,4H),1.27-1.42(m,20H),1.02(t,6H);

[0093] MALDI-TOF(m / z)calcd for C 64 H 60 N4Cu947.41, found 947.14[M+H + ].

[0094] As can be seen from the above, the product has the correct structure, which is 5,10-octylphenyltetrabenzoporphyrin copper(II) (0.364 g, yield 80.9%).

[0095] Example 5

[0096] Compound 5,10-dodecylphenyltetrabenzoporphyrin palladium(II) was prepared using a method similar to that in Example 1, except that 0.44 g (2.5 mmol, 1 eq) of 4-pentylbenzaldehyde in step (2) was replaced with 0.69 g (2.5 mmol, 1 eq) of 4-dodecylbenzaldehyde.

[0097]

[0098] Structural characterization data of the compound represented by Formula V:

[0099] 1 H NMR(400MHz,Chloroform-d)δ10.05(s,2H),8.97(s,8H),7.61-8.08(m,16H),7.5 9(d,4H),7.51(d,4H),3.12(t,4H),2.06(m,4H),1.46-1.73(m,36H),1.04(t,6H);

[0100] MALDI-TOF(m / z)calcd for C 72 H 76 N4Pd 1103.85,found 1103.25[M+H + ].

[0101] As can be seen from the above, the product has the correct structure, which is 5,10-dodecylphenyltetrabenzoporphyrin palladium(II) (0.451 g, yield 86.0%).

[0102] Example 6

[0103] Compound 5,10-dodecylphenyltetrabenzoporphyrin copper(II) was prepared using a method similar to that in Example 2, except that 0.44 g (2.5 mmol, 1 eq) of 4-pentylbenzaldehyde in step (2) was replaced with 0.69 g (2.5 mmol, 1 eq) of 4-dodecylbenzaldehyde.

[0104]

[0105] Structural characterization data of the compound represented by Formula VI:

[0106] 1 H NMR(400MHz,Chloroform-d)δ12.71(s,2H),10.03(s,4H),7.34-7.87(m,24H),2.96(t,4H),1.92(m,4H),1.27-1.42(m,36H),1.02(t,6H);

[0107] MALDI-TOF(m / z)calcd for C 72 H 76 N4Cu 1060.97,found 1060.33[M+H + ].

[0108] As can be seen from the above, the product has the correct structure, which is 5,10-dodecylphenyltetrabenzoporphyrin copper(II) (0.427 g, yield 84.7%).

[0109] Example 7

[0110] Compound 5,10-pentoxyphenyltetrabenzoporphyrin palladium(II) was prepared using a method similar to that in Example 1, except that 0.44 g (2.5 mmol, 1 eq) of 4-pentylbenzaldehyde in step (2) was replaced with 0.48 g (2.5 mmol, 1 eq) of 4-pentoxybenzaldehyde.

[0111]

[0112]

[0113] Structural characterization data of the compound represented by Formula VII:

[0114] 1 H NMR(400MHz,Chloroform-d)δ10.05(s,2H),8.96(s,8H),7.60-8.08(m,16H),7.5 9(d,4H),7.51(d,4H),4.12(t,4H),2.10(m,4H),1.47-1.73(m,8H),1.04(t,6H);

[0115] MALDI-TOF(m / z)calcd for C 58 H 48 N4O2Pd 939.47,found 939.26[M+H + ].

[0116] As can be seen from the above, the product has the correct structure, which is 5,10-pentoxyphenyltetrabenzoporphyrin palladium(II) (0.376 g, yield 84.3%).

[0117] Example 8

[0118] Compound 5,10-pentoxyphenyltetrabenzoporphyrin copper(II) was prepared using a method similar to that in Example 2, except that 0.44 g (2.5 mmol, 1 eq) of 4-pentylbenzaldehyde in step (2) was replaced with 0.48 g (2.5 mmol, 1 eq) of 4-pentoxybenzaldehyde.

[0119]

[0120] Structural characterization data of the compound represented by Formula VIII:

[0121] 1 H NMR(400MHz,Chloroform-d)δ12.71(s,2H),10.01(s,4H),7.37-7.87(m,24H),4.13(t,4H),1.92(m,4H),1.27-1.42(m,8H),1.02(t,6H);

[0122] MALDI-TOF(m / z)C 58 H 48 N4O2Cu 896.59, found 896.45 [M+H + ].

[0123] As can be seen from the above, the product has the correct structure, which is 5,10-pentoxyphenyltetrabenzoporphyrin copper(II) (0.319 g, yield 74.9%).

[0124] Example 9

[0125] Compound 5,10-octoxyphenyltetrabenzoporphyrin palladium(II) was prepared using a method similar to that in Example 1, except that 0.44 g (2.5 mmol, 1 eq) of 4-pentylbenzaldehyde in step (2) was replaced with 0.59 g (2.5 mmol, 1 eq) of 4-octoxybenzaldehyde.

[0126]

[0127] Structural characterization data of the compound represented by Formula IX:

[0128] 1 H NMR(400MHz,Chloroform-d)δ10.05(s,2H),8.96(s,8H),7.60–8.08(m,16H),7.5 9(d,4H),7.51(d,4H),4.12(t,4H),2.09(m,4H),1.47–1.73(m,20H),1.04(t,6H);

[0129] MALDI-TOF(m / z)calcd for C 64 H 60 N4O2Pd1023.63,found 1023.24[M+H + ].

[0130] As can be seen from the above, the product has the correct structure, which is 5,10-octyloxyphenyltetrabenzoporphyrin palladium(II) (0.407 g, yield 83.7%).

[0131] Example 10

[0132] Compound 5,10-octoxyphenyltetrabenzoporphyrin copper(II) was prepared using a method similar to that in Example 2, except that 0.44 g (2.5 mmol, 1 eq) of 4-pentylbenzaldehyde in step (2) was replaced with 0.59 g (2.5 mmol, 1 eq) of 4-octoxybenzaldehyde.

[0133]

[0134] Structural characterization data of the compound represented by Formula X:

[0135] 1H NMR(400MHz,Chloroform-d)δ12.73(s,2H),10.03(s,4H),7.35-7.87(m,24H),4.17(t,4H),2.02(m,4H),1.27-1.42(m,20H),1.02(t,6H);

[0136] MALDI-TOF(m / z)calcd for C 64 H 60 N4O2Cu 980.76,found 980.69[M+H + ].

[0137] As can be seen from the above, the product has the correct structure, namely, 10-octyloxyphenyltetrabenzoporphyrin copper(II) (0.393g, yield 84.4%).

[0138] Example 11

[0139] Compound 5,10-dodecyloxyphenyltetrabenzoporphyrin palladium(II) was prepared using a method similar to that in Example 1, except that 0.44 g (2.5 mmol, 1 eq) of 4-pentylbenzaldehyde in step (2) was replaced with 0.73 g (2.5 mmol, 1 eq) of 4-dodecyloxybenzaldehyde.

[0140]

[0141]

[0142] Structural characterization data of the compound represented by Formula XⅠ:

[0143] 1 H NMR(400MHz,Chloroform-d)δ10.05(s,2H),8.97(s,8H),7.61-8.08(m,16H),7.5 9(d,4H),7.51(d,4H),4.12(t,4H),2.06(m,4H),1.46-1.73(m,36H),1.04(t,6H);

[0144] MALDI-TOF(m / z)calcd for C 72 H 76 N4O2Pd 1135.85,found 1135.61[M+H + ].

[0145] As can be seen from the above, the product has the correct structure, which is 5,10-dodecyloxyphenyltetrabenzoporphyrin palladium(II) (0.427 g, yield 79.1%).

[0146] Example 12

[0147] Compound 5,10-dodecyloxyphenyltetrabenzoporphyrin copper(II) was prepared using a method similar to that in Example 2, except that 0.44 g (2.5 mmol, 1 eq) of 4-pentylbenzaldehyde in step (2) was replaced with 0.73 g (2.5 mmol, 1 eq) of 4-dodecyloxybenzaldehyde.

[0148]

[0149] Structural characterization data of the compound represented by Formula XII:

[0150] 1 H NMR(400MHz,Chloroform-d)δ12.71(s,2H),10.03(s,4H),7.34-7.87(m,24H),4.12(t,4H),1.92(m,4H),1.27-1.42(m,36H),1.02(t,6H);

[0151] MALDI-TOF(m / z)calcd for C 72 H 76 N4O2Cu 1092.97,found 1092.66[M+H + ].

[0152] As can be seen from the above, the product has the correct structure, which is 5,10-dodecyloxyphenyltetrabenzoporphyrin copper(II) (0.414 g, yield 79.7%).

[0153] Comparative Example 1

[0154] Compound 1, compound 3, trifluoroacetic acid, dichlorodicyanobenzoquinone (DDQ), and the first solvent were mixed and reacted at 20-25°C for 6-10 hours under an inert atmosphere, with monitoring performed by thin-layer chromatography. After the reaction was complete, the product was extracted from the reaction solution with dichloromethane (DCM), adsorbed onto silica gel, and the solvent was evaporated. The crude product was purified by column chromatography, and compound XIII (5,10-octylphenyltetrabenzoporphyrin) (0.360 g, yield 78%) was collected, wherein compound 3 was selected from 4-octylbenzaldehyde.

[0155]

[0156] Comparative Example 2

[0157] In a 100 mL round-bottom flask, add 0.02 mol of p-alkoxybenzaldehyde and 40 mL of propionic acid, and heat to reflux. Add 1.45 mL (approximately 0.02 mol) of freshly distilled pyrrole dropwise, and continue reflux for 1 h after the addition is complete. Cool to room temperature, add 40 mL of methanol, and let stand overnight. The compound precipitates as a blue flaky solid from the reaction system, which can be directly filtered. The filtrate is washed twice with 10 mL of propionic acid and dried under vacuum to obtain the crude product. The crude product is subjected to neutral Al₂O₃ column chromatography and recrystallization from CHCl₃-methanol to obtain the pure product, which is a blue-purple crystal.

[0158]

[0159] Examples 14-25 are examples of the fabrication of photo-stable transistors.

[0160] Example 14

[0161] like Figure 1 As shown, using SiO2 / Si as the substrate, Si as the gate, and Au as the source and drain, an OTS (octadecyltrichlorosilane) layer was modified on a 300nm thick SiO2 insulating layer by a vapor phase method. Then, the organic compound single crystal prepared in Example 1 was grown in situ on the OTS-modified SiO2 / Si substrate by a liquid phase droplet method as a charge transport layer (i.e., semiconductor layer). Two gold films were attached to the semiconductor layer as the source and drain, respectively, to construct a bottom-gate top-contact photo-stable field-effect transistor device.

[0162] Examples 15-25

[0163] The phototransistor was prepared using the same method as in Example 5, except that the organic compound prepared in Examples 2-12 was used instead of the organic compound prepared in Example 1 to prepare the charge transport layer (i.e., semiconductor layer).

[0164] Comparative Examples 3-4

[0165] The phototransistor was prepared using the same method as in Example 5, except that the organic compound prepared in Comparative Example 1 or 2 was used instead of the organic compound prepared in Example 1 to prepare the charge transport layer (i.e., the semiconductor layer).

[0166] Test case

[0167] The performance of the phototransistors and BP single-crystal devices prepared in Examples 14-25 and Comparative Examples 3-4 was tested using the following methods:

[0168] (1) Absorption spectra of solutions and thin films containing organic compounds:

[0169] The absorption spectra of solutions and films of Examples 1 and 2, as well as the organic compound 5,10-pentanylphenyltetrabenzoporphyrin (BP), were measured using a UV-Vis spectrophotometer. The results are as follows: Figure 2a and Figure 2b As shown in the figure, the absorption peak positions of both the solution and the thin film underwent a blue shift after metal complexation compared to before metal complexation.

[0170] (2) The photosensitive field-effect transistor was tested using a Keithly 4200 instrument under air and dark conditions. The optical microscope image is shown below. Figure 4a and Figure 4b As shown.

[0171] (3) Test of the properties of photo-stability field-effect transistors:

[0172] The transfer and output curves of the photosensitive field-effect transistor were tested using a Keithley 4200A-SCS electrical performance testing instrument in a probe station setup. The transfer and output curves of the photosensitive field-effect transistor based on the PdBP prepared in Example 1 are shown below. Figure 5a and Figure 5b As shown; the transfer and output curves of the photo-stable field-effect transistor based on the PdBP prepared in Example 2 are as follows. Figure 6a and Figure 6b As shown in the figure, the curves show that both long-effect transistors exhibit typical P-type charge transport performance. The on / off ratio, threshold voltage, and maximum hole mobility of the transistors are shown in Table 1, and other relevant properties of the transistors are also shown in Table 1, and so on.

[0173] (4) Stability test of photo-stable field-effect transistors:

[0174] a. Comparison of transfer curves before and after illumination with monochromatic light of different wavelengths

[0175] The transfer characteristic curves of the photo-stable field-effect transistor under darkness and illumination were tested using a probe station and a monochromator with a Keithley 4200A-SCS electrical performance test instrument.

[0176] Among them, such as Figure 7a , Figure 7b and Figure 7c As shown, the 5,10-octylphenyltetrabenzoporphyrin single crystal (hereinafter referred to as BP) device exhibits significant photoelectric response in the ultraviolet and visible light regions. After illumination, the source-drain current increases and the threshold voltage shifts positively. However, after metal complexation, the transfer curves of the PdBP device prepared in Example 1 and the CuBP device prepared in Example 2 show almost no change before and after illumination. This indicates that the photostability of the transistor is significantly improved after metal complexation.

[0177] b. Comparison of transfer curves before and after irradiation by halogen lamps with different power densities

[0178] The transfer and output curves of the photosensitive field-effect transistor were tested under halogen lamp irradiation with different power densities. Its maximum photosensitivity (P0) was also measured. max ) and threshold voltage change (ΔV th As shown in Table 1.

[0179] Among them, by Figure 8a , Figure 8b and Figure 8c The output curve shows that the BP single-crystal field-effect transistor achieves 1.74 mW / cm². 2 A clear photoresponse is observed under high light intensity, while PdBP and CuBP single-crystal field-effect transistors exhibit photoresponse even at 106.6 mW / cm². 2 The output current remains stable before and after illumination. For example... Figure 9a , Figure 9b and Figure 9c As shown, compared with devices based on BP single crystals, devices based on PdBP and CuBP single crystals are significantly more stable under illumination, even at 70.5 mW / cm². 2 Under intense illumination, the threshold voltage of a BP single-crystal field-effect transistor (FET) shows a significant positive shift, and the source-drain current increases significantly; while the PdBP FET shows very little change, and the CuBP FET shows almost no change, even at 193.2 mW / cm². 2 Even under strong light, the current and threshold voltage remain basically stable, indicating a significant difference from the BP single crystal before metal complexation.

[0180] Table 1

[0181]

[0182]

[0183] In Table 1, BP refers to a single-crystal device with a charge transport layer made of BP material.

[0184] As shown in Table 1, at the same 193.2 mW / cm 2 Under halogen lamp illumination, the maximum photosensitivity of the BP single-crystal device (P max The value is 4.8 × 10 5 Threshold voltage change (ΔV) th The voltage is 102.6V. A single-crystal device P based on the compound PdBP prepared in Example 1... max 1.8×10 4 ΔV th The voltage is 7.4V; the single-crystal device P based on the compound CuBP prepared in Example 2. max57.4, ΔV th At 3V, compared to BP single-crystal devices, the photosensitivity is reduced by five orders of magnitude, and the threshold voltage change is reduced by nearly 100V. CuBP single-crystal devices are very stable under light, achieving stability even under sunlight (138mW / cm²). 2 The requirement for stable work.

[0185] Therefore, the phototransistors prepared by using the organic compounds disclosed herein to prepare photo-stable field-effect transistors have good high hole mobility and stability.

[0186] The preferred embodiments of this disclosure have been described in detail above with reference to the accompanying drawings. However, this disclosure is not limited to the specific details of the above embodiments. Within the scope of the technical concept of this disclosure, various simple modifications can be made to the technical solutions of this disclosure, and these simple modifications all fall within the protection scope of this disclosure.

[0187] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, this disclosure will not describe the various possible combinations separately.

[0188] Furthermore, various different embodiments of this disclosure can be combined in any way, as long as they do not violate the spirit of this disclosure, they should also be regarded as the content disclosed in this disclosure.

Claims

1. The application of an organic compound in a photostable field-effect transistor, said organic compound having the structure shown in Formula 1: In Formula 1, R1 and R2 are the same and are selected from alkyl groups with 5-18 carbon atoms or alkoxy groups with 5-18 carbon atoms; X is selected from Pd or Cu.

2. The application according to claim 1, wherein, R1 and R2 are the same and are selected from alkyl groups with 5 carbon atoms, alkyl groups with 12 carbon atoms, alkoxy groups with 5 carbon atoms, and alkoxy groups with 12 carbon atoms.

3. The application according to claim 1, wherein, R1 and R2 are identical and are selected from pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, pentoxy, hexoxy, heptoxy, octoxy, nonoxy, decoxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecanyloxy, or octadecyloxy.

4. The application according to claim 1, wherein, The organic compound is selected from the group consisting of the following compounds:

5. A photo-stable field-effect transistor, wherein the photo-stable field-effect transistor contains the organic compound according to any one of claims 1-4.

6. The photo-stable field-effect transistor according to claim 5, wherein, The organic field-effect transistor includes a gate electrode, an insulating layer, a modification layer, a semiconductor layer, and source / drain electrodes, wherein the semiconductor layer contains the organic compound.

7. The photo-stable field-effect transistor according to claim 6, wherein, The semiconductor layer is an organic single crystal layer, and the thickness of the semiconductor layer is 10-50 nm.

8. The photo-stable field-effect transistor according to claim 8, wherein, The thickness of the gate electrode is 300-500 μm, and the material is nitrogen-doped silicon and / or phosphorus-doped silicon; The thickness of the insulating layer is 200-400 nm, and the material is silicon dioxide and / or aluminum oxide; The thickness of the modified layer is 5-20 nm, and the material is one or more of octadecyltrichlorosilane, perfluoro(1-butenyl vinyl ether) polymer and polymethyl methacrylate; The source and drain electrodes have a thickness of 40-150 nm and are made of gold and / or silver.

9. An electronic device comprising the photo-stable field-effect transistor according to any one of claims 5-8.

10. The electronic device according to claim 9, wherein, The electronic device includes a flexible organic light-emitting diode display and / or logic circuitry.

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