A p-type semiconductor, a manufacturing method, and an isotopic cell

Abstract

This invention discloses a P-type semiconductor, its preparation method, and an isotope battery, relating to the field of isotope battery technology. The P-type semiconductor comprises a P3HT conjugated polymer simultaneously doped with C-14 and H-3; and the P-type semiconductor uses diethyl malonate as the initial reactant, and obtains C-14-doped semiconductors through carboxylation, thiolation, and borate reactions. 14 C-thiophene borate ester 14 C-thiophene borate and poly(2-bromo-3-hexylthiophene) undergo a Suzuki coupling reaction to obtain a C-14-doped P3HT conjugated polymer. This C-14-doped P3HT conjugated polymer is then subjected to a tritium-hydrogen exchange reaction with tritium gas to obtain a C-14 and H-3-doped P3HT conjugated polymer. An isotope battery containing the C-14 and H-3-doped P3HT conjugated polymer is also disclosed. This invention provides a high-power, highly flexible isotope battery and a short-route, high-yield method for preparing P-type semiconductors.

Description

Technical Field

[0001] This invention relates to the field of isotope battery technology, specifically to a P-type semiconductor, its preparation method, and an isotope battery. Background Technology

[0002] A radiation-voltaic isotope battery (RIVB) is a power source that utilizes beta particles to generate electron-hole pairs within a semiconductor. These pairs are then separated and collected by the built-in electric field within the semiconductor, forming current and voltage. Its advantages include long lifespan, reliable performance, miniaturization, and the ability to operate in harsh or extreme environments (such as deep space, deep sea, polar glaciers, deserts, underground, and even on the human body). Therefore, RIVBs have significant potential applications in the Internet of Things (IoT), semiconductors, biomedicine, and microelectromechanical systems (MEMS). However, in existing technologies, the difficulty in loading high-activity radioactive sources means that the energy of the particles released by the radioactive source cannot be effectively utilized by the semiconductor transducer, resulting in very low output power (nW-μW level) and low energy conversion efficiency (0.01%-3%) for radiation-voltaic isotope batteries. This prevents a single battery from producing macroscopic power output, hindering the widespread adoption of radiation-voltaic isotope batteries. Furthermore, existing batteries use rigid semiconductors such as diamond and silicon, making them unsuitable for wearable devices or complex curved surfaces. Therefore, providing an isotope battery with high output power and flexibility that can adapt to flexibility requirements is an urgent technical problem to be solved. Summary of the Invention

[0003] The purpose of this invention is to solve the technical problems of low output power and low energy conversion efficiency of isotope batteries in the prior art, as well as the high rigidity and poor flexibility of isotope batteries. This invention provides a P-type semiconductor and its preparation method, and an isotope battery and its preparation method, including the following technical solutions:

[0004] A P-type semiconductor comprising a P3HT conjugated polymer simultaneously doped with C-14 and H-3.

[0005] A preparation method is applied to a P3HT conjugated polymer doped with C-14 and H-3, the preparation method of the P3HT conjugated polymer doped with C-14 and H-3 includes the following steps:

[0006] S1: Poly(2-bromo-3-hexylthiophene) )and 14 C-thiophene borate ( Under the conditions of catalyst I and solvent I, a Suzuki coupling reaction occurs to obtain a C-14-doped P3HT conjugated polymer. The reaction equation is as follows:

[0007]

[0008] S2: The C-14-doped P3HT conjugated polymer reacts with tritium gas under the conditions of catalyst II to undergo a tritium-hydrogen exchange reaction, yielding a P3HT conjugated polymer intercalated with C-14 and H-3. The reaction equation is as follows:

[0009]

[0010] Furthermore, in step S1, poly(2-bromo-3-hexylthiophene) )and 14 C-thiophene borate ( The molar ratio of ) is 1:(1.1-1.4).

[0011] Furthermore, in step S1, solvent I is a two-phase mixture of toluene and 2 mol / L sodium carbonate aqueous solution (volume ratio = 3:1).

[0012] Furthermore, the catalyst I is The amount of catalyst I was (2-3) mol% of the total reactants.

[0013] Furthermore, in step S2, the mass ratio of catalyst II to the C-14-doped P3HT conjugated polymer is 1:(3-10).

[0014] Furthermore, the catalyst II is The catalyst, wherein the Pt loading is 3 mol.

[0015] Furthermore, the aforementioned 14 C-thiophene borate ( The preparation method of ) is as follows:

[0016] S11: Diethyl malonate and A carboxylation reaction occurs to obtain The reaction equation is as follows:

[0017]

[0018] S12: and A thiolation reaction occurs to obtain 14 C-thiophene ( The reaction equation is as follows:

[0019] ;

[0020] S13: 14 C-thiophene ( ) and pinacol diboronate ( Under the conditions of catalyst III, a borylation reaction occurs to obtain... 14 C-thiophene borate ( ),

[0021] The reaction equation is as follows:

[0022]

[0023] Furthermore, in step S13, catalyst III is... .

[0024] An isotope battery includes a substrate, multiple P-type semiconductor layers, multiple N-type semiconductor layers, and an encapsulation layer. The P-type semiconductor layers and the N-type semiconductor layers are sequentially stacked between the substrate and the encapsulation layer. The bottommost P-type semiconductor layer is in contact with the substrate, and the topmost P-type semiconductor layer is in contact with the encapsulation layer. A PN junction is formed between the P-type semiconductor layers and the N-type semiconductor layers. The multiple P-type semiconductor layers and the multiple N-type semiconductor layers form a series stacked structure. The P-type semiconductor layers contain a P3HT conjugated polymer doped with C-14 and H-3, and the N-type semiconductor layers contain ZnO.

[0025] A method for preparing the isotope battery includes the following steps:

[0026] S10: P-type semiconductor layer and N-type semiconductor layer are sequentially and alternately prepared on the substrate layer. The P-type semiconductor layer is prepared by inkjet printing technology and the N-type semiconductor layer is prepared by magnetron sputtering technology.

[0027] S20: The packaging layer is prepared on the topmost N-type semiconductor using magnetron sputtering technology.

[0028] The present invention has the following advantages:

[0029] (1) This invention provides a P-type semiconductor and an isotope battery prepared by the P-type semiconductor, and a P3HT conjugated polymer doped with C-14 and H-3. By coupling C-14 (half-life 5730 years, β-ray energy 49.5 keV) and H-3 (half-life 12.3 years, β-ray energy 5.7 keV) and combining it with flexible organic semiconductor P3HT material, a high power density, flexible and long life isotope battery technology solution is proposed, which breaks through the limitations of the prior art.

[0030] (2) This invention provides a method for preparing a C-14 and H-3 doped P3HT conjugated polymer, using diethyl malonate as the initial reactant, and obtaining C-14 doped P3HT through carboxylation, thiolation and borate reactions.14 C-thiophene borate ester, 14 C-thiophene borate and poly(2-bromo-3-hexylthiophene) The Suzuki coupling reaction is carried out to obtain a C-14-doped P3HT conjugated polymer. This C-14-doped P3HT conjugated polymer is then subjected to a tritium-hydrogen exchange reaction with tritium gas to obtain a C-14 and H-3-doped P3HT conjugated polymer. The entire preparation process of the C-14 and H-3-doped P3HT conjugated polymer involves few reaction routes, mild reaction conditions, simple post-processing, and high yield.

[0031] (3) This invention also provides a structure and preparation method for an isotope battery using a P3HT conjugated polymer doped with C-14 and H-3 as a P-type semiconductor. The isotope battery prepared by the method provided in this invention, by directly embedding C-14 and H-3 into the organic semiconductor molecular chain, tightly integrates the radiation source with the semiconductor material, improving the utilization rate of β-ray energy. Simultaneously, the thinner flexible transistor film facilitates shorter electron transmission distances and reduces energy loss, thereby significantly improving the battery's power density. Compared to traditional rigid semiconductor isotope batteries, the power density can be increased by several times or even tens of times, meeting the energy demands of more application scenarios. The isotope battery prepared using flexible organic semiconductor P3HT as a substrate through solution processing exhibits excellent flexibility and bendability. This flexibility allows it to adapt to various complex curved surfaces and the shape requirements of wearable devices, providing possibilities for applications in the biomedical field (such as implantable medical devices) and flexible electronic products (such as flexible displays and wearable sensors), thus expanding the application scope of isotope batteries. C-14 has a half-life of 5730 years, and H-3 has a half-life of 12.3 years. This means that the batteries can continuously and stably release β particles, generating electron-hole pairs and thus outputting electrical energy for a very long time. Compared with traditional chemical batteries, their lifespan is far longer, making them particularly suitable for harsh environments and special applications where battery replacement is difficult or where long-term stable power supply is required, thus reducing maintenance costs and replacement risks. Attached Figure Description

[0032] Figure 1 This is a schematic diagram of the isotope battery structure of the present invention.

[0033] In the diagram: 1. Substrate layer, 2. P-type semiconductor layer, 3. N-type semiconductor layer, 4. Packaging layer. Detailed Implementation

[0034] The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings of the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments.

[0035] Therefore, the following detailed description of embodiments of the present invention is not intended to limit the scope of the claimed invention, but merely illustrates some embodiments of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0036] It should be noted that, unless otherwise specified, the embodiments and features and technical solutions in the embodiments of the present invention can be combined with each other.

[0037] It should be noted that similar labels and letters in the following figures indicate similar items. Therefore, once an item is defined in one figure, it does not need to be further defined and explained in subsequent figures.

[0038] In the description of this invention, it should be noted that the terms "upper," "lower," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings, or the orientation or positional relationship commonly used when the product of this invention is in use, or the orientation or positional relationship commonly understood by those skilled in the art. These terms are only for the convenience of describing this invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of this invention. In addition, the terms "first," "second," etc., are only used to distinguish descriptions and should not be construed as indicating or implying relative importance.

[0039] Example 1:

[0040] A method for preparing a P3HT conjugated polymer doped with C-14 and H-3 includes the following steps:

[0041] one, 14 Preparation of C-thiophene borate ester:

[0042] S11: Diethyl malonate and A carboxylation reaction occurs to obtain The reaction equation is as follows:

[0043]

[0044] The specific procedure is as follows: In a lead-shielded glove box, diethyl malonate ( (0.8 g, 5.0 mmol) and (1.4 g, 10 mmol) was added to a high-pressure reactor, followed by the injection of anhydrous tetrahydrofuran ( (THF) (50 mL), stir until completely dissolved. Slowly introduce into the high-pressure reactor through the gas introduction system. (2.5 mmol), pressure controlled at 1.3 MPa. Reaction temperature: 90℃, reaction time: 7 hours. After the reaction was complete, cooled to room temperature, and unreacted ions were slowly released. The solution is transferred to the NaOH solution absorption tower and removed by filtration. For solids, the filtered filtrate is concentrated under reduced pressure to 1 / 5 of its original volume using a rotary evaporator (temperature ≤40℃, vacuum degree ≤10 kPa).

[0045] S12: A thiolation reaction occurs to obtain 14 C-thiophene ( The reaction equation is as follows:

[0046]

[0047] The specific steps are as follows: Transfer the concentrated solution from step S12 to a round-bottom flask, add... (0.7 g, 3.0 mmol), mix thoroughly by stirring. React at 165°C (oil bath heating) for 7 hours. After the reaction solution cools, add 100 mL of ice water to quench any unreacted reaction. Then add dichloromethane ( Extract the organic phase (50 mL) three times, combine the organic phases (dichloromethane layer), and add anhydrous liquid to the organic phase. Dry the sample. Collect the sample by vacuum distillation (boiling point: 84℃ / 10 ​​mmHg). 14 C-thiophene ( ) fraction, 14 C-thiophene yield: 70%.

[0048] S13: 14 C-thiophene ( ) and pinacol diboronate ( In catalyst III ( Under the conditions of ), a borylation reaction occurs to obtain 14 C-thiophene borate ( ),

[0049] The reaction equation is as follows:

[0050]

[0051] The specific steps are as follows:

[0052] In a glove box filled with high-purity argon, 2.0 mmol (168.2 mg) of C-14-labeled argon was added sequentially to a dry 50 mL Schlenk flask. 14C-thiophene, 3.0 mmol (762 mg) pinacol diboronate (B2pin2) and 3 mol% of The catalyst (44 mg) was added, along with 15 mL of anhydrous 1,4-dioxane as solvent. The sealed reaction flask was removed from the glove box and the reaction was carried out under argon protection in an oil bath at 80 °C with stirring for 12 hours. After the reaction was completed, the mixture was cooled to room temperature and filtered under reduced pressure through a diatomaceous earth pad to remove palladium catalyst residue. The filtrate was concentrated under reduced pressure at ≤40 °C to obtain the crude product, which was then purified by column chromatography (silica gel stationary phase, petroleum ether / ethyl acetate = 9:1 as eluent). The fraction containing the target product was collected, concentrated, and yielded a pale yellow oily liquid or solid. Finally, the solid was dried in a vacuum drying oven at room temperature for 4 hours to obtain high-purity C-14 labeled thiophene-2-boronic acid pinacol ester, with a yield of approximately 85%.

[0053] II. Preparation of P3HT conjugated polymers embedded with C-14 and H-3:

[0054] S1: Poly(2-bromo-3-hexylthiophene) ) and obtained in step S13 14 C-thiophene borate ( Under the conditions of catalyst I and solvent I, a Suzuki coupling reaction occurs to obtain a C-14-doped P3HT conjugated polymer. The reaction equation is as follows:

[0055]

[0056] The specific operation is as follows: Add poly(2-bromo-3-hexylthiophene) (100 mg), 14C-thiophene borate ester obtained in step S13 (120 mg), and catalyst I to the tetrafluoroethylene reaction vessel (the tetrafluoroethylene reaction vessel has an opening at the top for introducing protective gas). (26 mg, 0.00002244 mol), then add 20 mL of solvent I and stir until completely dissolved, wherein solvent I is a two-phase mixed solution obtained by mixing toluene and 2 mol / L sodium carbonate aqueous solution in a volume ratio of 3:1; the tetrafluoroethylene reaction tank is filled with inert gas (nitrogen or argon) for protection, stirred at 500 rpm, and reacted at a reaction temperature of 100℃ for 30 h.

[0057] After the reaction is complete, first stop stirring and allow the reaction system to cool naturally to room temperature (approximately 25°C). Then, filter the reaction mixture through a diatomaceous earth filter to remove solid catalyst I ( The organic phase was separated from the aqueous phase, retaining only the organic phase. The organic phase was then thoroughly washed with deionized water, repeated three times. The washed organic phase was transferred to a pre-prepared silica gel column chromatography apparatus. When packing the column, the silica gel support was thoroughly wetted with an appropriate amount of eluent (chloroform and n-hexane mixed in a 7:3 volume ratio), ensuring no air bubbles remained at the bottom of the column. The washed organic phase was slowly poured into the top of the column, and chromatography was performed after the solution had completely entered the column. During fraction collection, the position of the target product was tracked by detecting the refractive index of the eluent; collection was stopped immediately after the target fraction was confirmed to have eluted. The collected target fraction was transferred to a clean container and dried in a vacuum drying oven at 40°C for 24 hours to remove residual solvent, finally obtaining the C-14-doped P3HT conjugated polymer product.

[0058] S2: The C-14-doped P3HT conjugated polymer reacts with tritium gas under the conditions of catalyst II to undergo a tritium-hydrogen exchange reaction, yielding a P3HT conjugated polymer intercalated with C-14 and H-3. The reaction equation is as follows:

[0059] .

[0060] Add 100 mg of the C-14-doped P3HT conjugated polymer prepared in step S1 to the tetrafluoroethylene reaction vessel (the tetrafluoroethylene reaction vessel has an opening at the top for introducing protective gas), and add catalyst II. (17 mg) In this reaction, Pt loading was 3 mol%, and anhydrous tetrahydrofuran (THF) (5 mL) was added. Tritium gas (T2) was introduced into the tetrafluoroethylene reaction vessel. The pressure in the tetrafluoroethylene reaction vessel was atmospheric pressure, the reaction temperature was 45 °C, and the reaction was carried out for 48 h. After the reaction was completed, the reaction solution was filtered to remove catalyst II. The filtrate was then subjected to vacuum distillation to remove the reaction solvent anhydrous tetrahydrofuran. The concentrated filtrate was purified by gel permeation chromatography (GPC) using chlorobenzene as the mobile phase to remove unreacted T2 and other byproducts. The eluent was dried in a vacuum drying oven at 60 °C for 12 h to obtain the target product, a P3HT conjugated polymer intercalated with C-14 and H-3. The yield of the P3HT conjugated polymer intercalated with C-14 and H-3 was 85%.

[0061] Example 2:

[0062] A method for preparing a P3HT conjugated polymer doped with C-14 and H-3 includes the following steps:

[0063] one, 14 Preparation of C-thiophene borate ester:

[0064] S11: Diethyl malonate and A carboxylation reaction occurs to obtain The reaction equation is as follows:

[0065]

[0066] The specific procedure is as follows: In a lead-shielded glove box, diethyl malonate ( (0.8g, 5.0 mmol) and (1.4 g, 10 mmol) was added to a high-pressure reactor, followed by the injection of anhydrous tetrahydrofuran ( (THF) (50 mL), stir until completely dissolved. Slowly introduce into the high-pressure reactor through the gas introduction system. (2.5 mmol), pressure controlled at 1.0 MPa. Reaction temperature: 80℃, reaction time: 6 hours. After the reaction was complete, cool to room temperature and slowly release unreacted... The solution is transferred to the NaOH solution absorption tower and removed by filtration. For solids, the filtered filtrate is concentrated under reduced pressure to 1 / 5 of its original volume using a rotary evaporator (temperature ≤40℃, vacuum degree ≤10 kPa).

[0067] S12: and A thiolation reaction occurs to obtain 14 C-thiophene ( The reaction equation is as follows:

[0068] ;

[0069] The specific steps are as follows: Transfer the concentrated solution from step S12 to a round-bottom flask, add... (0.7 g, 3.0 mmol), mix thoroughly. Reaction time: 6 hours at 150°C (oil bath heating). After the reaction solution cools, add 100 mL of ice water to quench unreacted P2S5; then add dichloromethane ( Extract the organic phase (50 mL) three times, combine the organic phases (dichloromethane layer), and add anhydrous liquid to the organic phase. Dry the sample. Collect the sample by vacuum distillation (boiling point: 84℃ / 10 ​​mmHg). 14 C-thiophene ( ) fraction, 14 C-thiophene yield: 69%.

[0070] S13: 14 C-thiophene ( ) and pinacol diboronate ( In catalyst III ( Under the conditions of ), a borylation reaction occurs to obtain 14 C-thiophene borate ( ),

[0071] The reaction equation is as follows:

[0072]

[0073] The specific steps are as follows:

[0074] In a glove box filled with high-purity argon, 2.0 mmol (168.2 mg) of C-14-labeled argon was added sequentially to a dry 50 mL Schlenk flask. 14 C-Thiophene, 3.0 mmol (762 mg) pinacol diboronate ( ) and 3 mol% The catalyst (44 mg) was added, along with 15 mL of anhydrous 1,4-dioxane as solvent. The sealed reaction flask was removed from the glove box and the reaction was carried out under argon protection in an oil bath at 80 °C with stirring for 12 hours. After the reaction was completed, the mixture was cooled to room temperature and filtered under reduced pressure through a diatomaceous earth pad to remove palladium catalyst residue. The filtrate was concentrated under reduced pressure at ≤40 °C to obtain the crude product, which was then purified by column chromatography (silica gel stationary phase, petroleum ether / ethyl acetate = 9:1 as eluent). The fraction containing the target product was collected, concentrated, and yielded a pale yellow oily liquid or solid. Finally, the solid was dried in a vacuum drying oven at room temperature for 4 hours to obtain high-purity C-14 labeled thiophene-2-boronic acid pinacol ester, with a yield of 84%.

[0075] II. Preparation of P3HT conjugated polymers embedded with C-14 and H-3:

[0076] S1: Poly(2-bromo-3-hexylthiophene) ) and obtained in step S13 14 C-thiophene borate ( Under the conditions of catalyst I and solvent I, a Suzuki coupling reaction occurs to obtain a C-14-doped P3HT conjugated polymer. The reaction equation is as follows:

[0077]

[0078] The specific operation is as follows: Add poly(2-bromo-3-hexylthiophene) (100 mg), 14C-thiophene borate ester obtained in step S13 (110 mg), and catalyst I to the tetrafluoroethylene reaction vessel (the tetrafluoroethylene reaction vessel has an opening at the top for introducing protective gas). (19.8 mg, 0.000017136 mol), then add 20 mL of solvent I and stir until completely dissolved, wherein solvent I is a two-phase mixed solution obtained by mixing toluene and 2 mol / L sodium carbonate aqueous solution in a volume ratio of 3:1; the tetrafluoroethylene reaction vessel is charged with inert gas (nitrogen or argon) for protection, stirred at 500 rpm, and reacted at a reaction temperature of 90℃ for 24 h.

[0079] After the reaction is complete, first stop stirring and allow the reaction system to cool naturally to room temperature (approximately 25°C). Then, filter the reaction mixture through a diatomaceous earth filter to remove solid catalyst I ( The organic phase was separated from the aqueous phase, retaining only the organic phase. The organic phase was then thoroughly washed with deionized water, repeated three times. The washed organic phase was transferred to a pre-prepared silica gel column chromatography apparatus. When packing the column, the silica gel support was thoroughly wetted with an appropriate amount of eluent (chloroform and n-hexane mixed in a 7:3 volume ratio), ensuring no air bubbles remained at the bottom of the column. The washed organic phase was slowly poured into the top of the column, and chromatography was performed after the solution had completely entered the column. During fraction collection, the position of the target product was tracked by detecting the refractive index of the eluent; collection was stopped immediately after the target fraction was confirmed to have eluted. The collected target fraction was transferred to a clean container and dried in a vacuum drying oven at 40°C for 24 hours to remove residual solvent, yielding the C-14-doped P3HT conjugated polymer product.

[0080] S2: The C-14-doped P3HT conjugated polymer reacts with tritium gas under the conditions of catalyst II to undergo a tritium-hydrogen exchange reaction, yielding a P3HT conjugated polymer intercalated with C-14 and H-3. The reaction equation is as follows:

[0081] .

[0082] Add 100 mg of the C-14-doped P3HT conjugated polymer prepared in step S1 to the tetrafluoroethylene reaction vessel (the tetrafluoroethylene reaction vessel has an opening at the top for introducing protective gas), and add catalyst II. (34 mg) In this reaction, Pt loading was 3 mol%, and anhydrous tetrahydrofuran (THF) (5 mL) was added. Tritium gas (T2) was introduced into the tetrafluoroethylene reaction vessel. The pressure in the tetrafluoroethylene reaction vessel was atmospheric pressure, the reaction temperature was 40 °C, and the reaction was carried out for 48 h. After the reaction was completed, the reaction solution was filtered to remove catalyst II. The filtrate was then subjected to vacuum distillation to remove the reaction solvent anhydrous tetrahydrofuran. The concentrated filtrate was purified by gel permeation chromatography (GPC) using chlorobenzene as the mobile phase to remove unreacted T2 and other byproducts. The eluent was dried in a vacuum drying oven at 60 °C for 12 h to obtain the target product, a P3HT conjugated polymer intercalated with C-14 and H-3. The yield of the P3HT conjugated polymer intercalated with C-14 and H-3 was 84%.

[0083] Example 3:

[0084] A method for preparing a P3HT conjugated polymer doped with C-14 and H-3 includes the following steps:

[0085] one, 14 Preparation of C-thiophene borate ester:

[0086] S11: Diethyl malonate and A carboxylation reaction occurs to obtain The reaction equation is as follows:

[0087]

[0088] The specific procedure is as follows: In a lead-shielded glove box, diethyl malonate ( (0.8g, 5.0 mmol) and (1.4 g, 10 mmol) was added to a high-pressure reactor, followed by the injection of anhydrous tetrahydrofuran ( (THF) (50 mL), stir until completely dissolved. Slowly introduce into the high-pressure reactor through the gas introduction system. (2.5 mmol), pressure controlled at 1.5 MPa. Reaction temperature: 100℃, reaction time: 8 hours. After the reaction was complete, cool to room temperature and slowly release unreacted... The solution is transferred to the NaOH solution absorption tower and removed by filtration. For solids, the filtered filtrate is concentrated under reduced pressure to 1 / 5 of its original volume using a rotary evaporator (temperature ≤40℃, vacuum degree ≤10kPa).

[0089] S12: and A thiolation reaction occurs to obtain 14 C-thiophene ( The reaction equation is as follows:

[0090]

[0091] The specific steps are as follows: Transfer the concentrated solution from step S12 to a round-bottom flask, add... (0.7 g, 3.0 mmol), mix thoroughly by stirring. React at 180°C (oil bath heating) for 8 hours. After the reaction solution cools, add 100 mL of ice water to quench any unreacted reaction. Then add dichloromethane ( Extract the organic phase (50 mL) three times, combine the organic phases (dichloromethane layer), and add anhydrous liquid to the organic phase. Dry the sample. Collect the sample by vacuum distillation (boiling point: 84℃ / 10 ​​mmHg). 14 C-thiophene ( ) fraction, 14 C-thiophene yield: 68%.

[0092] S13: 14 C-thiophene ( ) and pinacol diboronate ( In catalyst III ( Under the conditions of ), a borylation reaction occurs to obtain 14 C-thiophene borate ( ),

[0093] The reaction equation is as follows:

[0094]

[0095] The specific procedure is as follows: In a glove box filled with high-purity argon, add 2.0 mmol (168.2 mg) of C-14-labeled argon gas sequentially to a dry 50 mL Schlenk flask. 14 C-Thiophene, 3.0 mmol (762 mg) Pinaryl Boronate ) and 3 mol% The catalyst (44 mg) was added, along with 15 mL of anhydrous 1,4-dioxane as solvent. The sealed reaction flask was removed from the glove box and the reaction was carried out under argon protection in an oil bath at 80 °C with stirring for 12 hours. After the reaction was completed, the mixture was cooled to room temperature and filtered under reduced pressure through a diatomaceous earth pad to remove palladium catalyst residue. The filtrate was concentrated under reduced pressure at ≤40 °C to obtain the crude product, which was then purified by column chromatography (silica gel stationary phase, petroleum ether / ethyl acetate = 9:1 as eluent). The fraction containing the target product was collected, concentrated, and yielded a pale yellow oily liquid or solid. Finally, the solid was dried in a vacuum drying oven at room temperature for 4 hours to obtain high-purity C-14 labeled thiophene-2-boronic acid pinacol ester, with a yield of approximately 86%.

[0096] II. Preparation of P3HT conjugated polymers embedded with C-14 and H-3:

[0097] S1: Poly(2-bromo-3-hexylthiophene) ) and obtained in step S13 14 C-thiophene borate ( Under the conditions of catalyst I and solvent I, a Suzuki coupling reaction occurs to obtain a C-14-doped P3HT conjugated polymer. The reaction equation is as follows:

[0098]

[0099] The specific operation is as follows: Add poly(2-bromo-3-hexylthiophene) (100 mg), 14C-thiophene borate ester obtained in step S13 (140 mg), and catalyst I to the tetrafluoroethylene reaction vessel (the tetrafluoroethylene reaction vessel has an opening at the top for introducing protective gas). (33.96 mg, 0.000029376 mol), then add 20 mL of solvent I and stir until completely dissolved, wherein solvent I is a two-phase mixed solution obtained by mixing toluene and 2 mol / L sodium carbonate aqueous solution in a volume ratio of 3:1; the tetrafluoroethylene reaction tank is charged with inert gas (nitrogen or argon) for protection, stirred at 500 rpm, and reacted at a reaction temperature of 130℃ for 36 h, preferably at a temperature of 100~120℃.

[0100] After the reaction is complete, first stop stirring and allow the reaction system to cool naturally to room temperature (approximately 25°C). Then, filter the reaction mixture through a diatomaceous earth filter to remove solid catalyst I ( The organic phase was separated from the aqueous phase, retaining only the organic phase. The organic phase was then thoroughly washed with deionized water, repeated three times. The washed organic phase was transferred to a pre-prepared silica gel column chromatography apparatus. When packing the column, the silica gel support was thoroughly wetted with an appropriate amount of eluent (chloroform and n-hexane mixed in a 7:3 volume ratio), ensuring no air bubbles remained at the bottom of the column. The washed organic phase was slowly poured into the top of the column, and chromatography was performed after the solution had completely entered the column. During fraction collection, the position of the target product was tracked by detecting the refractive index of the eluent; collection was stopped immediately after the target fraction was confirmed to have eluted. The collected target fraction was transferred to a clean container and dried in a vacuum drying oven at 40°C for 24 hours to remove residual solvent, finally obtaining the C-14-doped P3HT conjugated polymer product.

[0101] S2: The C-14-doped P3HT conjugated polymer reacts with tritium gas under the conditions of catalyst II to undergo a tritium-hydrogen exchange reaction, yielding a P3HT conjugated polymer intercalated with C-14 and H-3. The reaction equation is as follows:

[0102] .

[0103] Add 100 mg of the C-14-doped P3HT conjugated polymer prepared in step S1 to the tetrafluoroethylene reaction vessel (the tetrafluoroethylene reaction vessel has an opening at the top for introducing protective gas), and add catalyst II. (10 mg) In this reaction, Pt loading was 3 mol%, and anhydrous tetrahydrofuran (THF) (5 mL) was added. Tritium gas (T2) was introduced into the tetrafluoroethylene reaction vessel. The pressure in the tetrafluoroethylene reaction vessel was atmospheric pressure, the reaction temperature was 60 °C, and the reaction was carried out for 48 h. After the reaction was completed, the reaction solution was filtered to remove catalyst II. The filtrate was then subjected to vacuum distillation to remove the reaction solvent anhydrous tetrahydrofuran. The concentrated filtrate was purified by gel permeation chromatography (GPC) using chlorobenzene as the mobile phase to remove unreacted T2 and other byproducts. The eluent was dried in a vacuum drying oven at 60 °C for 12 h to obtain the target product, a P3HT conjugated polymer intercalated with C-14 and H-3. The yield of the P3HT conjugated polymer intercalated with C-14 and H-3 was 82%.

[0104] Example 4:

[0105] A method for preparing a P3HT conjugated polymer doped with C-14 and H-3 includes the following steps:

[0106] one, 14 Preparation of C-thiophene borate ester:

[0107] S11: Diethyl malonate and A carboxylation reaction occurs to obtain The reaction equation is as follows:

[0108]

[0109] The specific procedure is as follows: In a lead-shielded glove box, diethyl malonate ( (0.8g, 5.0 mmol) and (1.4 g, 10 mmol) was added to a high-pressure reactor, followed by the injection of anhydrous tetrahydrofuran ( (THF) (50 mL), stir until completely dissolved. Slowly introduce into the high-pressure reactor through the gas introduction system. (2.5 mmol), pressure controlled at 1.4 MPa. Reaction temperature: 90℃, reaction time: 7.5 hours. After reaction, cool to room temperature, and slowly release unreacted... The solution is transferred to the NaOH solution absorption tower and removed by filtration. For solids, the filtered filtrate is concentrated under reduced pressure to 1 / 5 of its original volume using a rotary evaporator (temperature ≤40℃, vacuum degree ≤10kPa).

[0110] S12: A thiolation reaction occurs to obtain 14 C-thiophene ( The reaction equation is as follows:

[0111]

[0112] The specific steps are as follows: Transfer the concentrated solution from step S12 to a round-bottom flask, add... (0.7 g, 3.0 mmol), mix thoroughly by stirring. React at 150–180 °C (oil bath heating) for 6.5 hours. After the reaction solution cools, add 100 mL of ice water to quench any unreacted reaction. Then add dichloromethane ( Extract the organic phase (50 mL) three times, combine the organic phases (dichloromethane layer), and add anhydrous liquid to the organic phase. Dry the sample. Collect the sample by vacuum distillation (boiling point: 84℃ / 10 ​​mmHg). 14 C-thiophene ( ) fraction, 14 C-thiophene yield: 67%.

[0113] S13: 14 C-thiophene ( ) and pinacol diboronate ( In catalyst III ( Under the conditions of ), a borylation reaction occurs to obtain 14 C-thiophene borate ( ),

[0114] The reaction equation is as follows:

[0115]

[0116] The specific steps are as follows:

[0117] In a glove box filled with high-purity argon, 2.0 mmol (168.2 mg) of C-14-labeled thiophene and 3.0 mmol (762 mg) of pinacol diborate were added sequentially to a dry 50 mL Schlenk flask. ) and 3 mol% The catalyst (44 mg) was added, along with 15 mL of anhydrous 1,4-dioxane as solvent. The sealed reaction flask was removed from the glove box and the reaction was carried out under argon protection in an oil bath at 80 °C with stirring for 12 hours. After the reaction was completed, the mixture was cooled to room temperature and filtered under reduced pressure through a diatomaceous earth pad to remove palladium catalyst residue. The filtrate was concentrated under reduced pressure at ≤40 °C to obtain the crude product, which was then purified by column chromatography (silica gel stationary phase, petroleum ether / ethyl acetate = 9:1 as eluent). The fraction containing the target product was collected, concentrated, and yielded a pale yellow oily liquid or solid. Finally, the solid was dried in a vacuum drying oven at room temperature for 4 hours to obtain high-purity C-14 labeled thiophene-2-boronic acid pinacol ester, with a yield of approximately 85%.

[0118] II. Preparation of P3HT conjugated polymers embedded with C-14 and H-3:

[0119] S1: Poly(2-bromo-3-hexylthiophene) ) and obtained in step S13 14 C-thiophene borate ( Under the conditions of catalyst I and solvent I, a Suzuki coupling reaction occurs to obtain a C-14-doped P3HT conjugated polymer. The reaction equation is as follows:

[0120]

[0121] The specific operation is as follows: Add poly(2-bromo-3-hexylthiophene) (100 mg), 14C-thiophene borate ester obtained in step S13 (130 mg), and catalyst I to the tetrafluoroethylene reaction vessel (the tetrafluoroethylene reaction vessel has an opening at the top for introducing protective gas). (29.27 mg, 0.000029376 mol), then add 20 mL of solvent I and stir until completely dissolved. Solvent I is a two-phase mixed solution obtained by mixing toluene and 2 mol / L sodium carbonate aqueous solution in a volume ratio of 3:1. The tetrafluoroethylene reaction vessel is charged with an inert gas (nitrogen or argon) for protection, stirred at 500 rpm, and reacted at a reaction temperature of 120℃ for 28 h.

[0122] After the reaction is complete, first stop stirring and allow the reaction system to cool naturally to room temperature (approximately 25°C). Then, filter the reaction mixture through a diatomaceous earth filter to remove solid catalyst I ( The organic phase was separated from the aqueous phase, retaining only the organic phase. The organic phase was then thoroughly washed with deionized water, repeated three times. The washed organic phase was transferred to a pre-prepared silica gel column chromatography apparatus. When packing the column, the silica gel support was thoroughly wetted with an appropriate amount of eluent (chloroform and n-hexane mixed in a 7:3 volume ratio), ensuring no air bubbles remained at the bottom of the column. The washed organic phase was slowly poured into the top of the column, and chromatography was performed after the solution had completely entered the column. During fraction collection, the position of the target product was tracked by detecting the refractive index of the eluent; collection was stopped immediately after the target fraction was confirmed to have eluted. The collected target fraction was transferred to a clean container and dried in a vacuum drying oven at 40°C for 24 hours to remove residual solvent, finally obtaining the C-14-doped P3HT conjugated polymer product.

[0123] S2: The C-14-doped P3HT conjugated polymer reacts with tritium gas under the conditions of catalyst II to undergo a tritium-hydrogen exchange reaction, yielding a P3HT conjugated polymer intercalated with C-14 and H-3. The reaction equation is as follows:

[0124]

[0125] Add 100 mg of the C-14-doped P3HT conjugated polymer prepared in step S1 to the tetrafluoroethylene reaction vessel (the tetrafluoroethylene reaction vessel has an opening at the top for introducing protective gas), and add catalyst II. (20 mg) In this reaction, Pt loading was 3 mol%, and anhydrous tetrahydrofuran (THF) (5 mL) was added. Tritium gas (T2) was introduced into the tetrafluoroethylene reaction vessel. The pressure in the tetrafluoroethylene reaction vessel was atmospheric pressure, the reaction temperature was 55 °C, and the reaction was carried out for 48 h. After the reaction was completed, the reaction solution was filtered to remove catalyst II. The filtrate was then subjected to vacuum distillation to remove the reaction solvent anhydrous tetrahydrofuran. The concentrated filtrate was purified by gel permeation chromatography (GPC) using chlorobenzene as the mobile phase to remove unreacted T2 and other byproducts. The eluent was dried in a vacuum drying oven at 60 °C for 12 h to obtain the target product, a P3HT conjugated polymer intercalated with C-14 and H-3. The yield of the P3HT conjugated polymer intercalated with C-14 and H-3 was 85%.

[0126] In Examples 1-4, in step S11, the pressure of the high-pressure reactor is controlled at 1.0~1.5 MPa because when the pressure is below 1.0 MPa, Insufficient solubility can lead to a low reaction rate; above 1.5 MPa, the risk to equipment sealing increases.

[0127] The reaction temperature is (80-100) degrees Celsius. At temperatures below 80°C, the carboxylation rate decreases significantly (conversion <50%); at temperatures above 100°C, diethyl malonate may decompose. When the reaction time is less than 6 hours... Insufficient conversion rate (<80%); increased byproducts after >8 hours ( (Carbonated lipids)

[0128] In step S12, the oil bath heating temperature range is (150-180)℃ because when the temperature is <150℃, the thiophene reaction is incomplete (thiophene yield <60%); when the temperature is >180℃, Possible decomposition produces Gas (this requires strict exhaust treatment). When the time is <6 hours, the closed-loop reaction is incomplete; when >8 hours, byproducts ( (Sulfur oxides) increase.

[0129] In step S2, the selected reaction temperature is set at (40-60°C) because the reaction rate is too low (tritium substitution rate <70% after 48 hours) when the temperature is below 40°C, and thermal isomerization may occur in the organic semiconductor side chain alkyl group when the temperature is above 55°C.

[0130] Example 5:

[0131] See Figure 1 An isotope battery includes a substrate layer 1, multiple P-type semiconductor layers 2, multiple N-type semiconductor layers 3, and an encapsulation layer 4. The P-type semiconductor layers 2 and the N-type semiconductor layers 3 are sequentially stacked between the substrate layer 1 and the encapsulation layer 4. The bottommost P-type semiconductor layer 2 is in contact with the substrate layer 1, and the topmost P-type semiconductor layer 2 is in contact with the encapsulation layer 4. A PN junction is formed between the P-type semiconductor layers 2 and the N-type semiconductor layers 3. The multiple P-type semiconductor layers 2 and the multiple N-type semiconductor layers 3 form a series stacked structure. The P-type semiconductor layers 2 contain a P3HT conjugated polymer doped with C-14 and H-3. Specifically, the material of the P-type semiconductor layer contains a P3HT conjugated polymer doped with C-14 and H-3. The N-type semiconductor layer 2 contains ZnO.

[0132] In this embodiment, a P-type semiconductor containing a P3HT conjugated polymer of C-14 and H-3 forms a PN junction with an N-type semiconductor of ZnO. The PN junction formed by multiple layers of P3HT and ZnO forms a series stacked structure of the isotope battery. The series stacked design can improve the output power of the isotope battery.

[0133] Example 6:

[0134] A method for preparing an isotope battery includes the following steps:

[0135] S10: P-type semiconductor layers and N-type semiconductor layers are sequentially and alternately fabricated on a substrate. The P-type semiconductor layers are fabricated by inkjet printing technology, and the N-type semiconductor layers are fabricated by magnetron sputtering technology.

[0136] Specifically,

[0137] The process parameters for fabricating the P-type semiconductor layer using inkjet printing technology are as follows:

[0138] (1) Preparation of inkjet printing solution: Dissolve the P3HT conjugated polymer doped with C-14 and H-3 in a suitable organic solvent, such as chlorobenzene or toluene, to prepare a solution with a concentration of (10-30) mg / mL to ensure the formation of a uniform film during inkjet printing. Further, appropriate additives, such as surfactants and thickeners, can be added to the solution to improve its rheological properties and printing performance.

[0139] (2) The prepared P3HT conjugated polymer solution of C-14 and H-3 was loaded into an inkjet printer for inkjet printing. The inkjet printer parameters were set as follows: nozzle diameter 30 μm, droplet volume 10 pL, and substrate temperature 80 °C. During the printing process, a multi-pass printing method was used to increase the thickness and uniformity of the P-type semiconductor layer. An appropriate interval was set between each pass to allow the solution from the previous pass to dry initially, avoiding mutual diffusion and mixing between droplets. After printing, the substrate was placed in a nitrogen atmosphere for gradient annealing. The annealing temperature was gradually increased from 80 °C to 150 °C at a heating rate of 2 °C / min, and the holding time was 30-60 minutes to eliminate residual stress in the film and improve the crystallinity and electrical properties of the P-type semiconductor layer.

[0140] The process parameters for fabricating the N-type semiconductor layer using magnetron sputtering technology are as follows:

[0141] (1) Sputtering system configuration and process parameter setting

[0142] A high-purity zinc target (purity ≥ 99.99%) was used and fixed at the magnetron sputtering cathode. Argon (Ar) was selected as the sputtering gas, and the flow rate was adjusted to 6.67 × 10⁻⁶. −7 m 3 / s (40 sccm) to 8.33×10 −7 m 3 / s (50 sccm), oxygen (O2) is used as the reactant gas, and the flow rate is set to 1.33 × 10⁻⁶. −7 m 3 / s (8 sccm) to 1.67×10 −7 m 3 / s (10 sccm), with hydrogen (H2) as the auxiliary gas, the flow rate is controlled at 3.33 × 10 −8 m 3 / s (2 sccm) to 5.00×10 −8 m 3 / s (3 sccm). The RF power is set between 100-150 W, and the substrate temperature is stabilized between 60-80 °C to avoid thermal degradation of the P3HT substrate. The base vacuum level is ≤5×10⁻ 4 Pa, the sputtering time is preset to be between (30-60) min.

[0143] (2) Sputtering deposition and thin film performance control

[0144] After the radio frequency power supply is turned on, a zinc target is sputtered in a mixed atmosphere of argon, oxygen and hydrogen. Zinc atoms react with oxygen plasma to generate a ZnO thin film, i.e. an N-type semiconductor layer.

[0145] In this embodiment, hydrogen gas selectively etches the amorphous phase, promoting the preferential growth of ZnO along the crystal plane, which can suppress the oxygen vacancy defect density to <10. 17  cm −3 By adjusting the process parameters through real-time monitoring of the sputtering rate (≈10 nm / min), the final film thickness was controlled within 100-200 nm, with an error range of ±5 nm.

[0146] S20: A packaging layer is fabricated on the topmost N-type semiconductor using magnetron sputtering. The substrate and packaging layer can be used as bonding pads for wire bonding to draw out current and form an isotope cell.

[0147] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A P-type semiconductor, characterized in that, The P-type semiconductor includes a P3HT conjugated polymer simultaneously doped with C-14 and H-3.

2. A preparation method for preparing the P3HT conjugated polymer simultaneously doped with C-14 and H-3 as described in claim 1, characterized in that, The P3HT conjugated polymer doped with C-14 and H-3 Includes the following steps: S1: Poly(2-bromo-3-hexylthiophene) ([C 10 H 13 BrS] and 14 C-thiophene borate (C8H7) 14 CB(O)₂S), under the conditions of catalyst I and solvent I, undergoes a Suzuki coupling reaction to obtain a C-14-doped P₃HT conjugated polymer ([C 10 H 13 −mTmS- 14 [C-C8H6S]n); the reaction equation is as follows: n[C 10 H 13 BrS] +nC8H7 14 C-B(O)2S C[C 10 H 13 S- 14 C-C8H6S]n + nB(OH)3+ nHBr S2: The C-14-doped P3HT conjugated polymer reacts with tritium gas under the conditions of catalyst II to obtain a P3HT conjugated polymer intercalated with C-14 and H-3 ([C 10 H 13−m T m S- 14 C-C8H6S] n ); The reaction equation is as follows: [C 10 H 13 S- 14 C-C8H6S] n + mT2 [C 10 H 13−m T m S- 14 C-C8H6S] n + mH2。 3. The preparation method according to claim 2, characterized in that, In step S1, poly(2-bromo-3-hexylthiophene) ([C 10 H 13 BrS] and 14 C-thiophene borate (C8H7) 14 The mass ratio of CB(O)2S is 1:(1.1-1.4).

4. The preparation method according to claim 2, characterized in that, In step S1, solvent I is a two-phase mixture of toluene and 2 mol / L sodium carbonate aqueous solution (volume ratio = 3:1).

5. The preparation method according to claim 2, characterized in that, The catalyst I is Pd(PPh3)4, and the amount of catalyst I is (2-3) mol of the total reactants.

6. The preparation method according to claim 2, characterized in that, In step S2, the mass ratio of catalyst II to the C-14-doped P3HT conjugated polymer is 1:(3-10).

7. The preparation method according to claim 2, characterized in that, In step S2, the catalyst II is Pt / Al2O3, wherein the Pt loading is 3 mol.

8. The preparation method according to claim 2, characterized in that, The 14 C-thiophene borate (C8H7) 14 The preparation method of CB(O)2S is as follows: S11: Diethyl malonate and 14 CO2 undergoes a carboxylation reaction to produce CH2( 14 The reaction equation for COOCH2CH3(COOCH2CH3) is as follows: CH2(COOCH2CH3)2 + 14 CO2 CH2( 14 COOCH2CH3)(COOCH2CH3) + HCO3 − S12: CH2( 14 COOCH2CH3)(COOCH2CH3) and P2S5 undergo a thiolation reaction to obtain 14 C-thiophene (C3) 14 CH4S), the reaction equation is as follows: CH2( 14 COOCH2CH3)(COOCH2CH3) + P2S5 C3 14 CH4S + 2CH3CH2SH + CO2↑; S13: 14 C-thiophene (C3) 14 CH4S) and pinacol diboronate (C 12 H 24 B2O4 (B2(OCH2C(CH3)2O)2) undergoes a borylation reaction under the conditions of catalyst III to obtain 14 C-thiophene borate (C8H7) 14 CB(O)2S). The reaction equation is as follows: C3¹ 4 CH4S + B2(OCH2C(CH3)2O)2 C4H3 14 CS-B(OCH2C(CH3)2O)2 + HB(OCH2C(CH3)2O) 9. The preparation method according to claim 8, characterized in that, In step S13, catalyst III is Pd(dppf)Cl2.

10. An isotope battery, characterized in that, The device includes a substrate layer, multiple P-type semiconductor layers, multiple N-type semiconductor layers, and a packaging layer. The P-type semiconductor layers and the N-type semiconductor layers are sequentially overlapped between the substrate layer and the packaging layer. The bottommost P-type semiconductor layer is in contact with the substrate layer, and the topmost P-type semiconductor layer is in contact with the packaging layer. A PN junction is formed between the P-type semiconductor layers and the N-type semiconductor layers. The multiple P-type semiconductor layers and the multiple N-type semiconductor layers form a series stacked structure. The P-type semiconductor layers contain the P3HT conjugated polymer doped with C-14 and H-3 as described in any one of claims 1-9, and the N-type semiconductor layers contain ZnO.

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