An electron beam-induced Ge-Au amorphous thin film material and a method for rapid crystallization of amorphous thin films.

Abstract

This invention relates to the field of amorphous alloy materials technology, specifically disclosing an electron beam-induced Ge-Au amorphous thin film material and a method for rapid crystallization of the amorphous thin film. The amorphous thin film material comprises the following raw materials: Ge-Au amorphous nanoparticle liquid, a water-soluble film-forming agent, a freeze-drying crosslinking agent, a freeze-drying protective agent, an electron beam sensitizer, a thermogenic acid catalyst, and an antifoaming agent. The method for rapid crystallization of the amorphous thin film involves spin-coating a precursor liquid onto a substrate, followed by freeze-drying and thermal crosslinking to obtain an amorphous thin film, and then inducing crystallization through electron beam scanning irradiation. This invention utilizes glyoxal and boric acid as freeze-drying crosslinking agents to form a dynamic double crosslinking network between the water-soluble film-forming agent polyvinyl alcohol matrix and the terminal amino-terminated carbon nanotubes to dissipate phase transition shrinkage strain energy. Furthermore, modified multi-walled carbon nanotubes form high thermal conductivity channels and a flexible buffer network, significantly improving the crystallization expansion rate of the thin film and effectively suppressing the generation of microcracks.

Description

Technical Field

[0001] This invention relates to the field of amorphous alloy materials technology, and more specifically, to an electron beam-induced Ge-Au amorphous thin film material and a method for rapid crystallization of amorphous thin films. Background Technology

[0002] Germanium-gold (Ge-Au) amorphous thin films are an important class of functional materials with broad application prospects in phase change memory, micro / nanoelectronic devices, and photoelectric detection. The deposited state typically refers to the state of the thin film after preparation, without any thermal annealing or other post-treatment. The microstructure of deposited Ge-Au thin films (such as compositional uniformity, internal stress distribution, and atomic disorder) is highly sensitive to their subsequent crystallization kinetics and crystalline phase structure. Ideally, deposited thin films should possess high compositional uniformity and stress relaxation capabilities suitable for nucleation growth to ensure efficient crystallization and the integrity of the crystallized film.

[0003] However, existing technologies have the following significant drawbacks: First, traditional pure inorganic vapor deposition methods require stringent preparation conditions during the large-area deposition and forming stage of thin films, demanding that the entire deposition process be conducted under extremely high vacuum (3.5 × 10⁻⁶). -6 The process involves deposition on substrates cooled by liquid nitrogen (Tor) and requires stringent equipment, making large-scale, continuous industrial production difficult. Secondly, to circumvent the harsh conditions of vapor deposition, liquid-phase coating methods (such as polymer precursor methods) are often used to prepare amorphous thin films. However, in practical applications, the transition from amorphous to crystalline states is accompanied by a dramatic increase in atomic packing density, generating significant intrinsic tensile and shrinkage stresses. Furthermore, conventional liquid-phase polymer matrices are statically rigid, lacking effective stress release and dynamic buffering mechanisms. When subjected to high-energy electron beam irradiation, resulting in localized thermal activation and rapid crystallization, the film is prone to microcracks or even peeling at grain boundaries or multiphase interfaces, severely damaging the integrity of the film's microstructure. Thirdly, the disordered arrangement of atoms within pure amorphous Ge-Au alloys leads to extremely short phonon mean free paths and high interfacial thermal resistance. Simultaneously, the pure polymer matrix introduced by conventional liquid-phase deposition inherently has extremely poor thermal conductivity. Due to the lack of an efficient heat conduction network within the thin film, the efficiency of the localized energy injected by the electron beam to spread outwards is severely limited, resulting in highly localized heat. This not only exacerbates structural damage caused by thermal stress but also leads to a bottleneck in the crystal growth rate under high beam current, failing to meet the efficiency requirements of modern micro-nano fabrication for ultra-fast direct-write crystallization. Based on the above technical background, this invention provides an electron beam-induced Ge-Au amorphous thin film material and a method for rapid crystallization of amorphous thin films. Summary of the Invention

[0004] To address the technical challenges of traditional vapor deposition for Ge-Au amorphous thin films, such as stringent conditions and difficulty in large-area film formation, the lack of dynamic stress release mechanisms in conventional liquid-phase film formation systems leading to microcracks due to drastic volume contraction during rapid electron beam crystallization, and the lack of an efficient internal heat conduction network resulting in heat localization and limited crystal growth rate, this invention provides an electron beam-induced Ge-Au amorphous thin film material and a method for rapid crystallization of amorphous thin films.

[0005] In a first aspect, the present invention provides an electron beam-induced Ge-Au amorphous thin film material, employing the following technical solution: An electron beam-induced Ge-Au amorphous thin film material comprises the following raw materials in parts by weight: 55-62 parts of Ge-Au amorphous nanoparticle liquid, 12-16 parts of water-soluble film-forming agent, 10-14 parts of freeze-drying crosslinking agent, 2-4 parts of freeze-drying protectant, 4-6 parts of electron beam sensitizer, 0.5-1 part of thermo-acid catalyst, and 0.1-0.2 parts of defoamer.

[0006] Preferably, the Ge-Au amorphous nanoparticle liquid is prepared by mixing Ge-Au amorphous nanoparticles, nonionic surfactants, antioxidants, and deoxygenated deionized water in a mass ratio of 8-12:1-3:0.5-1:80-100.

[0007] Preferably, the Ge-Au amorphous nanoparticles are prepared by co-reduction of germanium tetrachloride and anhydrous gold trichloride in anhydrous tetrahydrofuran under inert gas protection via sodium naphthalene solution.

[0008] Preferably, the Ge-Au amorphous nanoparticles are prepared by the following method: Under argon protection, germanium tetrachloride and anhydrous gold trichloride were dissolved in anhydrous tetrahydrofuran. The reaction system was placed in an ice-water bath, and 0.4-0.6 mol / L sodium naphthalene-tetrahydrofuran solution was added dropwise while stirring. After the addition was complete, the temperature was raised to 20-30℃ and the reaction was stirred for 10-14 h. The precipitate was collected by centrifugation, washed, and vacuum dried to obtain Ge-Au amorphous nanoparticles.

[0009] Preferably, the molar ratio of germanium tetrachloride to anhydrous gold trichloride is 4-6:4-6.

[0010] Preferably, the amount of anhydrous tetrahydrofuran is 100-120 times the total mass of germanium tetrachloride and anhydrous gold trichloride.

[0011] Preferably, the molar ratio of sodium naphthalene to total metal salt (germanium tetrachloride and anhydrous gold trichloride) is 4-4.5:1.

[0012] Preferably, the temperature of the ice-water bath is 0-4℃.

[0013] Preferably, the stirring speed is 1000-1200 rpm.

[0014] Preferably, the centrifugation speed is 8000-10000 rpm and the centrifugation time is 8-15 min.

[0015] Preferably, the vacuum drying parameters are as follows: temperature 30-40℃, vacuum degree <100Pa, and time 20-24h.

[0016] Preferably, the nonionic surfactant is polyethylene glycol octylphenyl ether.

[0017] Preferably, the antioxidant is sodium hypophosphite.

[0018] Preferably, the water-soluble film-forming agent is polyvinyl alcohol with a degree of alcoholysis of 86-90%.

[0019] Preferably, the freeze-drying crosslinking agent is composed of glyoxal and boric acid mixed in a mass ratio of 6-8:2-4.

[0020] Preferably, the freeze-drying protectant is trehalose and / or mannitol.

[0021] Preferably, the electron beam sensitizer is a modified multi-walled carbon nanotube.

[0022] Preferably, the modified multi-walled carbon nanotubes are prepared by the following method: (1) Add multi-walled carbon nanotubes to a mixed acid, disperse by ultrasonication, heat to 70-80℃ and stir under reflux for 4-6 hours, wash, vacuum dry, grind to obtain surface carboxylated multi-walled carbon nanotubes. (2) Surface carboxylated multi-walled carbon nanotubes were dispersed in N,N-dimethylformamide, and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide were added and activated at 20-30℃ for 2-3h. Then, p-aminothiophenol and terminal amino polyether were added and reacted at 40-50℃ for 15-20h. After centrifugation, washing and vacuum drying, modified multi-walled carbon nanotubes were obtained.

[0023] Preferably, in step (1), the solid-liquid mass ratio of multi-walled carbon nanotubes to mixed acid is 1:40-50.

[0024] Preferably, in step (1), the mixed acid consists of concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 2-4:1.

[0025] Preferably, in step (1), the mass fraction of concentrated sulfuric acid is 98%.

[0026] Preferably, in step (1), the mass fraction of concentrated nitric acid is 65-68%.

[0027] Preferably, in step (1), the ultrasonic temperature is 20-30℃, the ultrasonic power is 300-400W, the ultrasonic frequency is 28-32kHz, and the ultrasonic time is 1-2h.

[0028] Preferably, in step (1), the vacuum drying temperature is 60-70℃ and the vacuum drying time is 12-16h.

[0029] Preferably, in step (1), grinding refers to grinding and passing through a 200-300 mesh sieve.

[0030] Preferably, in step (2), the amino-terminated polyether is trimethylolpropane tripropylene glycol ether (amino-terminated).

[0031] Preferably, in step (2), the mass ratio of surface carboxylated multi-walled carbon nanotubes, N,N-dimethylformamide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, N-hydroxysuccinimide, p-aminothiophenol and terminal amino polyether is 10:200:2:2:2-4:10-15.

[0032] Preferably, in step (2), the centrifugation speed is 8000-10000 rpm and the time is 10-15 min.

[0033] Preferably, in step (2), the vacuum drying temperature is 55-65℃, the vacuum degree is <100Pa, and the time is 20-24h.

[0034] Preferably, the thermogenic acid catalyst is p-toluenesulfonic acid pyridinium salt or ammonium chloride.

[0035] Preferably, the defoamer is a polydimethylsiloxane emulsion.

[0036] Secondly, this invention provides a method for rapid crystallization of Ge-Au amorphous thin films induced by an electron beam, employing the following technical solution: A method for rapid crystallization of Ge-Au amorphous thin films induced by electron beam includes the following steps: S1. The water-soluble film-forming agent is dissolved in deionized water and cooled to room temperature. Then, it is stirred and mixed with Ge-Au amorphous nanoparticle liquid, lyophilization crosslinking agent, lyophilization protectant, electron beam sensitizer, thermo-acid catalyst and defoamer and ultrasonically dispersed to obtain film-forming precursor liquid. S2. The film-forming precursor liquid is uniformly spin-coated onto the substrate surface, preheated for gelation and crosslinking, pre-frozen, and then transferred to a freeze dryer for sublimation drying to obtain an electron beam induced Ge-Au amorphous thin film. S3. Under vacuum conditions, an electron beam emission source is used to perform regional scanning irradiation to induce crystallization of amorphous thin films, thereby achieving rapid crystallization of Ge-Au amorphous thin films induced by electron beam.

[0037] Preferably, in step S1, the stirring temperature is 20-30℃, the stirring speed is 600-800 rpm, and the stirring time is 10-20 min.

[0038] Preferably, in step S1, the ultrasonic temperature is 25-35℃, the ultrasonic power is 400-500W, the ultrasonic frequency is 30-40kHz, the ultrasonic mode is 3s working, 2s intermittent, and the total ultrasonic time is 1-2h.

[0039] Preferably, in step S2, the substrate is a monocrystalline silicon wafer or quartz glass.

[0040] Preferably, in step S2, the spin coating speed is 2000-3000 rpm and the time is 30-50 s.

[0041] Preferably, in step S2, the preheating gelation crosslinking temperature is 50-60℃ and the time is 10-20 min.

[0042] Preferably, in step S2, the pre-freezing temperature is -40 to -50°C, and the time is 2-4 hours.

[0043] Preferably, in step S2, sublimation drying refers to: under a vacuum degree <10Pa, setting the cold trap temperature to -60 to -80°C and the partition sublimation temperature to -10 to -20°C, and performing sublimation drying for 12-24 hours.

[0044] Preferably, in step S3, the vacuum conditions refer to: a temperature of 20-30°C and a vacuum degree of 10. -5 Up to 10 -6 Torr.

[0045] Preferably, in step S3, the accelerating voltage of the electron beam is 8-14 kV, and the current density is 30-50 μA / cm². 2 The spot diameter is 0.5-2μm and the scanning rate is 700-800nm / s.

[0046] Preferably, in step S3, the stable crystalline phase induced during crystallization is a eutectic structure containing polycrystalline Ge and polycrystalline Au, as well as a partially metastable tetragonal Ge-Au composite phase.

[0047] In summary, the present invention has the following beneficial effects: (1) This invention introduces glyoxal and boric acid as freeze-drying crosslinking agents during the freeze-drying and heat-crosslinking process, forming a dynamic double crosslinking network between the water-soluble film-forming agent polyvinyl alcohol matrix and the carbon nanotubes grafted with terminal amino groups; wherein, the highly active aldehyde group of glyoxal undergoes an acetalization reaction with the hydroxyl groups of polyvinyl alcohol on the one hand, and a Schiff base reaction with the terminal amino groups on the surface of carbon nanotubes on the other hand, forming an irreversible covalent backbone, firmly anchoring the carbon nanotube thermally conductive network to the film-forming matrix, thereby maintaining the integrity of the macroscopic structure of the film; boric acid and polyvinyl alcohol Adjacent hydroxyl groups complex to form reversible dynamic diol-boron ester bonds. When a high-energy electron beam induces localized rapid crystallization and generates huge intrinsic tensile and contractile internal stresses, accompanied by localized rapid heating, the dynamic diol-boron ester bonds, as sacrificial bonds, undergo thermal dissociation and mechanical fracture first. Through the breaking of chemical bonds and subsequent molecular chain friction, the strain energy generated by phase transformation contraction is dissipated, thereby effectively avoiding stress concentration at grain boundaries, significantly reducing the probability of microcrack formation in the film, and maintaining the integrity of the macroscopic structure during the transformation from amorphous to crystalline phase. Simultaneously, this invention employs a liquid-phase mixing, spin-coating, and freeze-drying crosslinking film formation process, requiring only localized vacuum during the electron beam direct writing stage. This effectively solves the bottleneck of requiring extremely high vacuum for large-area film formation in traditional vapor deposition, enabling large-area, industrialized continuous production.

[0048] (2) In this invention, p-aminothiophenol and amino-terminated polyether are used to co-graft modified surface carboxylated multi-walled carbon nanotubes. The thiol (-SH) of p-aminothiophenol can specifically bind with Ge-Au amorphous nanoparticles to form stable Au-S covalent bonds, which firmly anchor them to the surface of carbon nanotubes, remove the amorphous polymer thermal resistance layer at the interface, and improve the heat spread conduction efficiency during direct electron beam writing. The long flexible chain segments of the amino-terminated polyether can entangle with the water-soluble film-forming agent network, enhance the compatibility and interfacial bonding of the organic-inorganic interface inside the film, and at the same time give the crosslinking network excellent flexibility, so that the film can undergo elastic deformation when the amorphous phase is rapidly transformed into the crystalline phase and causes severe volume shrinkage, thereby effectively absorbing and buffering internal stress. In this invention, p-aminothiophenol provides a highly thermally conductive lattice vibration coupling channel, which, together with the long flexible and highly elastic buffer chain of the amino-terminated polyether, can effectively suppress the generation of microcracks while improving the crystallization spread rate of the amorphous film.

[0049] (3) By introducing a thermo-acid catalyst, the present invention maintains the neutral stability of the system during the room temperature solution preparation and spin coating stages, thus avoiding premature gelation of polyvinyl alcohol and glyoxal. In the preheating gelation stage after spin coating, the thermo-acid catalyst is released by heat, triggering the acetalization crosslinking network. The subsequent freeze-drying process solidifies and retains the porous structure of the dynamic network, effectively ensuring the uniformity and film quality of the film. Detailed Implementation

[0050] The present invention will be further described in detail below with reference to the embodiments.

[0051] For experiments not specifically described in the examples, the procedures or conditions should be followed according to the conventional experimental procedures described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products.

[0052] Among them, multi-walled carbon nanotubes: CAS No. 68647-86-9, crystalline tubular shape, tube diameter 5-10nm, tube length <30um, purity 99.9%, purchased from Shanghai Maoguo Nanotechnology Co., Ltd. Trimethylolpropane tripropylene glycol ether (amino-terminated): namely polyetheramine ZT-403, CAS No. 39423-51-3, purchased from Hubei Weistin Technology Co., Ltd. Polyethylene glycol octylphenyl ether: Triton X-100, CAS No. 9002-93-1, purchased from Wuhan Huaxiang Kejie Biotechnology Co., Ltd.; Polyvinyl alcohol: Specifications 17-88, degree of alcoholysis 86-90%, purchased from Inner Mongolia Shuangxin Environmental Protection Materials Co., Ltd.; Polydimethylsiloxane emulsion: Model DF-7133, purchased from Anhui Zhongen Chemical Co., Ltd.

[0053] Preparation Examples 1-3 provide methods for preparing Ge-Au amorphous nanoparticles.

[0054] Preparation Example 1 Ge-Au amorphous nanoparticles were prepared by the following method: Under argon protection, germanium tetrachloride and anhydrous gold trichloride were dissolved in anhydrous tetrahydrofuran (the molar ratio of germanium tetrachloride to anhydrous gold trichloride was 4:6, and the amount of anhydrous tetrahydrofuran was 100 times the total mass of germanium tetrachloride and anhydrous gold trichloride). The reaction system was placed in an ice-water bath at 0℃, and a 0.4 mol / L sodium naphthalene-tetrahydrofuran solution (the molar ratio of sodium naphthalene to the total metal salt (the sum of germanium tetrachloride and anhydrous gold trichloride) was added dropwise at 1000 rpm, with the addition completed within 30 min. After the addition was completed, the temperature was raised to 20℃ and the reaction was stirred for 14 h. Finally, the mixture was centrifuged at 8000 rpm for 15 min, the precipitate was collected, and washed three times each with anhydrous ethanol and deionized water to remove naphthalene and salt byproducts. Finally, the mixture was vacuum dried at 30℃ and 75 Pa for 24 h to obtain Ge-Au amorphous nanoparticles.

[0055] Preparation Example 2 Ge-Au amorphous nanoparticles were prepared by the following method: Under argon protection, germanium tetrachloride and anhydrous gold trichloride were dissolved in anhydrous tetrahydrofuran (the molar ratio of germanium tetrachloride to anhydrous gold trichloride was 5:5, and the amount of anhydrous tetrahydrofuran was 110 times the total mass of germanium tetrachloride and anhydrous gold trichloride). The reaction system was placed in an ice-water bath at 2°C, and a 0.5 mol / L sodium naphthalene-tetrahydrofuran solution (the molar ratio of sodium naphthalene to the total metal salt (the sum of germanium tetrachloride and anhydrous gold trichloride) was added dropwise at 1100 rpm, with the addition completed within 30 min. After the addition was completed, the temperature was raised to 25°C and the reaction was stirred for 12 h. Finally, the mixture was centrifuged at 9000 rpm for 12 min, and the precipitate was collected. It was washed three times each with anhydrous ethanol and deionized water to remove naphthalene and salt byproducts. Finally, it was vacuum dried at 35°C and 85 Pa for 22 h to obtain Ge-Au amorphous nanoparticles.

[0056] Preparation Example 3 Ge-Au amorphous nanoparticles were prepared by the following method: Under argon protection, germanium tetrachloride and anhydrous gold trichloride were dissolved in anhydrous tetrahydrofuran (the molar ratio of germanium tetrachloride to anhydrous gold trichloride was 6:4, and the amount of anhydrous tetrahydrofuran was 120 times the total mass of germanium tetrachloride and anhydrous gold trichloride). The reaction system was placed in an ice-water bath at 4°C, and a 0.6 mol / L sodium naphthalene-tetrahydrofuran solution (the molar ratio of sodium naphthalene to the total metal salt (the sum of germanium tetrachloride and anhydrous gold trichloride) was added dropwise at 1200 rpm, with the addition completed within 30 min. After the addition was completed, the temperature was raised to 30°C and the reaction was stirred for 10 h. Finally, the mixture was centrifuged at 10000 rpm for 8 min, and the precipitate was collected. It was washed three times each with anhydrous ethanol and deionized water to remove naphthalene and salt byproducts. Finally, it was vacuum dried at 40°C and 95 Pa for 20 h to obtain Ge-Au amorphous nanoparticles.

[0057] Preparation Examples 4-6 and Comparative Preparation Examples 1-3 provide methods for preparing modified multi-walled carbon nanotubes.

[0058] Preparation Example 4 Modified multi-walled carbon nanotubes were prepared by the following method: (1) Multi-walled carbon nanotubes were added to a mixed acid (the mixed acid consisted of concentrated sulfuric acid with a mass fraction of 98% and concentrated nitric acid with a mass fraction of 65% in a volume ratio of 2:1) at a solid-liquid mass ratio of 1:40. The ultrasonic power was controlled at 300W and the ultrasonic frequency at 28kHz at 20℃. The mixture was ultrasonically dispersed for 2h. Then the temperature was raised to 70℃ and the mixture was refluxed and stirred at 400rpm for 6h. After the reaction was completed, the reaction product was washed with deionized water until the washing liquid was neutral. The washed reaction product was placed in a vacuum drying oven at 60℃ and dried for 16h. The product was then ground through a 200-mesh sieve to obtain surface carboxylated multi-walled carbon nanotubes. (2) The mass ratio of surface carboxylated multi-walled carbon nanotubes, N,N-dimethylformamide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, N-hydroxysuccinimide, p-aminobenzenethiophenol and trimethylolpropane tripropylene glycol ether (amino-terminated) was controlled to be 10:200:2:2:2:10. The surface carboxylated multi-walled carbon nanotubes were dispersed in N,N-dimethylformamide, and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride was added. Activation of (propyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide at 20 °C for 3 h was followed by the addition of p-aminothiophenol and trimethylolpropane tripropylene glycol ether (amino-terminated), and the reaction was carried out at 40 °C for 20 h. The precipitate was collected by centrifugation at 8000 rpm for 15 min, washed three times each with deionized water and anhydrous ethanol, and finally vacuum dried at 55 °C and 75 Pa for 24 h to obtain modified multi-walled carbon nanotubes.

[0059] Preparation Example 5 Modified multi-walled carbon nanotubes were prepared by the following method: (1) Multi-walled carbon nanotubes were added to a mixed acid (the mixed acid consisted of concentrated sulfuric acid with a mass fraction of 98% and concentrated nitric acid with a mass fraction of 66% in a volume ratio of 3:1) at a solid-liquid mass ratio of 1:45. The ultrasonic power was controlled at 350W and the ultrasonic frequency at 30kHz at 25℃. The mixture was ultrasonically dispersed for 1.5h. Then the temperature was raised to 75℃ and the mixture was refluxed and stirred at 500rpm for 5h. After the reaction was completed, the reaction product was washed with deionized water until the washing liquid was neutral. The washed reaction product was placed in a vacuum drying oven at 65℃ and dried for 14h. The product was then ground through a 250-mesh sieve to obtain surface carboxylated multi-walled carbon nanotubes. (2) The mass ratio of surface carboxylated multi-walled carbon nanotubes, N,N-dimethylformamide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, N-hydroxysuccinimide, p-aminobenzylthiophenol, and trimethylolpropane tripropylene glycol ether (amino-terminated) was controlled to be 10:200:2:2:3:12.5. The surface carboxylated multi-walled carbon nanotubes were dispersed in N,N-dimethylformamide, and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride was added. Modified multi-walled carbon nanotubes were obtained by activating 3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide at 25 °C for 2.5 h, followed by the addition of p-aminothiophenol and trimethylolpropane tripropylene glycol ether (amino-terminated), and reacting at 45 °C for 17.5 h. The precipitate was collected by centrifugation at 9000 rpm for 12 min, washed three times each with deionized water and anhydrous ethanol, and finally vacuum dried at 60 °C and 85 Pa for 22 h.

[0060] Preparation Example 6 Modified multi-walled carbon nanotubes were prepared by the following method: (1) Multi-walled carbon nanotubes were added to a mixed acid (the mixed acid consisted of concentrated sulfuric acid with a mass fraction of 98% and concentrated nitric acid with a mass fraction of 68% in a volume ratio of 4:1) at a solid-liquid mass ratio of 1:50. The ultrasonic power was controlled at 400W and the ultrasonic frequency at 32kHz at 30℃. The mixture was ultrasonically dispersed for 1h. Then the temperature was raised to 80℃ and the mixture was refluxed and stirred at 600rpm for 4h. After the reaction was completed, the reaction product was washed with deionized water until the washing liquid was neutral. The washed reaction product was placed in a vacuum drying oven at 70℃ and dried for 12h. The product was then ground through a 300-mesh sieve to obtain surface carboxylated multi-walled carbon nanotubes. (2) The mass ratio of surface carboxylated multi-walled carbon nanotubes, N,N-dimethylformamide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, N-hydroxysuccinimide, p-aminobenzylthiophenol, and trimethylolpropane tripropylene glycol ether (amino-terminated) was controlled to be 10:200:2:2:4:15. The surface carboxylated multi-walled carbon nanotubes were dispersed in N,N-dimethylformamide, and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride was added. Modified multi-walled carbon nanotubes were obtained by activating 3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide at 30 °C for 2 h, followed by the addition of p-aminothiophenol and trimethylolpropane tripropylene glycol ether (amino-terminated). The reaction was carried out at 50 °C for 15 h, and the precipitate was collected by centrifugation at 10,000 rpm for 10 min. The precipitate was washed three times each with deionized water and anhydrous ethanol, and finally vacuum dried at 65 °C and 95 Pa for 20 h.

[0061] Comparative Preparation Example 1 Modified multi-walled carbon nanotubes were prepared by the following method: The mass ratio of multi-walled carbon nanotubes, N,N-dimethylformamide, p-aminothiophenol, and trimethylolpropane tripropylene glycol ether (amino-terminated) was controlled at 10:200:2:10. The multi-walled carbon nanotubes were dispersed in N,N-dimethylformamide, and p-aminothiophenol and trimethylolpropane tripropylene glycol ether (amino-terminated) were added. The mixture was ultrasonically dispersed at 40℃ with an ultrasonic power of 300W and an ultrasonic frequency of 28kHz for 2 hours. The precipitate was collected by centrifugation at 8000rpm for 15 minutes and washed three times each with deionized water and anhydrous ethanol. Finally, the mixture was vacuum dried at 55℃ and a vacuum degree of 75Pa for 24 hours to obtain modified multi-walled carbon nanotubes.

[0062] Comparative Preparation Example 2 Modified multi-walled carbon nanotubes were prepared by the following method: (1) Multi-walled carbon nanotubes were added to a mixed acid (the mixed acid consisted of concentrated sulfuric acid with a mass fraction of 98% and concentrated nitric acid with a mass fraction of 65% in a volume ratio of 2:1) at a solid-liquid mass ratio of 1:40. The ultrasonic power was controlled at 300W and the ultrasonic frequency at 28kHz at 20℃. The mixture was ultrasonically dispersed for 2h. Then the temperature was raised to 70℃ and the mixture was refluxed and stirred at 400rpm for 6h. After the reaction was completed, the reaction product was washed with deionized water until the washing liquid was neutral. The washed reaction product was placed in a vacuum drying oven at 60℃ and dried for 16h. The product was then ground through a 200-mesh sieve to obtain surface carboxylated multi-walled carbon nanotubes. (2) The mass ratio of surface carboxylated multi-walled carbon nanotubes, N,N-dimethylformamide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, N-hydroxysuccinimide and p-aminothiophenol was controlled to be 10:200:2:2:12. The surface carboxylated multi-walled carbon nanotubes were dispersed in N,N-dimethylformamide. 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide were added and activated at 20°C for 3 h. Then p-aminothiophenol was added and reacted at 40°C for 20 h. The precipitate was collected by centrifugation at 8000 rpm for 15 min. The precipitate was washed three times each with deionized water and anhydrous ethanol. Finally, the precipitate was vacuum dried at 55°C and 75 Pa for 24 h to obtain modified multi-walled carbon nanotubes.

[0063] Comparative preparation example 3 Modified multi-walled carbon nanotubes were prepared by the following method: (1) Multi-walled carbon nanotubes were added to a mixed acid (the mixed acid consisted of concentrated sulfuric acid with a mass fraction of 98% and concentrated nitric acid with a mass fraction of 65% in a volume ratio of 2:1) at a solid-liquid mass ratio of 1:40. The ultrasonic power was controlled at 300W and the ultrasonic frequency at 28kHz at 20℃. The mixture was ultrasonically dispersed for 2h. Then the temperature was raised to 70℃ and the mixture was refluxed and stirred at 400rpm for 6h. After the reaction was completed, the reaction product was washed with deionized water until the washing liquid was neutral. The washed reaction product was placed in a vacuum drying oven at 60℃ and dried for 16h. The product was then ground through a 200-mesh sieve to obtain surface carboxylated multi-walled carbon nanotubes. (2) The mass ratio of surface carboxylated multi-walled carbon nanotubes, N,N-dimethylformamide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, N-hydroxysuccinimide and trimethylolpropane tripropylene glycol ether (amino-terminated) was controlled to be 10:200:2:2:12. The surface carboxylated multi-walled carbon nanotubes were dispersed in N,N-dimethylformamide. 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide were added and activated at 20°C for 3 h. Then trimethylolpropane tripropylene glycol ether (amino-terminated) was added and reacted at 40°C for 20 h. The precipitate was collected by centrifugation at 8000 rpm for 15 min. The precipitate was washed three times each with deionized water and anhydrous ethanol. Finally, the precipitate was vacuum dried at 55°C and 75 Pa for 24 h to obtain modified multi-walled carbon nanotubes.

[0064] Examples 1-3 provide an electron beam-induced Ge-Au amorphous thin film material and a method for rapid crystallization of amorphous thin films. Example 1 An electron beam-induced Ge-Au amorphous thin film material comprises the following raw materials in parts by weight: 55 parts of Ge-Au amorphous nanoparticle liquid, 12 parts of water-soluble film-forming agent, 10 parts of freeze-drying crosslinking agent, 2 parts of freeze-drying protectant, 4 parts of electron beam sensitizer, 0.5 parts of thermo-acid catalyst, and 0.1 parts of defoamer. The Ge-Au amorphous nanoparticle liquid was prepared by mixing Ge-Au amorphous nanoparticles obtained in Preparation Example 1, polyethylene glycol octylphenyl ether, sodium hypophosphite and deoxygenated deionized water in a mass ratio of 8:1:0.5:80, and then sonicating for 40 minutes under the conditions of ultrasonic power of 300W and ultrasonic frequency of 28kHz until uniformly dispersed. The water-soluble film-forming agent is polyvinyl alcohol; The freeze-drying crosslinking agent is composed of glyoxal and boric acid mixed in a mass ratio of 6:2; The freeze-drying protectant is trehalose; The electron beam sensitizer was the modified multi-walled carbon nanotubes prepared in Example 4; The thermogenic acid catalyst is ammonium chloride; The defoamer is a polydimethylsiloxane emulsion.

[0065] A method for rapid crystallization of Ge-Au amorphous thin films induced by electron beam includes the following steps: S1. Dissolve the water-soluble film-forming agent in deionized water at 80℃ and prepare a polyvinyl alcohol solution with a mass fraction of 8%. After cooling to room temperature, mix it with Ge-Au amorphous nanoparticle liquid, lyophilized crosslinking agent, lyophilized protectant, electron beam sensitizer, thermo-acid catalyst and defoamer at 20℃ and 600rpm for 20min. Then control the ultrasonic temperature at 25℃, the ultrasonic power at 400W, the ultrasonic frequency at 30kHz, the ultrasonic mode at 3s working and 2s intermittent, and the total ultrasonic dispersion time at 2h to obtain the film-forming precursor liquid. S2. Control the spin coating speed to 2000 rpm and the thickness to 50 nm. Spin coat the film-forming precursor liquid uniformly onto the surface of the monocrystalline silicon wafer substrate. Preheat at 50°C for 20 min to trigger the thermo-acid catalyst for in-situ gelation and crosslinking. Then, place it in an environment of -40°C for 4 h for pre-freezing. After fully freezing, transfer it to a freeze dryer. Under a vacuum of 5 Pa, set the cold trap temperature to -60°C and the separator sublimation temperature to -10°C, and perform sublimation drying for 24 h to obtain an electron beam induced Ge-Au amorphous thin film. S3, at a temperature of 20℃ and a vacuum degree of 10... -5 Under Torr conditions, the accelerating voltage of the electron beam was controlled at 8 kV, and the current density at 30 μA / cm². 2 With a spot diameter of 0.5 μm and a scanning rate of 700 nm / s, an electron beam emission source was used to perform regional scanning irradiation-induced crystallization of amorphous thin films, thereby achieving rapid crystallization of electron beam-induced Ge-Au amorphous thin films.

[0066] Example 2 An electron beam-induced Ge-Au amorphous thin film material comprises the following raw materials in parts by weight: 58 parts of Ge-Au amorphous nanoparticle liquid, 14 parts of water-soluble film-forming agent, 12 parts of freeze-drying crosslinking agent, 3 parts of freeze-drying protectant, 5 parts of electron beam sensitizer, 0.8 parts of thermo-acid catalyst, and 0.15 parts of defoamer; The Ge-Au amorphous nanoparticle liquid was prepared by mixing Ge-Au amorphous nanoparticles obtained in Preparation Example 2, polyethylene glycol octylphenyl ether, sodium hypophosphite, and deoxygenated deionized water in a mass ratio of 10:2:0.8:90, and then sonicating for 30 minutes under the conditions of ultrasonic power of 350W and ultrasonic frequency of 30kHz until uniformly dispersed. The water-soluble film-forming agent is polyvinyl alcohol; The freeze-drying crosslinking agent is composed of glyoxal and boric acid mixed in a mass ratio of 7:3; The freeze-drying protectant is trehalose; The electron beam sensitizer was the modified multi-walled carbon nanotubes prepared in Example 5; The thermogenic acid catalyst is ammonium chloride; The defoamer is a polydimethylsiloxane emulsion.

[0067] A method for rapid crystallization of Ge-Au amorphous thin films induced by electron beam includes the following steps: S1. Dissolve the water-soluble film-forming agent in deionized water at 85°C and prepare a 10% (w / w) polyvinyl alcohol solution. After cooling to room temperature, mix it with Ge-Au amorphous nanoparticle liquid, lyophilized crosslinking agent, lyophilized protectant, electron beam sensitizer, thermo-acid catalyst and defoamer at 25°C and 700 rpm for 15 min. Then, control the ultrasonic temperature at 30°C, the ultrasonic power at 450W, the ultrasonic frequency at 35kHz, the ultrasonic mode at 3s working and 2s intermittent, and the total ultrasonic dispersion time at 1.5h to obtain the film-forming precursor solution. S2. Control the spin coating speed to 2500 rpm and the thickness to 75 nm. Spin coat the film-forming precursor liquid uniformly onto the surface of the monocrystalline silicon wafer substrate. Preheat at 55°C for 15 min to trigger the thermo-acid catalyst for in-situ gelation and crosslinking. Then, place it in an environment of -45°C for 3 h for pre-freezing. After fully freezing, transfer it to a freeze dryer. Under a vacuum of 7 Pa, set the cold trap temperature to -70°C and the separator sublimation temperature to -15°C, and perform sublimation drying for 18 h to obtain an electron beam induced Ge-Au amorphous thin film. S3, at a temperature of 25℃ and a vacuum degree of 10... -6 Under Torr conditions, the accelerating voltage of the electron beam was controlled at 11 kV, and the current density at 40 μA / cm². 2 With a spot diameter of 1.2 μm and a scanning rate of 750 nm / s, an electron beam emission source was used to perform regional scanning irradiation-induced crystallization of amorphous thin films, thereby achieving rapid crystallization of electron beam-induced Ge-Au amorphous thin films.

[0068] Example 3 An electron beam-induced Ge-Au amorphous thin film material comprises the following raw materials in parts by weight: 62 parts of Ge-Au amorphous nanoparticle liquid, 16 parts of water-soluble film-forming agent, 14 parts of freeze-drying crosslinking agent, 4 parts of freeze-drying protectant, 6 parts of electron beam sensitizer, 1 part of thermo-acid catalyst, and 0.2 parts of defoamer. The Ge-Au amorphous nanoparticle liquid was prepared by mixing Ge-Au amorphous nanoparticles obtained in Preparation Example 3, polyethylene glycol octylphenyl ether, sodium hypophosphite and deoxygenated deionized water in a mass ratio of 12:3:1:100, and then sonicating for 20 minutes under the conditions of ultrasonic power of 400W and ultrasonic frequency of 32kHz until uniformly dispersed. The water-soluble film-forming agent is polyvinyl alcohol; The freeze-drying crosslinking agent is composed of glyoxal and boric acid mixed in a mass ratio of 8:4; The freeze-drying protectant is trehalose; The electron beam sensitizer was the modified multi-walled carbon nanotubes prepared in Example 6; The thermogenic acid catalyst is ammonium chloride; The defoamer is a polydimethylsiloxane emulsion.

[0069] A method for rapid crystallization of Ge-Au amorphous thin films induced by electron beam includes the following steps: S1. Dissolve the water-soluble film-forming agent in deionized water at 90℃ and prepare a 12% (w / w) polyvinyl alcohol solution. After cooling to room temperature, mix it with Ge-Au amorphous nanoparticle liquid, lyophilized crosslinking agent, lyophilized protectant, electron beam sensitizer, thermo-acid catalyst and defoamer at 30℃ and 800 rpm for 10 min. Then control the ultrasonic temperature at 35℃, the ultrasonic power at 500W, the ultrasonic frequency at 40kHz, the ultrasonic mode at 3s working and 2s intermittent, and the total ultrasonic dispersion time at 1h to obtain the film-forming precursor solution. S2. Control the spin coating speed to 3000 rpm and the thickness to 100 nm. Spin coat the film-forming precursor liquid uniformly onto the surface of the monocrystalline silicon wafer substrate. Preheat at 60°C for 10 min to trigger the thermo-acid catalyst for in-situ gelation and crosslinking. Then, place it in a -50°C environment for pre-freezing for 2 h. After fully freezing, transfer it to a freeze dryer. Under a vacuum of 9 Pa, set the cold trap temperature to -80°C and the separator sublimation temperature to -20°C, and perform sublimation drying for 12 h to obtain an electron beam induced Ge-Au amorphous thin film. S3, at a temperature of 30℃ and a vacuum degree of 10... -6 Under Torr conditions, the accelerating voltage of the electron beam was controlled at 14 kV, and the current density at 50 μA / cm². 2 With a spot diameter of 2μm and a scanning rate of 800nm / s, an electron beam emission source was used to perform regional scanning irradiation-induced crystallization of amorphous thin films, thereby achieving rapid crystallization of Ge-Au amorphous thin films induced by electron beam.

[0070] To verify the overall performance of the electron beam-induced Ge-Au amorphous thin film provided by this invention, comparative examples 1-5 were set up, wherein: Comparative Example 1 Comparative Example 1 is the same as Example 1, except that the electron beam sensitizer is the modified multi-walled carbon nanotubes prepared in Comparative Example 1. Details are as follows: An electron beam-induced Ge-Au amorphous thin film material comprises the following raw materials in parts by weight: 55 parts of Ge-Au amorphous nanoparticle liquid, 12 parts of water-soluble film-forming agent, 10 parts of freeze-drying crosslinking agent, 2 parts of freeze-drying protectant, 4 parts of electron beam sensitizer, 0.5 parts of thermo-acid catalyst, and 0.1 parts of defoamer. The Ge-Au amorphous nanoparticle liquid was prepared by mixing Ge-Au amorphous nanoparticles obtained in Preparation Example 1, polyethylene glycol octylphenyl ether, sodium hypophosphite and deoxygenated deionized water in a mass ratio of 8:1:0.5:80, and then ultrasonicated for 40 minutes until uniformly dispersed under the conditions of ultrasonic power of 300W and ultrasonic frequency of 28kHz. The water-soluble film-forming agent is polyvinyl alcohol; The freeze-drying crosslinking agent is composed of glyoxal and boric acid mixed in a mass ratio of 6:2; The freeze-drying protectant is trehalose; The electron beam sensitizer was the modified multi-walled carbon nanotubes prepared in Comparative Preparation Example 1; The thermogenic acid catalyst is ammonium chloride; The defoamer is a polydimethylsiloxane emulsion.

[0071] A method for rapid crystallization of Ge-Au amorphous thin films induced by electron beam includes the following steps: S1. Dissolve the water-soluble film-forming agent in deionized water at 80℃ and prepare a polyvinyl alcohol solution with a mass fraction of 8%. After cooling to room temperature, mix it with Ge-Au amorphous nanoparticle liquid, lyophilized crosslinking agent, lyophilized protectant, electron beam sensitizer, thermo-acid catalyst and defoamer at 20℃ and 600rpm for 20min. Then control the ultrasonic temperature at 25℃, the ultrasonic power at 400W, the ultrasonic frequency at 30kHz, the ultrasonic mode at 3s working and 2s intermittent, and the total ultrasonic dispersion time at 2h to obtain the film-forming precursor liquid. S2. Control the spin coating speed to 2000 rpm and the thickness to 50 nm. Spin coat the film-forming precursor liquid uniformly onto the surface of the monocrystalline silicon wafer substrate. Preheat at 50°C for 20 min to trigger the thermo-acid catalyst for in-situ gelation and crosslinking. Then, place it in an environment of -40°C for 4 h for pre-freezing. After fully freezing, transfer it to a freeze dryer. Under a vacuum of 5 Pa, set the cold trap temperature to -60°C and the separator sublimation temperature to -10°C, and perform sublimation drying for 24 h to obtain an electron beam induced Ge-Au amorphous thin film. S3, at a temperature of 20℃ and a vacuum degree of 10... -5 Under Torr conditions, the accelerating voltage of the electron beam was controlled at 8 kV, and the current density at 30 μA / cm². 2 With a spot diameter of 0.5 μm and a scanning rate of 700 nm / s, an electron beam emission source was used to perform regional scanning irradiation-induced crystallization of amorphous thin films, thereby achieving rapid crystallization of electron beam-induced Ge-Au amorphous thin films.

[0072] Comparative Example 2 Comparative Example 2 is the same as Example 1, except that the electron beam sensitizer is the modified multi-walled carbon nanotubes prepared in Comparative Example 2. Details are as follows: An electron beam-induced Ge-Au amorphous thin film material comprises the following raw materials in parts by weight: 55 parts of Ge-Au amorphous nanoparticle liquid, 12 parts of water-soluble film-forming agent, 10 parts of freeze-drying crosslinking agent, 2 parts of freeze-drying protectant, 4 parts of electron beam sensitizer, 0.5 parts of thermo-acid catalyst, and 0.1 parts of defoamer. The Ge-Au amorphous nanoparticle liquid was prepared by mixing Ge-Au amorphous nanoparticles obtained in Preparation Example 1, polyethylene glycol octylphenyl ether, sodium hypophosphite and deoxygenated deionized water in a mass ratio of 8:1:0.5:80, and then ultrasonicated for 40 minutes until uniformly dispersed under the conditions of ultrasonic power of 300W and ultrasonic frequency of 28kHz. The water-soluble film-forming agent is polyvinyl alcohol; The freeze-drying crosslinking agent is composed of glyoxal and boric acid mixed in a mass ratio of 6:2; The freeze-drying protectant is trehalose; The electron beam sensitizer was the modified multi-walled carbon nanotubes prepared in Comparative Preparation Example 2; The thermogenic acid catalyst is ammonium chloride; The defoamer is a polydimethylsiloxane emulsion.

[0073] A method for rapid crystallization of Ge-Au amorphous thin films induced by electron beam includes the following steps: S1. Dissolve the water-soluble film-forming agent in deionized water at 80℃ and prepare a polyvinyl alcohol solution with a mass fraction of 8%. After cooling to room temperature, mix it with Ge-Au amorphous nanoparticle liquid, lyophilized crosslinking agent, lyophilized protectant, electron beam sensitizer, thermo-acid catalyst and defoamer at 20℃ and 600rpm for 20min. Then control the ultrasonic temperature at 25℃, the ultrasonic power at 400W, the ultrasonic frequency at 30kHz, the ultrasonic mode at 3s working and 2s intermittent, and the total ultrasonic dispersion time at 2h to obtain the film-forming precursor liquid. S2. Control the spin coating speed to 2000 rpm and the thickness to 50 nm. Spin coat the film-forming precursor liquid uniformly onto the surface of the monocrystalline silicon wafer substrate. Preheat at 50°C for 20 min to trigger the thermo-acid catalyst for in-situ gelation and crosslinking. Then, place it in an environment of -40°C for 4 h for pre-freezing. After fully freezing, transfer it to a freeze dryer. Under a vacuum of 5 Pa, set the cold trap temperature to -60°C and the separator sublimation temperature to -10°C, and perform sublimation drying for 24 h to obtain an electron beam induced Ge-Au amorphous thin film. S3, at a temperature of 20℃ and a vacuum degree of 10... -5 Under Torr conditions, the accelerating voltage of the electron beam was controlled at 8 kV, and the current density at 30 μA / cm². 2With a spot diameter of 0.5 μm and a scanning rate of 700 nm / s, an electron beam emission source was used to perform regional scanning irradiation-induced crystallization of amorphous thin films, thereby achieving rapid crystallization of electron beam-induced Ge-Au amorphous thin films.

[0074] Comparative Example 3 Comparative Example 3 is the same as Example 1, except that the electron beam sensitizer is the modified multi-walled carbon nanotubes prepared in Comparative Example 3. Details are as follows: An electron beam-induced Ge-Au amorphous thin film material comprises the following raw materials in parts by weight: 55 parts of Ge-Au amorphous nanoparticle liquid, 12 parts of water-soluble film-forming agent, 10 parts of freeze-drying crosslinking agent, 2 parts of freeze-drying protectant, 4 parts of electron beam sensitizer, 0.5 parts of thermo-acid catalyst, and 0.1 parts of defoamer. The Ge-Au amorphous nanoparticle liquid was prepared by mixing Ge-Au amorphous nanoparticles obtained in Preparation Example 1, polyethylene glycol octylphenyl ether, sodium hypophosphite and deoxygenated deionized water in a mass ratio of 8:1:0.5:80, and then ultrasonicated for 40 minutes until uniformly dispersed under the conditions of ultrasonic power of 300W and ultrasonic frequency of 28kHz. The water-soluble film-forming agent is polyvinyl alcohol; The freeze-drying crosslinking agent is composed of glyoxal and boric acid mixed in a mass ratio of 6:2; The freeze-drying protectant is trehalose; The electron beam sensitizer was the modified multi-walled carbon nanotubes prepared in Comparative Preparation Example 3; The thermogenic acid catalyst is ammonium chloride; The defoamer is a polydimethylsiloxane emulsion.

[0075] A method for rapid crystallization of Ge-Au amorphous thin films induced by electron beam includes the following steps: S1. Dissolve the water-soluble film-forming agent in deionized water at 80℃ and prepare a polyvinyl alcohol solution with a mass fraction of 8%. After cooling to room temperature, mix it with Ge-Au amorphous nanoparticle liquid, lyophilized crosslinking agent, lyophilized protectant, electron beam sensitizer, thermo-acid catalyst and defoamer at 20℃ and 600rpm for 20min. Then control the ultrasonic temperature at 25℃, the ultrasonic power at 400W, the ultrasonic frequency at 30kHz, the ultrasonic mode at 3s working and 2s intermittent, and the total ultrasonic dispersion time at 2h to obtain the film-forming precursor liquid. S2. Control the spin coating speed to 2000 rpm and the thickness to 50 nm. Spin coat the film-forming precursor liquid uniformly onto the surface of the monocrystalline silicon wafer substrate. Preheat at 50°C for 20 min to trigger the thermo-acid catalyst for in-situ gelation and crosslinking. Then, place it in an environment of -40°C for 4 h for pre-freezing. After fully freezing, transfer it to a freeze dryer. Under a vacuum of 5 Pa, set the cold trap temperature to -60°C and the separator sublimation temperature to -10°C, and perform sublimation drying for 24 h to obtain an electron beam induced Ge-Au amorphous thin film. S3, at a temperature of 20℃ and a vacuum degree of 10... -5 Under Torr conditions, the accelerating voltage of the electron beam was controlled at 8 kV, and the current density at 30 μA / cm². 2 With a spot diameter of 0.5 μm and a scanning rate of 700 nm / s, an electron beam emission source was used to perform regional scanning irradiation-induced crystallization of amorphous thin films, thereby achieving rapid crystallization of electron beam-induced Ge-Au amorphous thin films.

[0076] Comparative Example 4 Comparative Example 4 is the same as Example 1, except that the lyophilization crosslinking agent is glyoxal. Details are as follows: An electron beam-induced Ge-Au amorphous thin film material comprises the following raw materials in parts by weight: 55 parts of Ge-Au amorphous nanoparticle liquid, 12 parts of water-soluble film-forming agent, 10 parts of freeze-drying crosslinking agent, 2 parts of freeze-drying protectant, 4 parts of electron beam sensitizer, 0.5 parts of thermo-acid catalyst, and 0.1 parts of defoamer. The Ge-Au amorphous nanoparticle liquid was prepared by mixing Ge-Au amorphous nanoparticles obtained in Preparation Example 1, polyethylene glycol octylphenyl ether, sodium hypophosphite and deoxygenated deionized water in a mass ratio of 8:1:0.5:80, and then ultrasonicated for 40 minutes until uniformly dispersed under the conditions of ultrasonic power of 300W and ultrasonic frequency of 28kHz. The water-soluble film-forming agent is polyvinyl alcohol; The lyophilization crosslinking agent is glyoxal; The freeze-drying protectant is trehalose; The electron beam sensitizer was the modified multi-walled carbon nanotubes prepared in Example 4; The thermogenic acid catalyst is ammonium chloride; The defoamer is a polydimethylsiloxane emulsion.

[0077] A method for rapid crystallization of Ge-Au amorphous thin films induced by electron beam includes the following steps: S1. Dissolve the water-soluble film-forming agent in deionized water at 80℃ and prepare a polyvinyl alcohol solution with a mass fraction of 8%. After cooling to room temperature, mix it with Ge-Au amorphous nanoparticle liquid, lyophilized crosslinking agent, lyophilized protectant, electron beam sensitizer, thermo-acid catalyst and defoamer at 20℃ and 600rpm for 20min. Then control the ultrasonic temperature at 25℃, the ultrasonic power at 400W, the ultrasonic frequency at 30kHz, the ultrasonic mode at 3s working and 2s intermittent, and the total ultrasonic dispersion time at 2h to obtain the film-forming precursor liquid. S2. Control the spin coating speed to 2000 rpm and the thickness to 50 nm. Spin coat the film-forming precursor liquid uniformly onto the surface of the monocrystalline silicon wafer substrate. Preheat at 50°C for 20 min to trigger the thermo-acid catalyst for in-situ gelation and crosslinking. Then, place it in an environment of -40°C for 4 h for pre-freezing. After fully freezing, transfer it to a freeze dryer. Under a vacuum of 5 Pa, set the cold trap temperature to -60°C and the separator sublimation temperature to -10°C, and perform sublimation drying for 24 h to obtain an electron beam induced Ge-Au amorphous thin film. S3, at a temperature of 20℃ and a vacuum degree of 10... -5 Under Torr conditions, the accelerating voltage of the electron beam was controlled at 8 kV, and the current density at 30 μA / cm². 2 With a spot diameter of 0.5 μm and a scanning rate of 700 nm / s, an electron beam emission source was used to perform regional scanning irradiation-induced crystallization of amorphous thin films, thereby achieving rapid crystallization of electron beam-induced Ge-Au amorphous thin films.

[0078] Comparative Example 5 Comparative Example 5 is the same as Example 1, except that the lyophilization crosslinking agent is boric acid. Details are as follows: An electron beam-induced Ge-Au amorphous thin film material comprises the following raw materials in parts by weight: 55 parts of Ge-Au amorphous nanoparticle liquid, 12 parts of water-soluble film-forming agent, 10 parts of freeze-drying crosslinking agent, 2 parts of freeze-drying protectant, 4 parts of electron beam sensitizer, 0.5 parts of thermo-acid catalyst, and 0.1 parts of defoamer. The Ge-Au amorphous nanoparticle liquid was prepared by mixing Ge-Au amorphous nanoparticles obtained in Preparation Example 1, polyethylene glycol octylphenyl ether, sodium hypophosphite and deoxygenated deionized water in a mass ratio of 8:1:0.5:80, and then ultrasonicated for 40 minutes until uniformly dispersed under the conditions of ultrasonic power of 300W and ultrasonic frequency of 28kHz. The water-soluble film-forming agent is polyvinyl alcohol; The lyophilization crosslinking agent is boric acid; The freeze-drying protectant is trehalose; The electron beam sensitizer was the modified multi-walled carbon nanotubes prepared in Example 4; The thermogenic acid catalyst is ammonium chloride; The defoamer is a polydimethylsiloxane emulsion.

[0079] A method for rapid crystallization of Ge-Au amorphous thin films induced by electron beam includes the following steps: S1. Dissolve the water-soluble film-forming agent in deionized water at 80℃ and prepare a polyvinyl alcohol solution with a mass fraction of 8%. After cooling to room temperature, mix it with Ge-Au amorphous nanoparticle liquid, lyophilized crosslinking agent, lyophilized protectant, electron beam sensitizer, thermo-acid catalyst and defoamer at 20℃ and 600rpm for 20min. Then control the ultrasonic temperature at 25℃, the ultrasonic power at 400W, the ultrasonic frequency at 30kHz, the ultrasonic mode at 3s working and 2s intermittent, and the total ultrasonic dispersion time at 2h to obtain the film-forming precursor liquid. S2. Control the spin coating speed to 2000 rpm and the thickness to 50 nm. Spin coat the film-forming precursor liquid uniformly onto the surface of the monocrystalline silicon wafer substrate. Preheat at 50°C for 20 min to trigger the thermo-acid catalyst for in-situ gelation and crosslinking. Then, place it in an environment of -40°C for 4 h for pre-freezing. After fully freezing, transfer it to a freeze dryer. Under a vacuum of 5 Pa, set the cold trap temperature to -60°C and the separator sublimation temperature to -10°C, and perform sublimation drying for 24 h to obtain an electron beam induced Ge-Au amorphous thin film. S3, at a temperature of 20℃ and a vacuum degree of 10... -5 Under Torr conditions, the accelerating voltage of the electron beam was controlled at 8 kV, and the current density at 30 μA / cm². 2 With a spot diameter of 0.5 μm and a scanning rate of 700 nm / s, an electron beam emission source was used to perform regional scanning irradiation-induced crystallization of amorphous thin films, thereby achieving rapid crystallization of electron beam-induced Ge-Au amorphous thin films.

[0080] The overall performance of the films prepared in Examples 1-3 and Comparative Examples 1-5 of this invention was tested respectively.

[0081] 1. Surface crack density test: Electron beam scanning was used to induce crystallization in a designated area (1 mm × 1 mm field of view) on the thin film surface using a scanning electron microscope (SEM). The scanning acceleration voltage was 14 kV and the current density was 50 μA / cm². 2 The spot diameter was 2 μm, and the scanning rate was 800 nm / s. After the crystallization operation, within a 1 mm × 1 mm field of view, the number of microcracks longer than 100 nm was counted using image processing software, and the microcrack density per unit area (cracks / mm²) was calculated. 2 ).

[0082] 2. Crystal growth rate test: In-situ transmission electron microscopy (In-situ TEM) was used with an accelerating voltage of 14 kV and a current density of 50 μA / cm².2 Under continuous electron beam scanning irradiation, the growth process of crystal nuclei in the thin film was recorded in real time, the movement distance of the amorphous-crystalline phase interface was measured over time, and the intrinsic maximum crystallization expansion rate (nm / s) of the thin film material was calculated.

[0083] 3. Flexibility (bending radius) test: The prepared thin film was fabricated on a 50 μm thick flexible polyimide (PI) substrate and crystallization was induced. Bending experiments were performed on the composite film using a bending fatigue tester. The radius of curvature was continuously reduced and the surface sheet resistance was monitored in real time. When the resistance increased sharply (>10% of the initial value) or macroscopic cracks appeared under an optical microscope, the critical bending radius (mm) was recorded.

[0084] The results are shown in Table 1 below.

[0085] Table 1: As shown in Table 1, the films prepared in Examples 1-3 of this invention have low surface microcrack density, high crystallization propagation rate, and small critical bending radius. They also have excellent flexibility and resistance to microcracks, and their overall performance is far superior to that of Comparative Examples 1-5.

[0086] Comparing Example 1 with Comparative Examples 1-3, it can be seen that: Comparative Example 1 uses uncarboxylated multi-walled carbon nanotubes and modifiers (p-aminobenzylthiophenol and terminal amino polyether) in a physical blend. No chemical grafting occurs between the two, resulting in severe phase separation and aggregation of the carbon nanotubes, which cannot form strong interfacial bonds with the matrix. This leads to a sharp increase in surface crack density, a decrease in crystallization propagation rate, and a significant increase in the critical bending radius of the film. Comparative Example 2 uses p-aminobenzylthiophenol to replace the terminal amino polyether by an equal mass. The film lacks the interfacial entanglement and elastic buffering effect of long flexible chain segments, increasing the system rigidity and making it more susceptible to cracking. The shrinkage stress generated by the crystal phase transformation cannot effectively absorb energy through elastic deformation, resulting in a significant deterioration in its crack resistance and flexibility. In Comparative Example 3, an equal amount of amino-terminated polyether was used to replace p-aminothiophenol. Due to the lack of highly reactive thiol groups (-SH), the system could not specifically bind with Ge-Au amorphous nanoparticles to form Au-S covalent bonds. This resulted in a significant polymer thermal resistance layer between the carbon nanotube thermally conductive network and the Ge-Au particles. The heat injected by the local electron beam could not be rapidly extended and conducted along the carbon nanotube network, leading to a significant decrease in the crystallization expansion rate.

[0087] Comparing Example 1 with Comparative Examples 4-5, it can be seen that: Comparative Example 4 uses glyoxal to replace boric acid by an equal mass, and the system only has an irreversible covalent cross-linked framework, lacking a reversible dynamic diol-boron ester bond network. When local electron beam-induced rapid crystallization causes severe volume shrinkage, the rigid network cannot dissipate strain energy through the dissociation of chemical bonds, leading to internal stress concentration and macroscopic structural damage, and a significant increase in crack density; Comparative Example 5 uses boric acid to replace glyoxal by an equal mass, and the system lacks the irreversible covalent framework provided by acetalization and Schiff base reaction, resulting in the inability of carbon nanotubes to be firmly anchored, poor macroscopic film structure stability, displacement of the heat conduction network, and consequently a decrease in the crystallization propagation rate, and a similarly high microcrack density.

[0088] This specific embodiment is merely an explanation of the present invention and is not intended to limit the invention. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they are within the scope of the claims of the present invention.

Claims

1. An electron beam induced Ge-Au amorphous thin film material, characterized in that, The raw materials include the following parts by weight: 55-62 parts of Ge-Au amorphous nanoparticle liquid, 12-16 parts of water-soluble film-forming agent, 10-14 parts of freeze-drying crosslinking agent, 2-4 parts of freeze-drying protectant, 4-6 parts of electron beam sensitizer, 0.5-1 part of thermo-acid catalyst, and 0.1-0.2 parts of defoamer.

2. The electron beam-induced Ge-Au amorphous thin film material of claim 1, wherein, The Ge-Au amorphous nanoparticle liquid is prepared by mixing Ge-Au amorphous nanoparticles, nonionic surfactants, antioxidants, and deoxygenated deionized water in a mass ratio of 8-12:1-3:0.5-1:80-100.

3. The electron beam-induced Ge-Au amorphous thin film material of claim 2, wherein, The Ge-Au amorphous nanoparticles were prepared by co-reduction of germanium tetrachloride and anhydrous gold trichloride in anhydrous tetrahydrofuran under inert gas protection via sodium naphthalene solution.

4. The electron beam-induced Ge-Au amorphous thin film material of claim 1, wherein, The water-soluble film-forming agent is polyvinyl alcohol with a degree of alcoholysis of 86-90%.

5. The electron beam-induced Ge-Au amorphous thin film material of claim 1, wherein, The freeze-drying crosslinking agent is composed of glyoxal and boric acid mixed in a mass ratio of 6-8:2-4.

6. The electron beam-induced Ge-Au amorphous thin film material of claim 1, wherein, The electron beam sensitizer is a modified multi-walled carbon nanotube, which is prepared by the following method: (1) Add multi-walled carbon nanotubes to a mixed acid, disperse by ultrasonication, heat to 70-80℃ and stir under reflux for 4-6 hours, wash, vacuum dry, grind to obtain surface carboxylated multi-walled carbon nanotubes. (2) Surface carboxylated multi-walled carbon nanotubes were dispersed in N,N-dimethylformamide, and 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide were added and activated at 20-30℃ for 2-3h. Then, p-aminothiophenol and terminal amino polyether were added and reacted at 40-50℃ for 15-20h. After centrifugation, washing and vacuum drying, modified multi-walled carbon nanotubes were obtained.

7. The electron beam-induced Ge-Au amorphous thin film material of claim 6, wherein, In step (1), the solid-liquid mass ratio of multi-walled carbon nanotubes to mixed acid is 1:40-50; the mixed acid is composed of concentrated sulfuric acid and concentrated nitric acid in a volume ratio of 2-4:

1.

8. The electron beam-induced Ge-Au amorphous thin film material of claim 6, wherein, In step (2), the mass ratio of surface carboxylated multi-walled carbon nanotubes, N,N-dimethylformamide, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, N-hydroxysuccinimide, p-aminobenzylthiophenol and terminal amino polyether is 10:200:2:2:2-4:10-15.

9. A method for rapid crystallization of Ge-Au amorphous thin films induced by electron beam according to any one of claims 1-8, characterized in that, Includes the following steps: S1. The water-soluble film-forming agent is dissolved in deionized water and cooled to room temperature. Then, it is stirred and mixed with Ge-Au amorphous nanoparticle liquid, lyophilization crosslinking agent, lyophilization protectant, electron beam sensitizer, thermo-acid catalyst and defoamer and ultrasonically dispersed to obtain film-forming precursor liquid. S2. The film-forming precursor liquid is uniformly spin-coated onto the substrate surface, preheated for gelation and crosslinking, pre-frozen, and then transferred to a freeze dryer for sublimation drying to obtain an electron beam induced Ge-Au amorphous thin film. S3. Under vacuum conditions, an electron beam emission source is used to perform regional scanning irradiation to induce crystallization of amorphous thin films, thereby achieving rapid crystallization of Ge-Au amorphous thin films induced by electron beam.

10. The method for rapid crystallization of Ge-Au amorphous thin films induced by electron beam according to claim 9, characterized in that, In the step S3, the acceleration voltage of the electron beam is 8-14 kV, the current density is 30-50 μA / cm 2 , the spot diameter is 0.5-2 μm, and the scanning speed is 700-800 nm / s.

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