Nanoscale metal 3D printing method based on ultrafast laser multiphoton decomposition and application

Abstract

The application discloses a kind of nanoscale metal 3D printing method and application based on ultrafast laser multiphoton decomposition, the method includes S1, providing a substrate with liquid pool, there is metal carbonyl compound solution in the liquid pool, at least including one metal element in the metal carbonyl compound solution;S2, under the protection atmosphere, to the metal carbonyl compound solution in the liquid pool is carried out ultrafast laser 3D printing;S3, remove impurities to obtain nanoscale metal of 3D structure.The application is under the action of ultrafast laser and induces carbonyl metal compound to decompose, its product is metal and trace carbon monoxide, does not contain other solid components, therefore product metal purity is high, with higher mechanical strength and bending resistance, can be realized to the component proportion control in alloy product by changing the concentration ratio of different metal carbonyl compounds;Meanwhile based on the flexibility of laser 3D printing, the line width of printed metal material can be easily adjusted, so as to improve its performance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of laser preparation of micro-nano metal materials, and particularly relates to a nano-scale metal 3D printing method based on ultrafast laser multi-photon decomposition and application. BACKGROUND

[0002] Laser micro-nano 3D printing is a cutting-edge revolutionary micro-nano manufacturing technology, which can exceed the resolution limit of optical diffraction, and can print complex three-dimensional nano structures that are difficult to achieve by traditional manufacturing processes. However, laser micro-nano 3D printing usually relies on multi-photon polymerization reaction, and therefore is mainly applied to 3D printing of organic materials, which greatly limits the application potential of laser micro-nano 3D printing technology. Therefore, developing a laser micro-nano 3D printing technology for inorganic materials that does not rely on polymerization, especially a laser micro-nano 3D printing technology for metal and alloy materials with excellent performance, has important significance for promoting the development of 3D printing.

[0003] In order to further explore the material range suitable for laser micro-nano 3D printing and broaden its application scenarios. In recent years, some researches use precursor dispersion liquid with inorganic functionalized nanoparticles to print inorganic functional materials by laser micro-nano 3D printing. However, at present, laser micro-nano 3D printing of inorganic functional materials is often realized by nanoparticle composite, and the directly printed inorganic materials are often noble metals that are easy to reduce, such as Eva Blasco et al. published Fabrication of Conductive 3D Gold-Containing Microstructures via Direct Laser Writing in Advanced Materials in 2016, which prepared a bridge-shaped 3D gold wire structure as shown in Figure 1 Atsushi Ishikawa et al. published Improvement in the reduction of silver ions in aqueous solution using two-photon sensitive dye in Applied Physics Letters in 2006, which prepared a silver 3D structure as shown in Figure 2 These products present rough and porous structures, which greatly affect the mechanical properties of the products. However, there are few research reports on laser micro-nano 3D printing of high-quality base metals and alloys. SUMMARY

[0004] In order to solve the problems in the prior art and further broaden the application performance of laser micro-nano 3D printing, the application provides a nano-scale metal 3D printing method based on ultrafast laser multi-photon decomposition, which comprises the following steps,

[0005] S1, providing a substrate with a liquid pool, wherein the liquid pool contains a metal carbonyl compound solution, and the metal carbonyl compound solution contains at least one metal element;

[0006] S2, performing 3D printing on the metal carbonyl compound solution in the liquid pool under a protective atmosphere by using an ultrafast laser;

[0007] S3, removing impurities to obtain a nano-scale metal of a 3D structure.

[0008] Further, the metal element can be at least one of cobalt, molybdenum, tungsten, iron, manganese, nickel, chromium and the like, and the metal carbonyl compound solution is 1-20 mM.

[0009] Further, the solvent of the metal carbonyl compound solution comprises alkanes which are liquid at room temperature and have a boiling point higher than 150 DEG C, and preferably, the alkanes can be at least one of tetradecane, pentadecane, hexadecane, heptadecane and the like.

[0010] Further, the depth of the metal carbonyl compound solution is 10-100 microns.

[0011] It should be noted that in the application, the material of the substrate is not limited and can be metal, silicon wafer, glass and the like, as long as it is not dissolved by alkanes; meanwhile, the length and width of the liquid pool are not limited and can be freely selected according to the size of the product to be printed. The liquid pool can be formed in the structure of the substrate (i.e. the substrate with a groove structure); or the liquid pool can be made on the surface of the substrate, in which case the material of the liquid pool should satisfy the condition that it cannot be dissolved by alkanes.

[0012] Further, the parameters of the ultrafast laser include a pulse width less than 500 fs, a wavelength of 400-1050 nm, a power lower than 100 mW, a spot diameter less than 1 micron and a scanning speed of 0.2-5 microns / s.

[0013] Further, the repetition accuracy of the ultrafast laser is higher than 10 nm.

[0014] Further, the protective gas comprises nitrogen and rare gas.

[0015] It is easy to understand that in the present application, the metal carbonyl compound solution is prepared and stored in a protective atmosphere. Due to the need to maintain the metal carbonyl compound solution in the molten pool in a protective atmosphere during ultrafast laser 3D printing, in some application scenarios, the entire ultrafast laser 3D printing platform cannot be ensured to be in a protective atmosphere. At this time, a sealing cover matching the size of the liquid pool space can be prepared, and the sealing cover is used to ensure that the metal carbonyl compound solution is in a protective atmosphere during ultrafast laser 3D printing.

[0016] Further, the thickness of the metal carbonyl compound solution is 10-100 μm, and the thickness of the liquid pool is the same as or slightly greater than the thickness of the infused metal carbonyl compound solution.

[0017] The present application also provides the application of the above-mentioned nanoscale metal 3D printing method based on ultrafast laser multiphoton decomposition in the preparation of nanoscale metal materials.

[0018] Compared with the prior art, the present application has the following beneficial effects:

[0019] 1. Compared with composite ink laser 3D printing, the composition of the nanoscale 3D structure needs to be changed by changing the composition of the nanoparticles. In the present application, by adding a plurality of metal carbonyl compounds, different metal carbonyl compounds can be decomposed, nucleated and aggregated to form an alloy. Further, by changing the concentration ratio of different metal carbonyl compounds in the precursor solution, the composition ratio of the alloy product can be adjusted.

[0020] 2. The present application induces the decomposition of the metal carbonyl compound under the action of ultrafast laser, and the product is metal and trace carbon monoxide, without other solid components, so that the product metal has high purity, high mechanical strength and high bending resistance;

[0021] 3. Based on the flexibility of laser 3D printing, the line width of the printed metal material can be easily adjusted to improve its performance. BRIEF DESCRIPTION OF DRAWINGS

[0022] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the following will briefly introduce the drawings needed to be used in the embodiments or prior art description. Obviously, the drawings in the following description are some embodiments of the present application, and those skilled in the art can also obtain other drawings according to these drawings without creative labor.

[0023] Figure 1 A scanning electron microscope image of a bridge-shaped wire structure printed by two-photon reduction in the prior art is shown;

[0024] Figure 2A scanning electron microscope image of a silver 3D structure printed by two-photon reduction printing in the prior art is shown;

[0025] Figure 3 A scanning electron microscope image of a product prepared in Example 1 of the present application is shown;

[0026] Figure 4 A schematic diagram of the preparation of a metal alloy by ultrafast laser 3D printing in Example 2 of the present application is shown;

[0027] Figure 5 A scanning electron microscope image of a product prepared in Example 2 of the present application is shown;

[0028] Figure 6 An elemental energy spectrum of a product prepared in Example 2 of the present application is shown;

[0029] Figure 7 A mechanical property diagram of a single molybdenum nanowire and a molybdenum cobalt tungsten alloy nanowire prepared by the method of Example 1 and Example 2 of the present application is shown;

[0030] Figure 8 A raw material element molar ratio and a product element molar ratio in Example 3 of the present application are shown;

[0031] Figure 9 A printing line width result of nanoscale molybdenum of a 3D structure prepared in Example 4 and Example 5 of the present application is shown. DETAILED DESCRIPTION

[0032] The endpoints of the ranges and any values described herein are not limited to the precise values stated. The endpoints of the ranges are included in the range unless specifically stated otherwise. The ranges are inclusive of the endpoints.

[0033] The technical solutions in the embodiments of the present application will be described clearly and completely below with reference to the specific embodiments of the present application and the accompanying drawings. Obviously, the described embodiments are only some of the embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative work are within the scope of protection of the present application.

[0034] Example 1

[0035] A nanoscale molybdenum 3D printing method based on ultrafast laser multi-photon decomposition, comprising the following steps:

[0036] 1) In an Ar atmosphere, 0.04 mmol of molybdenum hexacarbonyl was dissolved in 20 mL of tetradecane solution, and was magnetically stirred at a speed of 150 r / min for 3 h until it was completely dissolved to obtain a precursor solution;

[0037] 2) A substrate with a liquid pool was provided, and the precursor solution prepared in step 1) was injected into the liquid pool using a pipette under an Ar atmosphere, with an injection depth of 50 μm. The liquid pool was sealed using a sealing cover, and was then transferred to a three-axis moving platform (repeating accuracy of 5 nm) of an ultrafast laser 3D printing device;

[0038] 3) The laser parameters were set as follows: pulse width of 400 fs, wavelength of 515 nm, power of 20 mW, repetition frequency of 5 MHz, scanning speed of 4 μm / s, and spot diameter of 0.5 μm. The precursor solution in the liquid pool was subjected to ultrafast laser 3D printing by setting a scanning path of a 3D structure;

[0039] 4) The liquid pool was removed, and the remaining impurity liquid was removed by repeatedly washing with tetradecane. The substrate was then placed in a vacuum drying box for drying, so that the remaining tetradecane was volatilized to obtain a 3D structure of nanoscale molybdenum.

[0040] In the process of preparing the substrate with the liquid pool, the glass slide was cleaned to remove impurities on the surface to obtain a clean substrate. A layer of polydimethylsiloxane (PDMS) film with a thickness of 50 μm was adsorbed on the clean glass slide, and then the groove structure of the glass slide was cut to obtain the liquid pool. The sealing cover matching the size of the liquid pool was prepared by using PDMS to solidify at room temperature.

[0041] The substrate used in this embodiment is a glass slide, and is not limited thereto, and can be a metal sheet, a silicon wafer or the like.

[0042] Figure 3 The scanning electron microscope image of the 3D structure of nanoscale molybdenum of Example 1 is shown, and it can be seen that the printed metal material has the characteristics of high progressiveness and good compactness.

[0043] Example 2

[0044] A nanoscale molybdenum 3D printing method based on ultrafast laser multi-photon decomposition, comprising the following steps:

[0045] 1) In an Ar atmosphere, 0.04 mmol of molybdenum hexacarbonyl, 0.02 mmol of tungsten hexacarbonyl, and 0.08 mmol of dicobalt octacarbonyl were dissolved in 20 mL of tetradecane solution, and were magnetically stirred at a speed of 150 r / min for 3 h until they were completely dissolved to obtain a precursor solution;

[0046] 2) providing a substrate with a reservoir, under Ar atmosphere, using a pipette to fill the reservoir with the precursor solution prepared in step 1) to a depth of 50 μm, using a sealing cover to seal the reservoir, and then transferring to a three-axis moving platform (repeating accuracy 5 nm) of an ultrafast laser 3D printing device;

[0047] 3) setting laser parameters: pulse width 400 fs, wavelength 515 nm, power 20 mW, repetition frequency 5 MHz, scanning speed 4 μm / s, spot diameter 0.5 μm, and setting a scanning path of the 3D structure to perform ultrafast laser 3D printing on the precursor solution in the reservoir, Figure 4 A schematic diagram showing the preparation of the product of the embodiment by ultrafast laser 3D printing is shown.

[0048] 4) removing the reservoir, repeatedly cleaning with tetradecane to remove excess impurity liquid, and then placing in a vacuum drying box to dry, so that the excess tetradecane volatilizes, to obtain a 3D structure of nanoscale molybdenum-cobalt-tungsten alloy.

[0049] The substrate and the sealing cover are prepared in the same manner as in embodiment 1.

[0050] Figure 5 and Figure 6 Scanning electron microscope images and corresponding energy spectrum images of the 3D structure of nanoscale molybdenum-cobalt-tungsten alloy of embodiment 2 are shown, and it can be seen that the printed molybdenum-cobalt-tungsten alloy is successfully prepared, and the structure presents a 3D fullerenes. This shows that compared with the current 3D printing method, the nanoscale alloy material with a complex 3D structure can be easily prepared by the method of the present application.

[0051] In order to verify the mechanical properties of the material, the same method as in embodiment 1 and embodiment 2 was used to print a single molybdenum nanowire and a molybdenum-cobalt-tungsten alloy nanowire, both with a length of 10 μm, and a tensile test was performed, and the results are shown in Figure 7 It can be seen that the mechanical properties of the prepared metal product can be easily optimized by adjusting the types of metal elements in the precursor.

[0052] Embodiment 3

[0053] A nanoscale molybdenum-cobalt alloy 3D printing method based on ultrafast laser multi-photon decomposition, comprising the following steps:

[0054] 1) under Ar atmosphere, dissolving molybdenum hexacarbonyl and octacarbonyldicobalt in 20 mL of tetradecane solution according to the molar amounts shown in Table 1, magnetically stirring at a speed of 150 r / min for 3 h until fully dissolved, to obtain a precursor solution;

[0055] 2) providing a substrate with a reservoir, under Ar atmosphere, using a pipette to fill the reservoir with the precursor solution prepared in step 1) to a depth of 50 pm, using a sealing cover to seal the reservoir, and then transferring to a three-axis moving platform (repetition accuracy 5 nm) of an ultrafast laser 3D printing device;

[0056] 3) setting laser parameters: pulse width 400 fs, wavelength 515 nm, power 20 mW, repetition frequency 5 MHz, scanning speed 4 pm / s, spot diameter 0.5 pm, and setting a 3D structure scanning path, and performing ultrafast laser 3D printing on the precursor solution in the reservoir;

[0057] 4) removing the reservoir, repeatedly cleaning with tetradecane to remove excess impurity liquid, and then placing in a vacuum drying box for drying to volatilize the excess tetradecane, to obtain a series of 3D structure molybdenum-cobalt alloys.

[0058] Table 1 Molar ratio and molar ratio results

[0059]

[0060] Figure 8 The results of the raw material molar ratio and the product molar ratio are also shown in Table 1 and Figure 8 From the data in Table 1 and

[0061] Example 4

[0062] A nanoscale molybdenum 3D printing method based on ultrafast laser multi-photon decomposition, comprising the following steps:

[0063] 1) under Ar atmosphere, dissolving 0.04 mmol of molybdenum hexacarbonyl in 20 mL of tetradecane solution, magnetically stirring at a speed of 150 r / min for 3 h to fully dissolve, to obtain a precursor solution;

[0064] 2) providing a substrate with a reservoir, under Ar atmosphere, using a pipette to fill the reservoir with the precursor solution prepared in step 1) to a depth of 50 pm, using a sealing cover to seal the reservoir, and then transferring to a three-axis moving platform (repetition accuracy 5 nm) of an ultrafast laser 3D printing device;

[0065] 3) setting laser parameters: pulse width 400 fs, wavelength 515 nm, power 20 mW, repetition frequency 5 MHz, spot diameter 0.5 pm, and scanning speeds of 0.5, 1, 2, 3 and 4 pm / s, respectively, and setting a 3D structure scanning path, and performing ultrafast laser 3D printing on the precursor solution in the reservoir;

[0066] 4) remove the reservoir, repeatedly clean the excess impurity liquid with tetradecane, and then place it in a vacuum drying box to dry, so that the excess tetradecane volatilizes, to obtain a series of 3D structure nanoscale molybdenum.

[0067] Example 5

[0068] A nanoscale molybdenum 3D printing method based on ultrafast laser multi-photon decomposition, comprising the following steps:

[0069] 1) In an Ar atmosphere, 0.04 mmol of molybdenum hexacarbonyl is dissolved in 20 mL of tetradecane solution, and is magnetically stirred at a speed of 150 r / min for 3 h until it is fully dissolved to obtain a precursor solution;

[0070] 2) Provide a substrate with a reservoir, in an Ar atmosphere, use a pipette to fill the precursor solution prepared in step 1) into the reservoir, the filling depth is 50 μm, use a sealing cover to seal the reservoir, and then transfer to the three-axis moving platform (repeating accuracy 5 nm) of the ultrafast laser 3D printing equipment;

[0071] 3) Set the laser parameters: pulse width 400 fs, wavelength 515 nm, power 13, 17.5, 22.5, 28.5, 33.4 mW, respectively, repetition frequency 5 MHz, scanning speed 4 μm / s, spot diameter 0.5 μm, and set the 3D structure scanning path, and perform ultrafast laser 3D printing on the precursor solution in the reservoir;

[0072] 4) remove the reservoir, repeatedly clean the excess impurity liquid with tetradecane, and then place it in a vacuum drying box to dry, so that the excess tetradecane volatilizes, to obtain a series of 3D structure nanoscale molybdenum.

[0073] Figure 9 The printing line width of the 3D structure nanoscale molybdenum prepared in Example 4 and Example 5 is summarized, from Figure 9 The results show that the line width of the product can be flexibly controlled by controlling the laser parameters.

[0074] To further verify the mechanical strength of the metal molybdenum prepared by the embodiment 1 of the present application, and compare with the metal molybdenum prepared by different methods in other literatures. For example, Jiachen Wang et al. published in International Journal of Refractory Metals and Hard Materials in 2022 Microstructure and mechanical properties of unalloyed molybdenum fabricated via wire arc additive manufacturing used wire arc 3D printing to prepare metal molybdenum. P. Rebesan et al. published in Additive Manufacturing in 2021 Pure molybdenum manufactured by Laser Powder Bed Fusion: Thermal and mechanical characterization at room and high temperature used laser selective ablation method to prepare pure molybdenum. Guoqing Chen et al. published in Vacuum in 2018 Study on microstructure and performance of molybdenum joint welded by electron beam studied the mechanical properties of electron beam deposited molybdenum. The tensile strength results of the test are shown in Table 2.

[0075] Table 2 tensile strength results of materials prepared by different methods

[0076] Tensile strength (GPa) Printing method 3.3 Method of the invention 0.31 Fused filament 3D printing 0.71 Laser selective ablation 0.84 Electron beam deposition

[0077] From the test results in Table 2, it can be seen that the product prepared by the present application has better mechanical properties compared with some existing 3D printing technologies.

[0078] Finally, it should be noted that the above only describes the preferred embodiments of the present application and is not intended to limit the present application. Although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art will appreciate that the technical solutions described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalent features, and any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A nanoscale metal 3D printing method based on ultrafast laser multiphoton decomposition, characterized in that, Comprising, S1, providing a substrate with a reservoir, the reservoir containing a metal carbonyl compound solution, the metal carbonyl compound solution containing at least one metal element; S2, performing ultrafast laser 3D printing on the metal carbonyl compound solution in the reservoir under a protective atmosphere; S3, removing impurities to obtain a 3D nano-metal structure; The concentration of the metal carbonyl compound solution is 1-20 mM, and the solvent of the metal carbonyl compound solution includes an alkane that is liquid at room temperature and has a boiling point higher than 150°C. The thickness of the metal carbonyl compound solution is 10-100 μm.

2. The ultrafast laser multiphoton decomposition based nanoscale metal 3D printing method according to claim 1, characterized in that, The metal element includes cobalt, molybdenum, tungsten, iron, manganese, nickel, and chromium.

3. The ultrafast laser multiphoton decomposition based nanoscale metal 3D printing method according to claim 1, wherein, The parameters of the ultrafast laser include a pulse width less than 500 fs, a wavelength of 400-1050 nm, a power lower than 100 mW, a spot diameter less than 1 μm, and a scanning speed of 0.2-5 μm / s.

4. The ultrafast laser multiphoton decomposition based nanoscale metal 3D printing method according to claim 1, wherein, The repetition accuracy of the ultrafast laser is higher than 10 nm.

5. The ultrafast laser multiphoton decomposition based nanoscale metal 3D printing method according to claim 1, wherein, The protective atmosphere includes nitrogen and a noble gas.

6. Use of the nano-metal 3D printing method based on ultrafast laser multiphoton decomposition according to any one of claims 1-5 in the preparation of a nano-metal material.

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