A method for electron beam irradiation vapor phase 3D printing of nanoglass

Abstract

The present invention relates to a method for electron beam irradiation vapor phase 3D printing of nanoglass, comprising: preparing a nanoglass sample, controlling contact between the nanoglass sample and the sample using piezoelectric ceramics, introducing a reaction gas, and irradiating the sample with an electron beam; in-situ welding the nanoglass by the reaction gas and the electron beam; cleaning the nanoglass sample with plasma after welding to remove surface impurities and promote interfacial diffusion; annealing the printed nanoglass sample at high temperature in an Ar / O2 atmosphere to eliminate defects such as vacancies; and finally, shot peening the annealed nanoglass to impact the surface with nanosilica spheres to nanonize the surface and increase 3D printing strength. The present invention is simple and efficient, with minimal damage and precise connection. The mechanical properties and chemical composition of the weld are consistent with those of the substrate, achieving perfect connection of the nanoglass, which is of great significance for optical fiber welding and 3D printing of nanoglass.

Description

Technical Field

[0001] The present invention relates to the technical field of 3D printing nanoglass, and in particular to a method for electron beam irradiation vapor phase 3D printing nanoglass. Background Art

[0002] Silica glass is one of the most important materials for engineering applications in fields such as micro-optics, photonics, microelectromechanical systems (MEMS), microfluidics, and biomedicine. However, the inadequate fabrication technology for complex micro- and nanoscale three-dimensional structures in silica glass has limited its application in microsystems, hindering major technological breakthroughs. Additive manufacturing (3D printing) is an effective method for creating complex three-dimensional structures. However, creating complex 3D structures in silica glass using 3D printing remains elusive, primarily due to the softening point of silica glass at 1100°C. State-of-the-art 3D printing and molding methods still rely on the same melting or pellet sintering steps as ancient blow molding techniques and established industrial processes. Current techniques primarily bond particles loaded with polymer binders into the desired shape. To remove the binder and fuse the silica particles into a solid structure, sintering at temperatures between 1100°C and 1300°C, performed over several days in a vacuum or inert atmosphere, is required. The high sintering temperature can easily damage the nanoglass structure, limiting the applicability of this method. Summary of the Invention

[0003] The purpose of the present invention is to provide a method for electron beam irradiation vapor phase 3D printing of nanoglass, which is simple and efficient, with minimal damage and precise connection. Most importantly, the mechanical properties and chemical composition at the interface are consistent with those of the matrix, achieving perfect connection of the nanoglass, which is of great significance for optical fiber welding and 3D printing of nanoglass.

[0004] To achieve the above object, the present invention provides the following solutions:

[0005] A method for electron beam irradiation vapor phase 3D printing of nanoglass, comprising:

[0006] A nano-glass sample is prepared, the nano-glass sample is controlled to contact with each other by piezoelectric ceramics, a reaction gas is introduced, and an electron beam is irradiated, and the nano-glass is in-situ welded by the reaction gas and the electron beam in coordination;

[0007] After welding is completed, the nanoglass sample is cleaned with plasma to remove surface impurities and promote interface diffusion. The printed nanoglass sample is annealed at high temperature in an Ar / O2 atmosphere to eliminate defects such as vacancies. The annealed nanoglass is shot peened, and nano-silica balls are used to impact the surface to nano-nize the surface and increase the 3D printing strength.

[0008] Optionally, the nanoglass sample is a silicon-based material.

[0009] Optionally, the reaction gas is a mixed gas of F-containing gas and O2.

[0010] Optionally, the ratio of the F gas to O2 is between 1 and 10.

[0011] Optionally, the intensity of the electron beam is 10 -3 ~10 3 Acm -2 .

[0012] Optionally, the room temperature condition for the in-situ welding is -50-500° C., and the sample is heated by a heating chip.

[0013] Optionally, the nanoglass sample is cleaned with plasma to remove surface impurities, promote interface diffusion, and clean the surface. Optionally, the annealing atmosphere is an Ar / O2 mixed gas in different proportions, the annealing temperature is 400°C-800°C, and the temperature is maintained for 1-10 hours.

[0014] The beneficial effects of the present invention are:

[0015] This invention achieves room-temperature 3D printing of nanoglass using electron beam irradiation combined with reactive gases under atmospheric conditions. The interface material's crystal structure and composition are identical to the original material, enabling seamless connection of the nanoglass and enabling the connection of complex, critical components. Compared to traditional techniques, this technology is simpler, more efficient, less damaging, and more precisely controllable.

[0016] This invention utilizes electron beam irradiation and gas synergy to bond nanoglass. The reactive gas is a mixture of fluorine and oxygen. The electron beam activates the reactive gas. The ionized fluorine reacts with the SiO2 under electron beam irradiation, first corroding it and exposing unformed Si and O bonds. Fresh Si and O bonds then combine to form SiO2, completing the nanoglass connection. The reaction is rapid, and the composition and structure of the solder joint remain unchanged before and after the reaction. This process is pollution-free, energy-efficient, and produces no residual stress.

[0017] After the nanoglass is connected, the method uses plasma cleaning to remove surface impurities and promote interfacial diffusion. The printed nanoglass is then subjected to high-temperature annealing in an Ar / O2 atmosphere to eliminate defects such as oxygen vacancies. Finally, the annealed nanoglass sample is shot peened, impacting the surface with nanosilica spheres to nanoscale the surface and increase 3D printing strength. The mechanical and chemical properties of the connected nanoglass remain consistent with those of the substrate, and the temperature is low, enabling direct connection to key semiconductor devices with high efficiency and excellent controllability. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0019] Figure 1 Schematic diagram of an apparatus for electron beam irradiation vapor phase 3D printing of nano-glass according to an embodiment of the present invention;

[0020] Figure 2 This is a schematic diagram of the connection of electron beam irradiated vapor phase 3D printed nano-glass according to an embodiment of the present invention;

[0021] Figure 3 This is a flow chart of electron beam irradiation vapor phase 3D printing of nanoglass according to an embodiment of the present invention;

[0022] Figure 4 The SF6:CHF3:O2 reaction gas of the embodiment of the present invention is introduced in a ratio of 4:1:1, the nano glass temperature is 25°C, and the electron beam intensity is 4A cm -2 Irradiate the contact points of the nanoglass to perform in-situ connection mapping of the nanoglass;

[0023] Figure 5 The CF4 and O2 reaction gases are introduced in the embodiment of the present invention at a ratio of 3:1, the fiber temperature is 260°C, and the electron beam intensity is 10A cm -2 Irradiate the contact point of the optical fiber to perform in-situ welding of the optical fiber;

[0024] Figure 6 The C4F8 and O2 reaction gases of the embodiment of the present invention are introduced in a ratio of 2:1, the nano glass temperature is 480°C, and the electron beam intensity is 5A cm -2 Irradiate the contact points of the nanoglass to perform in-situ connection mapping of the nanoglass;

[0025] Figure 7 The SF6:CH4:O2 reaction gas is introduced into the embodiment of the present invention, the nano glass temperature is 80°C, the ratio is 2:1:1, and the electron beam intensity is 1A cm -2 Irradiate the contact points of the nanoglass to perform in-situ connection of the nanoglass. DETAILED DESCRIPTION

[0026] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0027] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the present invention is further described in detail below with reference to the accompanying drawings and specific embodiments.

[0028] The present invention discloses a method for electron beam irradiation vapor phase 3D printing of nanoglass, comprising: preparing a nanoglass sample, controlling the contact of the nanoglass sample with piezoelectric ceramics, introducing a reaction gas, and irradiating the sample with an electron beam, wherein the reaction gas and the electron beam cooperate to perform in-situ welding of the nanoglass. After welding, the nanoglass sample is cleaned with plasma to remove surface impurities and promote interfacial diffusion. The welded sample is then subjected to high-temperature annealing in an Ar / O2 atmosphere to eliminate defects such as oxygen vacancies. Finally, a shot peening treatment is performed, in which nano-silica spheres are impacted on the surface to nanonize the surface and increase the strength of the 3D printing.

[0029] Nanoglass samples are SiO2, Si and other silicon-based materials, such as 10nm-5μm SiO2, Si nanospheres, optical fibers, etc.

[0030] After the nanoglass is 3D printed by the reaction gas and the electron beam, the nanoglass is subjected to plasma treatment. The reaction gas can be air or Ar / O2 mixed gas in different proportions to promote complete interface diffusion of the welding point and clean the surface at the same time.

[0031] The annealing temperature is 400℃-800℃, and the heat preservation time is 1-10 hours to eliminate defects such as vacancies.

[0032] like Figure 1-3As shown, the present invention relates to a method for electron beam irradiation vapor phase 3D printing of nanoglass, comprising: using real nanoglass to make a sample that can be loaded into a transmission electron microscope, then gluing the sample to an aluminum spatula and attaching it to a probe sample rod (the samples are respectively loaded into the two ends of the probe sample rod, and the two ends of the probe sample device rod include: a fixed end and a probe end). The piezoelectric ceramic probe is controlled by a probe controller to move the probe so that the sample at the fixed end of the sample rod contacts the sample at the probe end. The nanoglass sample at the fixed end is placed on a heating chip to control the sample temperature, and the sample at the probe end is placed on the aluminum spatula. Then, a reaction gas is introduced into the transmission electron microscope, and electron beam irradiation is turned on to achieve in-situ connection of the nanoglass. The present invention can achieve self-welding of the nanoglass. By connecting a computer to a camera, it is used to directly observe the perfect welding of the samples together. The welding strength can reach the mechanical strength of the nanoglass material itself. This provides important guidance for the precision welding of nanoglass and has extremely high application prospects.

[0033] Spherical nanoglass is electrostatically attached to the heating chip and mounted on a probe sample holder, which is placed at the fixed end of the holder. The probe end is a corroded tungsten needle tip. Alternatively, a sample suitable for a transmission electron microscope can be made from real optical fiber and then attached to an aluminum spatula. Mounting the probe sample holder involves first removing the outer insulation layer of the optical fiber, cutting the stripped fiber into 2mm long segments, and then attaching them to the aluminum spatula with silver glue. After drying, the segments are then placed on the probe end of the holder. Some crushed optical fiber is electrostatically attached to the heating chip.

[0034] The probe controller is used to control the piezoelectric ceramic to move the probe so that the sample at the fixed end of the sample rod contacts the sample at the probe end. The sample rod used is a transmission electron microscope in-situ probe rod. The piezoelectric ceramic at the probe end can be adjusted to accurately move the sample so that the samples at both ends of the sample rod contact each other.

[0035] The gas introduced into the electron microscope can be a mixture of SF6 / CHF3 / O2, SF6 / O2, CHF3 / O2, SF6 / CF4 / O2, CF4 / O2, SF6 / C4F8 / O2, and C4F8 / O2, where the ratio of total welding F gas to O2 is between 1 and 10.

[0036] Other samples that can be welded include silicon-based materials such as SiO2 and Si. Sample size is arbitrary and can be amorphous or crystalline. To clearly observe the atomic-level welding process in a transmission electron microscope, the thickness should be less than 150nm.

[0037] The electron beam intensity is 10 -3 ~10 3 A cm-2, welding is carried out under temperature conditions (50 ~ 500 ℃).

[0038] Different gas types, ratios, and electron beam intensities lead to different nanoglass connection efficiencies. - and Ox+. Because F-containing gases are more difficult to ionize than O2, higher electron beam intensity results in more F- ionized gases and a stronger corrosion effect. Weaker electron beam intensity results in a more pronounced growth effect. At even weaker electron beams (<0.5A cm-2), no gas is ionized, resulting in virtually no effect on nanoglass. At the same electron beam intensity, a higher ratio of F-containing gas to O2 results in a stronger corrosion effect and slower welding.

[0039] like Figure 4 As shown, the prepared nanoglass sample is first mounted on a sample rod and inserted into an ETEM (environmental spherical aberration transmission electron microscope). The nanoglass at the probe end is moved forward infinitely close to the nanoglass to be welded at the other end. SF6:CHF3:O2 reaction gas is introduced in a ratio of 4:1:1. The nanoglass temperature is 25°C, and the electron beam intensity of 4A cm-2 is irradiated at the contact point of the nanoglass. The nanoglass is perfectly welded together.

[0040] like Figure 5 As shown, the prepared optical fiber sample is first mounted on a sample rod and inserted into an ETEM (environmental spherical aberration transmission electron microscope). The optical fiber at the probe end is moved forward infinitely close to the optical fiber to be welded at the other end. CF4 and O2 reaction gases are introduced in a ratio of 3:1. The optical fiber temperature is 260°C, and the electron beam intensity of 10A cm-2 is irradiated at the contact point of the optical fiber. The nanoglass is perfectly welded together.

[0041] like Figure 6 As shown, the prepared nanoglass sample is first mounted on a sample rod and inserted into an ETEM (environmental spherical aberration transmission electron microscope). The nanoglass at the probe end is moved forward infinitely close to the nanoglass to be welded at the other end. C4F8 and O2 reaction gases are introduced in a ratio of 2:1. The nanoglass temperature is 480°C and the electron beam intensity is 5A cm -2 Irradiating the contact points of the nanoglass, the nanoglass is perfectly welded together.

[0042] like Figure 7 As shown, the prepared nanoglass sample is first mounted on a sample rod, placed on a plasma cleaner for cleaning, and then inserted into an ETEM (environmental spherical aberration transmission electron microscope). The nanoglass at the probe end is moved forward infinitely close to the nanoglass to be welded at the other end. SF6:CH4:O2 reaction gas is introduced in a ratio of 2:1:1. The nanoglass temperature is 80°C, and the electron beam intensity of 1A cm-2 is irradiated at the contact point of the nanoglass. The nanoglass is perfectly welded together.

[0043] The embodiments described above are merely descriptions of preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Without departing from the spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by persons skilled in the art should fall within the scope of protection defined by the claims of the present invention.

Claims

1. A method for electron beam irradiation vapor phase 3D printing of nano glass, characterized in that: include: A nano-glass sample is prepared, the nano-glass sample is controlled to contact with each other by piezoelectric ceramics, a reaction gas is introduced, and an electron beam is irradiated, and the nano-glass is in-situ welded by the reaction gas and the electron beam in coordination; After welding, the nanoglass sample is cleaned with plasma to remove surface impurities and promote interface diffusion. The printed nanoglass sample is annealed at high temperature in an Ar / O2 atmosphere to eliminate vacancy defects. Finally, the annealed nanoglass is shot peened, using nano-silica balls to impact the surface, nano-crystallizing the surface and increasing the 3D printing strength.

2. The method for electron beam irradiation vapor phase 3D printing nanoglass according to claim 1, characterized in that: The nano glass sample is a silicon-based material.

3. The method for electron beam irradiation vapor phase 3D printing nanoglass according to claim 1, characterized in that: The reaction gas is a mixed gas of F-containing gas and O2.

4. The method for electron beam irradiation vapor phase 3D printing nano-glass according to claim 3, characterized in that: The ratio of the F-containing gas to O2 is between 1 and 10.

5. The method for electron beam irradiation vapor phase 3D printing nano glass according to claim 1, characterized in that: The intensity of the electron beam is 10 -3 ~10 3 Acm -2 .

6. The method for electron beam irradiation vapor phase 3D printing nano-glass according to claim 1, characterized in that: The temperature condition of the in-situ welding is -50 to 500° C., and the sample is heated by a heating chip.

7. The method for electron beam irradiation vapor phase 3D printing nano-glass according to claim 1, characterized in that: Plasma is used to clean the welded nanoglass samples to remove surface impurities and promote interface diffusion.

8. The method for electron beam irradiation vapor phase 3D printing nano-glass according to claim 1, characterized in that: The annealing atmosphere is a mixed gas of Ar / O2 in different proportions, the annealing temperature is 400°C-800°C, and the heat preservation time is 1-10 hours.

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