CN115826364A - High-flux super-resolution nanometer writing method and device based on double-step two-photon effect - Google Patents
High-flux super-resolution nanometer writing method and device based on double-step two-photon effect Download PDFInfo
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Abstract
The invention discloses a high-flux super-resolution nanometer inscription method and a device based on a double-step two-photon effect.A delayed excitation light and a beam promoting photosynthesis are emitted to a digital micro-mirror device and then imaged on a photoresist with the double-step two-photon effect coated on a substrate of a three-dimensional sample platform; controlling the digital micromirror device according to the required writing structure to complete the exposure of the focal plane of the substrate, and simultaneously controlling the three-dimensional sample stage and the time delay of the excitation light and the promotion light to make the time delay be greater than the excited state S of the singlet state of the photoresist molecules 1 To multiple states T 1 Further realizing double-step two-photon effect and realizing the writing of any three-dimensional nano structure; the excitation light and the promotion light are laser beams with the same wavelength and the same repetition frequency, the pulse width of the excitation light is femtosecond, and the pulse width of the promotion light is picoseconds or nanoseconds. The invention realizes super-resolution laser writing and combines a digital micromirror device to further realize high-flux writing capability.
Description
Technical Field
The invention belongs to the field of super-resolution laser nanometer direct writing photoetching, and particularly relates to a high-flux super-resolution nanometer writing method and device based on a double-step two-photon effect.
Background
In the direct writing type writing technology, the processing resolution of electron beam direct writing and ion beam direct writing can usually reach below 5 nanometers, but the equipment is high, the processing efficiency is low, large-area preparation cannot be realized, and the processing material is limited depending on a vacuum environment. Two-photon laser direct writing is relatively cheap, can be used for writing in a conventional environment, has high precision and true three-dimensional processing capability, and is applied to research in various fields, such as preparation of micro optical elements, micromachines, micro-fluidic chips, bionic structures and the like.
Although the two-photon laser direct writing 3D photoetching technology has unique processing advantages, the processing precision still faces the problem of deficiency, the existing technology is difficult to realize the engraving with the precision of less than hundred nanometers, and the processing of complex fine structures cannot be completed. In addition, the current laser direct writing mode based on single beam scanning is low in efficiency, and the development of the technology is greatly limited, for example, the GT2 type laser direct writing system of Germany Nanocribe company writes 1mm in the process of writing 3 The three-dimensional structure of the volume takes several days.
The insufficient precision influences the important application of the technology in the fields of chip, nano-manufacturing and the like, the long time consumption not only greatly reduces the writing efficiency, but also greatly increases uncertain factors brought in the processing process, and the popularization of the technology in practical application is seriously influenced. If the laser direct writing 3D photoetching technology can realize great improvement on precision and stable increase on combination speed, the advantages of the technology are brought into play while the disadvantages of the carving precision and the carving efficiency are made up, new breakthroughs can be made for the domestic photoetching technology, the manufacturing requirements of key sensitive units, micro-nano structures and space interconnection circuits in a multifunctional sensing system are better met, and the micro-nano processing technology and equipment with high flux, high precision, ultra-high speed, three-dimensionality, complexity and large area are made possible.
Disclosure of Invention
The invention aims to provide a high-flux super-resolution nanometer writing method and a device based on a double-step two-photon effect aiming at the defects of the prior art, and the specific technical scheme is as follows:
a high flux super-resolution nanometer inscription method based on double-step two-photon effect, an excitation light and a beam promoting photosynthesis with time delay are incident to a digital micro-mirror device and then imaged on a photoresist with double-step two-photon effect coated on a substrate of a three-dimensional sample stage; controlling the digital micromirror device according to the required writing structure to complete the exposure of the focal plane of the substrate, and simultaneously controlling the three-dimensional sample stage and the time delay of the excitation light and the promotion light to make the time delay be larger than the excited state S of the singlet state of the photoresist molecules 1 To multiple states T 1 Further realizing double-step two-photon effect and realizing the writing of any three-dimensional nano structure; the excitation light and the promotion light are laser beams with the same wavelength and the same repetition frequency, the pulse width of the excitation light is femtosecond, and the pulse width of the promotion light is picoseconds or nanoseconds.
Further, the excitation light and the promotion light have a wavelength range of 400nm to 800nm.
Further, the excitation light and the boost light are delayed by more than 0.2 nanoseconds, and the excitation light pulse is irradiated on the sample before the boost light.
Further, the photoinitiator material of the double-step two-photon effect photoresist is any one of benzil, benzophenone, diacetyl and spiro [1, 3-trimethylindole- (6' -nitrobenzdihydropyran) ].
Further, the substrate is a silicon wafer substrate, a K9 glass substrate or a cover glass substrate.
A device for realizing a high-flux super-resolution nanometer writing method based on a double-step two-photon effect comprises a first light source, a second light source, a time delay module, a beam combination module, a beam expansion module, a first reflector, a digital micromirror device, a first lens, an objective lens and a three-dimensional sample stage; the first light source emits exciting light, the second light source emits modulated light, the modulated light is delayed by the delay module, the exciting light and the delayed modulated light are combined by the beam combining module, the combined light is irradiated onto the digital micromirror device after being expanded by the beam expanding module and passing through the second reflector, and the combined light is imaged on the three-dimensional sample stage through the first lens and the objective lens; and the digital micromirror device, the three-dimensional sample stage and the time delay module are matched to complete the rapid and high-precision writing of any three-dimensional pattern.
Further, the beam combining module comprises a first half glass slide, a second reflecting mirror, a polarization beam splitter prism and a quarter glass slide; the first second-half glass slide is used for modulating the polarization state of the modulated light after time delay, so that all energy is reflected after the modulated light enters the polarization splitting prism after being reflected by the second reflecting mirror; the second half glass slide modulates the polarization state of exciting light, so that all energy is transmitted after the exciting light passes through the polarization beam splitting prism; the quarter-glass is used for modulating the polarization states of the excitation light and the modulation light into circular polarization.
Further, the beam expanding module comprises a second lens, an aperture and a third lens; the aperture is located at the focal planes of the second lens and the third lens, the second lens and the third lens are used for expanding beam combining light, and the aperture is used for filtering the beam combining light.
Furthermore, the delay module is an electronic delayer, and triggers the first light source after delaying the synchronization signal of the second light source.
Further, the digital micromirror device, the first lens, the objective lens and the three-dimensional sample stage satisfy a 4F imaging relationship, that is, the distance between the digital micromirror device and the first lens is equal to the focal length of the first lens, the distance between the first lens and the objective lens is the sum of the focal lengths of the two, and the three-dimensional sample stage is located at the focal plane of the objective lens during writing.
The beneficial effects of the invention are:
based on the double-step two-photon effect, the invention utilizes two light sources with the same wavelength and with a certain time delay to irradiate the photoresist, so that the photoinitiator in the photoresist realizes two-photon absorption and triplet absorption in sequence, the similar three-photon absorption effect is completed, and the writing precision smaller than the two-photon absorption effect is realized. The invention realizes high-flux two-dimensional area array exposure by utilizing a digital micromirror array projection writing mode, realizes the writing of a three-dimensional nanostructure by combining the high-precision displacement of a three-dimensional displacement platform in the axial direction, and greatly improves the writing efficiency. And the first light source and the second light source have the same wavelength, so that the problem of center deviation of double light beams caused by system chromatic aberration is avoided. The super-diffraction limit and super-high-speed 3D writing capability realized by the method and the device can be effectively applied to emerging fields such as silicon optical chips, novel sensors, artificial intelligence, novel materials and the like.
Drawings
FIG. 1 is a graph showing the absorption of the photoinitiator in the benzil ground state and the triplet state at different wavelengths.
Fig. 2 is a schematic diagram of a high-throughput super-resolution nano-writing apparatus based on a two-step two-photon effect according to one embodiment of the present invention.
Fig. 3 is a light path diagram of the beam combining module of the present invention.
FIG. 4 is an optical path diagram of a beam expanding module according to the present invention.
FIG. 5 is a schematic diagram of the super-resolution nano-writing capability of the present invention based on the double-step two-photon effect.
In the figure, 1-a first light source, 2-a second light source, 3-a time delay module, 4-a beam combination module, 5-a beam expansion module, 6-a first reflector, 7-a digital micromirror device, 8-a first lens, 9-an objective lens, 10-a three-dimensional sample stage, 11-a first second half glass sheet, 12-a second half glass sheet, 13-a second reflector, 14-a polarization beam splitter prism, 15-a fourth glass sheet, 16-a second lens, 17-a pinhole, and 18-a third lens.
Detailed Description
Reference will now be made in detail to the exemplary embodiments, examples of which are illustrated in the accompanying drawings. When the following description refers to the accompanying drawings, like numbers in different drawings represent the same or similar elements unless otherwise indicated. The implementations described in the following exemplary examples do not represent all implementations consistent with the present application. Rather, they are merely examples of apparatus and methods consistent with certain aspects of the present application, as detailed in the appended claims.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It should also be understood that the term "and/or" as used herein refers to and encompasses any and all possible combinations of one or more of the associated listed items.
It should be understood that although the terms first, second, third, etc. may be used herein to describe various information, such information should not be limited to these terms. These terms are only used to distinguish one type of information from another. For example, first information may also be referred to as second information, and similarly, second information may also be referred to as first information, without departing from the scope of the present application. The word "if," as used herein, may be interpreted as "at \8230; \8230when" or "when 8230; \823030when" or "in response to a determination," depending on the context.
As one aspect of the invention, the high-flux super-resolution nanometer inscription method based on the double-step two-photon effect of the invention is that an excitation light and a beam promoting light combination with time delay are incident to a digital micro-mirror device and then imaged on a photoresist with the double-step two-photon effect coated on a substrate of a three-dimensional sample platform; controlling the digital micromirror device according to the required writing structure to complete the exposure of the focal plane of the substrate, and simultaneously controlling the three-dimensional sample stage and the time delay of the excitation light and the promotion light to make the time delay be larger than the excited state S of the singlet state of the photoresist molecules 1 To a plurality ofHeavy state T 1 Further realizing double-step two-photon effect and realizing the writing of any three-dimensional nano structure; the excitation light and the promotion light are laser beams with the same wavelength and the same repetition frequency, the pulse width of the excitation light is femtosecond, and the pulse width of the promotion light is picoseconds or nanoseconds.
The wavelength of the first light source 1 is selected to be 532nm, the repetition frequency is 80MHz, the pulse width is 140fs, and the diameter of emergent light is 2mm; the wavelength of the second light source 2 is selected to be 532nm, the repetition frequency is 80MHz, the pulse width is 600ps, and the diameter of emergent light is 2mm. And the time delay of the excitation light and the promotion light is controlled to be more than 0.2 nanosecond, and the excitation light pulse irradiates on the sample before the promotion light.
The photoinitiator material for the two-step two-photon effect photoresist in the example was benzil, and the other mixtures were selected from bis (2, 6-tetramethyl-4-piperidyl-1-oxy) sebacate (BTPOS) with a mass fraction of 1.7wt% benzil and pentaerythritol triacrylate (PETA), with a mass fraction of 2.1wt% bis (2, 6-tetramethyl-4-piperidyl-1-oxy) sebacate. The absorption conditions of the photoinitiator benzil ground state and the triplet state under different wavelengths are shown in fig. 1, wherein the extinction coefficient of the triplet state is uniformly divided by 100, so that the fact that the ground state has larger absorption in the wavelength range of less than 400nm, the triplet state has larger absorption in the wavelength range of more than 400nm, and the ground state has no absorption in the wavelength range of more than 450nm, namely that a better two-photon absorption phenomenon exists under the action of 532fs laser beam, and the ground state can not realize single photon absorption can be found.
As another aspect, a device for implementing a high-throughput super-resolution nano-writing method based on a two-step two-photon effect, as shown in fig. 2, includes a first light source 1, a second light source 2, a delay module 3, a beam combining module 4, a beam expanding module 5, a first reflector 6, a digital micromirror device 7, a first lens 8, an objective 9, and a three-dimensional sample stage 10; the first light source 1 emits exciting light, the second light source 2 emits modulated light, the modulated light is delayed by the delay module 3, the exciting light and the delayed modulated light are combined by the beam combining module, the combined light is expanded by the beam expanding module, and then irradiates the digital micromirror device 7 after passing through the second reflecting mirror 6, and is imaged on the three-dimensional sample table 10 through the first lens 8 and the objective lens 9; the digital micro-mirror device 7, the three-dimensional sample stage 10 and the delay module 3 are matched to complete the fast and high-precision inscribing of any three-dimensional pattern.
In the example, after the laser beam 2 is emitted by the second light source 2, the laser beam passes through the delay module 3, in the example, an electronic delay timer (PSD-065-a-MOD, micro photon devices) is adopted, and the delay of the first light source 1 is controlled to achieve the function of pulse modulation, wherein the minimum delay precision is 10ps, and the range is 50ns. The beam combining module 4 is shown in fig. 3 and comprises a first half glass sheet 11, a second half glass sheet 12, a second reflecting mirror 13, a polarization beam splitter prism 14 and a quarter glass sheet 15. The laser beam 2 is incident into the polarization beam splitter prism 14 through the second half glass 12, the second half glass 12 is rotated, and the polarization state of the laser beam 2 is adjusted to make the transmittance thereof reach the maximum value. After the laser beam 1 is emitted by the first light source 1, the laser beam passes through the first half glass 11, the second reflecting mirror 13 and the polarization beam splitter prism 14, and then is combined with the laser beam 2 to form a combined beam. Similarly, the first half slide 11 is adjusted to adjust the polarization state of the laser beam 1 so that the reflectance thereof reaches a maximum value.
The first half glass 11 and the second half glass 12 and the polarization beam splitter 14 are glass slides suitable for 532nm wavelength. The combined light at this time is composed of the laser beam 1 and the laser beam 2 with the vertical polarization states, and the combined light becomes the combination of the circularly polarized laser beam 1 and the laser beam 2 after passing through the quarter glass 15 by adjusting the quarter glass 15. And, the quarter glass 15 is selected to be suitable for a 532nm wavelength glass.
The combined beam then enters the beam expanding module 5, which as shown in fig. 4 comprises a second lens 16, an aperture 17, a third lens 18, the aperture 17 being located at the focal plane of the second lens 16 and the third lens 18, the second lens 16 and the third lens 18 being used for expanding the combined beam, the aperture 17 being used for filtering the combined beam.
In this embodiment, the focal length of the second lens 16 is 50mm, the focal length of the third lens 18 is 500mm, the magnification is 10 times, and the diameter of the small hole 17 is 15 μm, thereby completing filtering and beam expanding.
The combined beam light enters the digital micro-mirror device 7 at a certain angle after passing through the first reflecting mirror 6, the digital micro-mirror device 7 selects V-7001 of VIALUX company of Germany, the pixel is 1024 x 768, the combined beam light is suitable for a visible light wave band, and the refresh rate can reach 22Khz. When the digital micromirror device 7 is in a full-open mode, the combined beam light is transmitted to the three-dimensional sample stage 10 through the first lens 8 and the objective lens 9, the first lens 8 is a sleeve lens with the model number of TTL200, the focal length is 200mm, and the working waveband is 450-700nm. The digital micromirror device 7, the first lens 8 and the objective lens 9 meet the 4F imaging relationship, and the three-dimensional sample stage 10 can complete the motion of XYZ axes, so that the splicing of a two-dimensional printing structure and the rapid and high-precision writing of three-dimensional patterns are realized.
The first light source 1 and the second light source 2 are turned on, the relative time delay of the pulses of the first light source 1 and the second light source 5 is adjusted by the time delay module 3, in the example, the time delay is adjusted to be 2ns, and the femtosecond beam pulse is in front and the picosecond beam pulse is in back. Then, the dmd 7 is turned on and turned to the off state, and the combined beam light cannot enter the first lens 8 and further cannot reach the image plane.
The substrate is a silicon wafer substrate, a K9 glass substrate or a cover glass substrate. The method comprises the steps of coating photoresist with a double-step two-photon effect on a substrate, placing the photoresist on a focal plane of an objective lens 9, selecting benzil as a photoinitiator material of the photoresist, placing the photoresist with the double-step two-photon effect on a three-dimensional sample stage 10, and simultaneously controlling a surface exposure pattern of a digital micro-mirror device 7 and the displacement condition of the three-dimensional sample stage 10 according to the required three-dimensional structure to be inscribed, thereby realizing the inscription of any three-dimensional nano structure. In the writing process, two pulse beams in the combined beam light are used for irradiating the photoresist in sequence, so that the photoinitiator in the photoresist realizes two-photon absorption and triplet absorption in sequence, and the effect similar to three-photon absorption is achieved, as shown in fig. 5, and the writing precision smaller than the two-photon absorption effect is achieved. And the high-flux two-dimensional area array exposure is realized by utilizing a digital micromirror array projection writing mode, the writing of the three-dimensional nanostructure is realized by combining the high-precision displacement of the three-dimensional displacement table in the axial direction, and the writing efficiency is greatly improved.
Other embodiments of the present application will be apparent to those skilled in the art from consideration of the specification and practice of the disclosure disclosed herein. This application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the application and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the application being indicated by the following claims.
It will be understood that the present application is not limited to the precise arrangements described above and shown in the drawings and that various modifications and changes may be made without departing from the scope thereof. The scope of the application is limited only by the appended claims.
Claims (10)
1. A high flux super-resolution nanometer inscription method based on two-step two-photon effect is characterized in that an excitation light and a beam promoting photosynthesis with time delay are incident to a digital micro-mirror device and then imaged on a photoresist with two-step two-photon effect coated on a substrate of a three-dimensional sample stage; controlling the digital micromirror device according to the required writing structure to complete the exposure of the focal plane of the substrate, and simultaneously controlling the three-dimensional sample stage and the time delay of the excitation light and the promotion light to make the time delay be larger than the excited state S of the singlet state of the photoresist molecules 1 To multiple states T 1 Further realizing double-step two-photon effect and realizing the writing of any three-dimensional nano structure; the excitation light and the promotion light are laser beams with the same wavelength and the same repetition frequency, the pulse width of the excitation light is femtosecond, and the pulse width of the promotion light is picoseconds or nanoseconds.
2. The method of claim 1, wherein the excitation light and the promoting light have a wavelength ranging from 400nm to 800nm.
3. The method of claim 1, wherein the excitation light and the promoting light are delayed by more than 0.2 ns, and the excitation light pulse is irradiated on the sample before the promoting light.
4. The method for high-throughput super-resolution nano-writing based on two-step two-photon effect according to claim 1, wherein the photo-initiator material of the photoresist based on two-step two-photon effect is any one of benzil, benzophenone, diacetyl, spiro [1, 3-trimethylindole- (6' -nitrobenzdihydropyran) ].
5. The method for high-flux super-resolution nanometer writing based on the double-step two-photon effect according to claim 1, wherein the substrate is a silicon wafer substrate, a K9 glass substrate or a cover glass substrate.
6. A device for realizing the high-flux super-resolution nanometer writing method based on the double-step two-photon effect in any one of claims 1 to 5 is characterized by comprising a first light source (1), a second light source (2), a time delay module (3), a beam combination module (4), a beam expansion module (5), a first reflector (6), a digital micromirror device (7), a first lens (8), an objective lens (9) and a three-dimensional sample stage (10); the first light source (1) emits exciting light, the second light source (2) emits modulated light, the modulated light is delayed by the delay module (3), the exciting light and the delayed modulated light are combined by the beam combining module, the combined light is irradiated onto the digital micromirror device (7) after being expanded by the beam expanding module and passing through the second reflecting mirror (6), and the combined light is imaged on the three-dimensional sample table (10) through the first lens (8) and the objective lens (9); the digital micromirror device (7), the three-dimensional sample stage (10) and the time delay module (3) are matched to complete the rapid and high-precision writing of any three-dimensional pattern.
7. The device according to claim 6, characterized in that the beam combining module (4) comprises a first half-slide (11), a second half-slide (12), a second mirror (13), a polarizing beam splitter prism (14), a quarter-slide (15); the first half glass (11) is used for modulating the polarization state of the modulated light after time delay, so that all energy is reflected after the modulated light is reflected by the second reflecting mirror (13) and enters the polarization beam splitter prism (14); the second half glass (12) modulates the polarization state of the exciting light, so that all energy is transmitted after the exciting light passes through the polarization beam splitter prism (14); the quarter-glass (15) is used for modulating the polarization states of the excitation light and the modulated light into circular polarization.
8. The device according to claim 6, characterized in that the beam expanding module (5) comprises a second lens (16), an aperture (17), a third lens (18); the aperture (17) is located at the focal plane of the second lens (16) and the focal plane of the third lens (18), the second lens (16) and the third lens (18) are used for expanding beam combining light, and the aperture (17) is used for filtering the beam combining light.
9. The device according to claim 6, wherein the delay module (3) is an electronic delay device which delays the synchronization signal of the second light source (2) and then triggers the first light source (1).
10. The apparatus according to claim 6, wherein the digital micromirror device (7), the first lens (8), the objective lens (9) and the three-dimensional sample stage (10) satisfy a 4F imaging relationship, that is, the digital micromirror device (7) is separated from the first lens (8) by a distance equal to the focal length of the first lens (8), the first lens (8) is separated from the objective lens (9) by a distance equal to the sum of the focal lengths, and the three-dimensional sample stage (10) is located at the focal plane of the objective lens (9) during writing.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116430687A (en) * | 2023-06-14 | 2023-07-14 | 之江实验室 | High-flux super-resolution three-dimensional inscription method and system based on double light beams |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116430687A (en) * | 2023-06-14 | 2023-07-14 | 之江实验室 | High-flux super-resolution three-dimensional inscription method and system based on double light beams |
| CN116430687B (en) * | 2023-06-14 | 2023-12-15 | 之江实验室 | High-flux super-resolution three-dimensional inscription method and system based on double light beams |
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