CN116430687B - High-flux super-resolution three-dimensional inscription method and system based on double light beams - Google Patents
High-flux super-resolution three-dimensional inscription method and system based on double light beams Download PDFInfo
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Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/70—Microphotolithographic exposure; Apparatus therefor
- G03F7/70416—2.5D lithography
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- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2051—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source
- G03F7/2053—Exposure without an original mask, e.g. using a programmed deflection of a point source, by scanning, by drawing with a light beam, using an addressed light or corpuscular source using a laser
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- G—PHYSICS
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/70—Microphotolithographic exposure; Apparatus therefor
- G03F7/70008—Production of exposure light, i.e. light sources
- G03F7/70025—Production of exposure light, i.e. light sources by lasers
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/70—Microphotolithographic exposure; Apparatus therefor
- G03F7/70008—Production of exposure light, i.e. light sources
- G03F7/7005—Production of exposure light, i.e. light sources by multiple sources, e.g. light-emitting diodes [LED] or light source arrays
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/70—Microphotolithographic exposure; Apparatus therefor
- G03F7/70383—Direct write, i.e. pattern is written directly without the use of a mask by one or multiple beams
Abstract
The application relates to a super-resolution laser nanometer direct-writing lithography technology, in particular to a high-flux super-resolution three-dimensional writing method and a system based on double light beams, wherein the method comprises the steps that combined light is parallelly incident into a digital micro-mirror device and is reflected by the digital micro-mirror device to be incident into a micro-lens array, forming a focusing lattice at the focal plane of the micro lens array, imaging the focusing lattice on the surface of the double-beam photoresist to form a writing lattice with the excitation beam overlapped with the inhibition beam, and exposing the double-beam photoresist; the combined beam is obtained by combining an excitation beam and a suppression beam; the energy of each point in the inscription lattice is regulated and controlled by regulating the on-off state of the micro mirror in the digital micro mirror device area; by adjusting the energy of the inhibition beam, each point in the inscription lattice forms photoresist polymerization promotion in the central area and photoresist polymerization inhibition in the peripheral area. Compared with the prior art, the application realizes the inscription of the three-dimensional nano structure with high flux and super resolution, greatly improves the writing precision and efficiency.
Description
Technical Field
The application relates to a super-resolution laser nanometer direct-writing lithography technology, in particular to a high-flux super-resolution three-dimensional writing method and system based on double light beams.
Background
The two-photon laser direct writing technology has the characteristics of high resolution processing capability, low heat influence, wide processing materials, low environmental requirement, true three-dimensional processing capability and the like, and is always a research hot spot in the three-dimensional micro-nano processing technology. The effective improvement of two important indexes of the writing resolution and the writing speed is the core of research and development of the laser direct writing technology and is also the key for meeting the development requirements of various fields.
For writing resolution, in a strict sense, writing of any size can be achieved by strict control of laser energy and photoresist material threshold. However, in the actual writing process, the closer to the writing threshold, the more sensitive the manufacturing process is to laser energy fluctuation, and the uniformity of the writing structure is rapidly deteriorated, so that a scientific research person often adopts the diffraction resolution limit in the optical imaging field as the writing limit of the direct writing technical system. The two-photon direct writing technology is based on the nonlinear action mechanism of the femtosecond laser and the material (usually a two-photon absorption mechanism, namely, exposure dose is proportional to the square of incident light intensity), and the transverse and axial (about 2.5 times of the transverse) writing size limit of the system can be reduced to 1/. V.2. That is, if a femtosecond laser source with a wavelength of 405 nm and an objective lens with a numerical aperture of 1.4 are used, the lateral and axial inscription size limits of the system are about 125 nm and 312.5 nm.
On the other hand, for the writing efficiency, the most mature two-photon direct writing equipment in the market at present, namely Photonic Professional GT series rapid high-resolution system of Germany NanoScribe company, can achieve the writing precision of about 160 nm and the writing speed of 10mm/s, and write 1 mm 3 It takes days for the three-dimensional structure of the volume. The defect of precision influences the important application of the technology in the fields of chips, nano-manufacturing and the like, and the unique advantages of the technology are difficult to develop; the time consumption greatly reduces the inscription efficiency, and the uncertainty factor brought in the processing process is also greatly increased, which seriously influences the popularization of the technology in practical application. Therefore, the two-photon direct writing device is difficult to be truly applied to industrial production, and is difficult to produceA real technical innovation is generated.
If the laser direct writing 3D lithography technology can realize great improvement in precision and combine with steady increase in speed, the advantages of the laser direct writing 3D lithography technology are developed, the disadvantages of writing precision and writing efficiency are made up, new breakthrough can be made for the domestic lithography technology, the manufacturing requirements of key sensitive units, micro-nano structures and space interconnection circuits in a multifunctional sensing system can be better met, and the micro-nano processing technology and equipment with high flux, high precision, ultrarapidness, three-dimension, complexity and large area are possible.
Chinese patent CN202111528094.6 discloses a high-flux super-resolution laser direct writing system based on a microlens array and a DMD, the system uses a microlens array comprising m×m lens elements to generate m×m parallel beams, and combines an optical path formed by an ultraviolet femtosecond laser, a four-beam splitter, the DMD, a beam combiner, a flat beam displacement element, a lens and an objective lens to form 2m×2m focus lattice distribution on the focal plane of the objective lens, so that the laser direct writing flux based on the microlens array and the DMD is improved to 4 times of the original laser direct writing flux, the direct writing speed is greatly improved, and each focus can be independently adjusted by the DMD to realize parallel super-resolution laser direct writing of any graph by combining a direct writing algorithm. The main improvement in the technical proposal is to improve the direct writing speed by improving the laser direct writing flux; however, more supporting equipment and units are required to be additionally arranged to improve the laser direct writing flux correspondingly, so that the whole system structure is quite complex, the operation is more troublesome, and the system does not further improve the writing precision.
Chinese patent CN202211493606.4 discloses a high-flux super-resolution nanowriting method and apparatus based on two-step two-photon effect, which is to make delayed excitation light and a beam for promoting photosynthesis incident on a digital micromirror device, and then image onto a photoresist coated on a substrate of a three-dimensional sample stage and having two-step two-photon effect; controlling the digital micromirror device according to the needed writing structure to complete the exposure of the focal plane of the substrate, and simultaneously controlling the three-dimensional sample stage, the excitation light and the delay of the promotion light to ensure that the delay is greater than the singlet excited state S of the photoresist molecules 1 To multiple states T 1 Thereby realizing the two-step two-photon effect and the inscription 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 picosecond or nanosecond. In the technical proposal, the two-photon absorption and the triplet absorption are realized on the photoresist through the time delay effect, forming an effect similar to three-photon absorption, and further realizing smaller inscription precision; however, the time delay needs to be precisely controlled, the operation requirement and the control precision requirement are high, the effect similar to three-photon absorption is utilized, the writing size is difficult to be greatly reduced, the proximity effect between the time points of multi-point writing is difficult to be effectively eliminated, and the writing period is difficult to reach the expectations.
From the foregoing, the feasible solution of the two-photon laser direct writing technology proposed in the prior art still has some defects, which make it difficult to apply the two-photon laser direct writing technology on a practical scale, and thus there is still a need for improving the technology to meet the lithography requirement.
Disclosure of Invention
The application aims to solve at least one of the problems and provide a high-flux super-resolution three-dimensional inscription method and system based on double light beams, which are used for solving the problem that the laser direct-writing 3D lithography technology in the prior art is difficult to meet the demands of inscription precision and inscription efficiency, realizing inscription of a high-flux super-resolution three-dimensional nano structure and greatly improving inscription precision and efficiency.
The aim of the application is achieved by the following technical scheme:
the application discloses a high-flux super-resolution three-dimensional inscription method based on double beams, which comprises the steps that combined beams are parallelly incident to a Digital Micromirror Device (DMD) and reflected by the digital micromirror device and then are incident to a Micro Lens Array (MLA), a focusing lattice is formed at the focal plane of the micro lens array, the focusing lattice is imaged on the surface of double-beam photoresist to form inscription lattices of which excitation beams and inhibition beams coincide, the intensity distribution of the focusing points of the excitation beams and the inhibition beams is Gaussian distribution, and the double-beam photoresist is exposed;
the beam combination light is obtained by combining an excitation beam and a suppression beam;
the energy of each point in the inscription lattice is regulated and controlled by regulating the on-off state of the micro mirror in the digital micro mirror device area;
by adjusting the energy of the inhibiting light beam, each point in the inscription lattice forms photoresist polymerization promotion in the central area, photoresist polymerization inhibition is formed in the peripheral region.
Preferably, the excitation light beam is a femtosecond laser light beam, and the wavelength range is 400-800nm; the inhibition beam is any one of a continuous laser beam, a picosecond laser beam and a nanometer laser beam, and the wavelength range is 400-800nm.
Preferably, the excitation beam is of equal wavelength as the suppression beam, with minimal effect of chromatic aberration.
Preferably, the photoinitiator material in the double-beam photoresist is any one of benzil, benzophenone, diacetyl, spiro [1, 3-trimethyl indole- (6' -nitrobenzodihydropyran) ], 7-diethylamino-3-thiophenecarboxyl coumarin and 2-isopropyl thioxanthone.
The second aspect of the application discloses a system of a high-flux super-resolution three-dimensional inscription method based on double beams, which adopts any one of the methods to carry out three-dimensional inscription;
the system comprises a light source, a beam combination module, a digital micro-mirror device, a micro-lens array, an objective lens and a three-dimensional sample stage;
the light source emits an excitation light beam and a suppression light beam respectively;
the beam combination module combines the excitation beam and the inhibition beam from the light source and then makes the excitation beam and the inhibition beam enter the digital micro-mirror device, the digital micro-mirror device reflects the combined beam and makes the combined beam enter the micro-lens array, the micro-lens array forms a focusing lattice at a focal plane, and the focusing lattice forms a inscription lattice on the three-dimensional sample stage through the objective lens imaging;
the double-beam photoresist is arranged on the three-dimensional sample stage.
Preferably, the beam combining module comprises a first half glass slide, a polarization splitting prism, a second half glass slide and a second reflecting mirror;
the first half glass slide carries out polarization state modulation on a first laser beam emitted by the light source, so that all energy is transmitted after the first laser beam passes through the polarization beam splitting prism;
the second half glass plate carries out polarization state modulation on a second laser beam emitted by the light source, so that all energy is reflected after the second laser beam passes through the second reflecting mirror and enters the polarization beam splitting prism.
Preferably, the system further comprises a beam expanding module arranged between the beam combining module and the digital micro-mirror device, so that the combined beam is expanded to be matched with the effective acting area of the digital micro-mirror device;
the beam expanding module comprises a fourth lens, a small hole and a fifth lens; the small hole is arranged at the focal plane between the fourth lens and the fifth lens and is used for filtering the combined beam, and the magnification formed by the fourth lens and the fifth lens is larger than 1 and is used for expanding the combined beam.
Preferably, a first lens and a second lens are further arranged between the digital micro-mirror device and the micro-lens array in sequence, and the digital micro-mirror device, the first lens, the second lens and the micro-lens array form a 4F imaging relationship.
The 4F imaging relation is specifically that the distance between the digital micro-mirror array DMD and the first lens is equal to the focal length of the first lens, the distance between the first lens and the second lens is equal to the sum of the focal lengths of the first lens and the second lens, and the distance between the second lens and the micro-lens array MLA is equal to the focal length of the second lens.
Preferably, a first reflecting mirror is further arranged between the second lens and the micro lens array.
Preferably, a third lens is further arranged between the micro lens array and the objective lens, and a focal plane of the micro lens array, the third lens, the objective lens and the three-dimensional sample stage form a 4F imaging relationship.
The distance between the focal plane of the micro lens array MLA and the third lens is equal to the focal length of the third lens, the distance between the third lens and the objective lens is the sum of the focal lengths, and the distance between the objective lens and the three-dimensional sample stage is equal to the focal length of the objective lens.
The working principle of the application is as follows:
the double-beam photoresist has special inhibition phenomenon of inhibition light beams to excitation light beams in a super-resolution writing method, the inhibition effect is enhanced firstly along with the inhibition of the polymerization of the photoresist with the enhancement of light energy, then the inhibition effect is weakened, and then the inhibition effect is converted into a promotion phenomenon, so that the polymerization promotion phenomenon of the photoresist occurs in the three-dimensional central area of the two focused light beams, and the polymerization inhibition phenomenon of the photoresist occurs in the peripheral area; by adjusting the energy of the incident inhibition beam and utilizing the principle, super-resolution inscription of the three-dimensional structure can be realized.
Compared with the prior art, the application has the following beneficial effects:
the application utilizes the special inhibition phenomenon of the inhibition light beam to the excitation light beam in the double-beam super-resolution writing method, namely, the inhibition effect is enhanced firstly along with the enhancement of the inhibition light energy, then the inhibition effect is weakened, and then the phenomenon is converted into the promotion phenomenon, the excitation light beam and the inhibition light beam are focused on the same space region through the objective lens, and then the special phenomenon is utilized to promote the centers of two focusing points, so that the inhibition phenomenon occurs at the part with weak edge energy, not only the three-dimensional writing line width can be reduced, but also the proximity effect during multi-point writing can be effectively inhibited, and the super-resolution writing of the three-dimensional structure can be realized. The application utilizes the principle to combine two beams with the same wavelength (excitation beam and inhibition beam), combines a digital micromirror array DMD and a micro lens array MLA, forms a parallel inscription lattice at the focal plane of an objective lens, wherein each point in the inscription lattice is composed of focusing points of the excitation beam and the inhibition beam, the energy distribution of the excitation beam and the inhibition beam coincide in space, a switch of a fixed area micro mirror on the digital micromirror DMD is used for regulating and controlling the energy of each point in the inscription lattice, and combines the high-precision movement of a three-dimensional displacement table to realize inscription of a high-flux super-resolution three-dimensional nano structure, thereby greatly improving inscription precision and efficiency, and being effectively applied to the emerging fields of silicon optical chips, novel sensors, artificial intelligence, novel materials and the like.
Drawings
FIG. 1 is a schematic diagram of the system of the present application in one example;
FIG. 2 is a schematic diagram of a beam combining module according to an embodiment of the present application;
FIG. 3 is a schematic view of the beam expanding module according to the present application in an exemplary configuration;
FIG. 4 is a graph of the test results of the special suppression of the excitation beam by the suppression beam in the present application;
FIG. 5 is a graph showing the comparative test results of example 1 (double beam) and comparative example 1 (single beam);
in the figure: 1-a first light source; 2-a second light source; a 3-beam combining module; 4-a beam expanding module; a 5-digital micromirror device; 6-a first lens; 7-a second lens; 8-a first mirror; 9-a microlens array; 10-a third lens; 11-an objective lens; 12-a three-dimensional sample stage; 13-a controller; 14-a first half slide; 15-a polarization beam splitter prism; 16-second half slide; 17-a second mirror; 18-a fourth lens; 19-small holes; 20-fifth lens.
Detailed Description
The application will now be described in detail with reference to the drawings and specific examples.
Reference will now be made in detail to exemplary embodiments, examples of which are illustrated in the accompanying drawings. When the following description refers to the accompanying drawings, the same numbers in different drawings refer to the same or similar elements, unless otherwise indicated. The implementations described in the following exemplary examples do not represent all implementations consistent with the application. Rather, they are merely examples of apparatus and methods consistent with aspects of the application as detailed in the accompanying 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 specification 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 or 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, these information should not be limited by 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 application. The word "if" as used herein may be interpreted as "at … …" or "at … …" or "responsive to a determination", depending on the context.
As one aspect of the present application, a high-flux super-resolution three-dimensional writing method based on dual beams of the present application combines an excitation beam with a suppression beam (and expands the beam as needed), then makes the combined beam parallel to a digital micromirror device 5 (abbreviated as DMD), and makes the combined beam reflected by the DMD (preferably via 4F imaging) make the combined beam incident on a microlens array 9 (abbreviated as MLA), and forms a focusing lattice at the focal plane position of the combined beam after passing through the MLA, and the focusing lattice is imaged on a dual-beam photoresist to form a writing lattice where the excitation beam overlaps with the suppression beam, and the intensity distribution of the focusing points of the excitation beam and the suppression beam is gaussian.
In the method, a switch of a micromirror in a fixed area on the DMD is used for regulating and controlling the energy of each point in the inscription lattice;
in the super-resolution writing process, the energy of the incident inhibition light beam is regulated, and the special inhibition phenomenon of the inhibition light beam to the excitation light beam is inhibited in the super-resolution writing method by utilizing the double-beam photoresist, namely, the inhibition effect is enhanced firstly along with the enhancement of the photoresist polymerization by the inhibition light energy, then the inhibition effect is weakened, and then the inhibition effect is converted into the promotion phenomenon, so that the photoresist polymerization promotion phenomenon occurs in the three-dimensional central area of the two light beams focused on the surface of the double-beam photoresist, the photoresist polymerization inhibition phenomenon occurs in the peripheral area, and the super-resolution writing of the three-dimensional structure is realized.
In the method, the excitation beam can be a femtosecond laser beam, the wavelength range of which can be 400-800nm, and the inhibition beam can be a continuous laser beam, a picosecond laser beam or a nanometer laser beam, and the wavelength range of which can be 400-800nm. More preferably, if the wavelength selected by the excitation light beam and the suppression light beam is consistent, the generated chromatic aberration influence can be effectively reduced.
In this technique, the dual beam photoresist used may be any one of the existing dual beam photoresists in the art, such as benzil, benzophenone, diacetyl, spiro [1, 3-trimethylindole- (6' -nitrobenzodihydropyran) ], 7-diethylamino-3-thiophenecarboxamide coumarin and 2-isopropylthioxanthone, which are included in the dual beam photoresist.
As another aspect of the present application, an apparatus for implementing a high-flux super-resolution three-dimensional inscription method based on dual beams mainly includes a light source, a beam combination module 3, a DMD, an MLA, an objective lens 11, and a three-dimensional sample stage 12; the excitation light beam and the inhibition light beam emitted by the light source respectively enter the beam combination module 3 to be combined light and then enter the DMD, the DMD reflects the combined light beam to the MLA and enters the MLA, the MLA forms a focusing lattice with equal point-to-point distance at the focal plane, then the focusing lattice is irradiated and imaged on the surface of the double-beam photoresist carried by the three-dimensional sample stage 12 through the objective lens 11 to form a inscription lattice where the excitation light beam and the inhibition light beam coincide, the double-beam photoresist is exposed, and then the rapid and high-precision inscription of any three-dimensional pattern can be completed.
In the system, the light source comprises a first light source 1 and a second light source 2, which respectively emit an excitation light beam and a suppression light beam, and the two light sources can be arranged in a form of parallel incidence beam combination module 3.
In the system, the beam combination module 3 is at least composed of a first half glass slide 14, a polarization beam splitter prism 15, a second half glass slide 16 and a second reflecting mirror 17; the first half glass slide 14 is used for modulating the polarization state of the laser (excitation beam or inhibition beam) emitted by the first light source 1, so that all energy can be transmitted after the laser passes through the polarization beam splitter prism 15; the second half glass slide 16 modulates the polarization state of the laser (excitation beam or inhibition beam) emitted by the second light source 2, so that after the laser is reflected by the second reflecting mirror 17 and passes through the polarization splitting prism 15, all energy can be reflected, and then the beam combination of the two incident beams is realized. According to the beam combination requirement in actual use, appropriate components can be correspondingly added in the beam combination module 3 to improve the beam combination condition and improve the beam combination effect. Based on the excitation light beam and the suppression light beam which are parallel to each other, a first half glass slide 14 and a second half glass slide 16 in the beam combining module 3 are correspondingly arranged in parallel, wherein one light beam directly enters the polarization beam splitting prism 15 after passing through the first half glass slide 14 and is transmitted in the polarization beam splitting prism 15, and the other light beam enters the polarization beam splitting prism 15 after being reflected by a second reflecting mirror 17 arranged at 45 degrees and is reflected at 45 degrees again in the polarization beam splitting prism 15, so that the light beam of the polarization beam splitting prism 15 is the combined light beam of the excitation light beam and the suppression light beam.
In the system, the beam expanding module 4 can be arranged between the beam expanding module 3 and the DMD according to the requirements, so that the combined beam light which completes beam expansion after passing through the beam expanding module 4 can be matched with the effective acting area on the DMD, and can be designed into a kepler design or a Galileo design according to different use requirements. The present system may generally be of the kepler design, and in particular, the beam expanding module 4 includes a fourth lens 18 (input lens), an aperture 19 and a fifth lens 20 (output lens); wherein the aperture 19 is located at a focal plane between the fourth lens 18 and the fifth lens 20 for filtering the combined beam, and the fourth lens 18 and the fifth lens 20 are used for expanding the combined beam by a beam expanding effect generated by a focal length ratio (a beam expanding ratio is larger than 1) smaller than 1; the combined light is incident on the fourth lens 18, filtered by the small hole 19 and output by the fifth lens 20.
In the system, a first lens 6 and a second lens 7 can be sequentially arranged between the DMD and the MLA, and the DMD, the first lens 6, the second lens 7 and the MLA together form a 4F imaging relationship, namely, the distance between the DMD and the first lens 6 is equal to the focal length of the first lens 6, the distance between the first lens 6 and the second lens 7 is equal to the sum of the focal lengths of the two lenses, and the distance between the second lens 7 and the MLA is equal to the focal length of the second lens 7. In addition, a first reflecting mirror 8 is additionally arranged between the second lens 7 and the MLA, and the first reflecting mirror 8 deflects the combined beam transmitted through the second lens 7 to make the combined beam horizontally enter the MLA.
In this system, a third lens 10 is further disposed between the MLA and the objective lens 11, and the focal plane of the MLA, the third lens 10, the objective lens 11 and the three-dimensional sample stage 12 together form a 4F imaging relationship, that is, the distance between the focal plane of the MLA and the third lens 10 is equal to the focal length of the third lens 10, the distance between the third lens 10 and the objective lens 11 is the sum of both focal lengths, and the distance between the objective lens 11 and the three-dimensional sample stage 12 is equal to the focal length of the objective lens 11.
Example 1
In the scheme of the embodiment, a high-flux super-resolution three-dimensional inscription method based on double light beams comprises the following steps:
the excitation light beam emitted by the first light source 1 and the inhibition light beam emitted by the second light source 2 are firstly subjected to beam combination and beam expansion, are parallelly incident on the DMD of the digital micro-mirror device 5, are then subjected to 4F imaging on the micro-lens array 9MLA, form a focusing lattice on the focal plane of the combined light beam after the MLA, and are then imaged on the focal plane of the objective lens 11 (the double-beam photoresist is positioned on the focal plane) through the third lens 10 and the objective lens 11 to form a inscription lattice where the excitation light beam and the inhibition light beam are overlapped.
The switch of the micromirror in the fixed area on the DMD is used for regulating and controlling the energy of each point in the inscribed dot matrix; in the super-resolution writing process, the energy of the incident inhibition light beam is regulated, and the special inhibition phenomenon of the inhibition light beam to the excitation light beam is inhibited in the super-resolution writing method by utilizing the double-light beam photoresist, namely, the inhibition effect is firstly enhanced and then weakened along with the enhancement of the photoresist polymerization by the inhibition light energy, and then the inhibition effect is converted into the promotion phenomenon, so that the photoresist polymerization promotion phenomenon occurs in the three-dimensional central area of the two focused light beams, the photoresist polymerization inhibition phenomenon occurs in the peripheral area, and the super-resolution writing of the three-dimensional structure is realized.
More specifically, in this embodiment, the wavelengths of the laser beams emitted by the first light source 1 and the second light source 2 are both 532 nm, wherein the excitation beam emitted by the first light source 1 is a femtosecond beam, the pulse width in this embodiment is 140 fs, the repetition frequency is 80 MHz, and the diameter of the emergent light is 2 mm; the suppressed beam emitted from the second light source 2 was a beam of continuous wavelength, and the diameter of the emitted light was 2 mm. The photoinitiator material of the dual beam photoresist in this example was benzil, and the other mixtures were selected from bis (2, 6-tetramethyl-4-piperidinyl-1-oxy) sebacate (BTPOS) and pentaerythritol triacrylate (PETA), wherein the mass fraction of benzil was 1.7wt%, and the mass fraction of bis (2, 6-tetramethyl-4-piperidinyl-1-oxy) sebacate was 2.1wt%.
In the scheme of the embodiment, a device of a high-flux super-resolution three-dimensional inscription method based on double light beams is as follows:
as shown in fig. 1, the three-dimensional sample stage comprises a first light source 1, a second light source 2, a beam combination module 3, a beam expansion module 4, a DMD, a first lens 6, a second lens 7, a first reflecting mirror 8, an MLA, a third lens 10, an objective lens 11, a three-dimensional sample stage 12 and a controller 13; the first light source 1 emits excitation light beams, the second light source 2 emits inhibition light beams, the two light beams enter the beam combination module 3 to achieve beam combination, then the beam combination light beam passes through the beam expansion module 4 to achieve beam expansion to match the effective acting area on the DMD, the combined light beam passes through the first lens 6 and the second lens 7 to be irradiated onto the first reflecting mirror 8 after being reflected by the DMD, the combined light beam reflected by the first reflecting mirror 8 passes through the MLA to form focusing lattices with equal distance at the focal plane position, and then the focusing lattices further pass through the third lens 10 and the objective lens 11 to be irradiated onto the three-dimensional sample table 12 to form an array writing lattice, exposure of photoresist is achieved, and rapid and high-precision writing of any three-dimensional pattern is achieved.
The beam combining module 3 in this embodiment includes, as shown in fig. 2, a first half slide 14, a polarization splitting prism 15, a second half slide 16, and a second reflecting mirror 17; the first half glass slide 14 is used for modulating the polarization state of the excitation light beam emitted by the first light source 1, so that all energy can be transmitted through the polarization beam splitter prism 15 after passing through the polarization beam splitter prism 15; the second half glass slide 16 modulates the polarization state of the second light source 2, so that all energy is reflected after the second light source passes through the polarization splitting prism 15, and then the two incident light beams are combined. In this embodiment, a first half glass slide 14, a polarization splitting prism 15 and a second half glass slide 16 which are applicable to 532 nm wavelength are selected; in the beam combining module 3, as shown in fig. 2, the first half glass slide 14 and the second half glass slide 16 are arranged in parallel one above the other, the polarization splitting prism 15 is arranged behind the first half glass slide 14, the second reflecting mirror 17 is arranged behind the second half glass slide 16, so that the excitation beam (i.e. the first beam in the figure) entering the beam combining module 3 enters the polarization splitting prism 15 after being modulated by the polarization state of the first half glass slide 14, and is transmitted completely, and the inhibition beam (i.e. the second beam in the figure) entering the beam combining module 3 is reflected to the polarization splitting prism 15 after being modulated by the polarization state of the second half glass slide 16 and is reflected completely, so that the excitation beam and the inhibition beam are combined.
The combined light then enters the beam expanding module 4, which as shown in fig. 3, includes a fourth lens 18, an aperture 19 and a fifth lens 20; the aperture 19 is located at the focal plane between the fourth lens 18 and the fifth lens 20, i.e. the aperture 19 is located at the back focal plane of the fourth lens 18 and also at the front focal plane of the fifth lens 20, the fourth lens 18 and the fifth lens 20 are used for expanding the combined beam, and the aperture 19 is used for filtering the combined beam. In this embodiment, the focal length of the fourth lens element 18 is selected to be 50 mm, the focal length of the fifth lens element 20 is selected to be 300 mm, the magnification is 6 times, and the diameter of the small hole 19 is selected to be 15 μm, so as to complete the filtering and beam expansion.
The beam-combined light is incident on the DMD after being expanded by the beam-expanding module 4, and is further incident on the MLA after being reflected by the DMD.
The DMD of this example was selected from the dlp9500 texas instruments with 1920 x 1080 pixels for the visible light band, with an effective area of 20.7 mm x 11.7mm and a single micromirror size of 10.8 μm. When the DMD is in the fully-on mode, the combined light is reflected into the subsequent optical path.
In this example, the number of MLAs with 70X 70 and a microlens spacing of 162 μm was selected, so that the effective area was 11.34 mm X11.34 mm.
The effective control area of the DMD is selected to be 11.34 mm multiplied by 11.34 mm, the ratio of the effective areas of the DMD to the effective area of the second lens 7 is 1:1, so that the first lens 6 and the second lens 7 are selected to have the same focal length, the focal lengths of the DMD, the first lens 6 and the second lens 7 are 100 mm, and the MLA meets the 4F imaging relation, namely, the distance between the DMD and the first lens 6 is equal to the focal length of the first lens 6 and is 100 mm, the distance between the first lens 6 and the second lens 7 is equal to the focal length of the second lens 7 and is 200 mm, and the distance between the second lens 7 and the MLA is equal to the focal length of the second lens 7 and is 100 mm.
The size of a single micro-mirror is 10.8 mu m, the imaging proportion of the light beam passing through the DMD and the MLA is 1:1, and the area of 15 multiplied by 15 micro-mirrors corresponds to the area of one micro-lens, so that the energy of the light beam passing through the micro-lens can be quickly adjusted by adjusting the on-off state of the micro-lens in the area.
In this embodiment, the third lens 10 is a lens with a focal length of 200 mm, preferably a field lens is selected as the third lens 10, the objective lens 11 is an oil lens with a focal length of 2 mm, a magnification of 100 times, and a numerical aperture of 1.4; the focal plane of the MLA, the third lens 10, the objective lens 11 and the three-dimensional sample stage 12 satisfy a 4F imaging relationship, i.e. the distance between the focal plane of the MLA and the third lens 10 is equal to the focal length of the third lens 10, 200 mm, the distance between the third lens 10 and the objective lens 11 is the sum of the two focal lengths, 202 mm, and the distance between the objective lens 11 and the three-dimensional sample stage 12 is equal to the focal length of the objective lens 11, 2 mm.
The three-dimensional sample stage 12 is provided with double-beam photoresist, and the three-dimensional movement in the X, Y, Z axial direction can be realized through a high-precision driving motor in the three-dimensional sample stage 12, so that the splicing of a two-dimensional printing structure and the rapid and high-precision inscription of a three-dimensional pattern can be realized.
In addition, a controller 13 is also connected to the system, and the system can be automatically controlled by a PLC controller 13, a computer, and the like. The controller 13 is electrically connected with the first light source 1, the second light source 2 and the switch of the DMD respectively, and the controller 13 is also electrically connected with the switch of the driving motor of the three-dimensional sample stage 12, and the controller 13 can control the first light source 1 and the second light source 2 to be started and stopped, control the opening and closing states of the micromirrors in each fixed area in the DMD and the DMD, and control the precise three-dimensional movement of the three-dimensional sample stage.
Before writing, the controller 13 controls the first light source 1 and the second light source 2 to be turned on, and controls the DMD to be in a turned-off state, and at this time, the combined light cannot enter the first lens 6, and thus cannot reach the imaging surface. The dual beam photoresist is placed on the substrate, and then the substrate is mounted on the three-dimensional sample stage 12, and the dual beam photoresist is adjusted to the focal length of the objective lens 11 by adjusting the axial distance.
In the writing process, the energy of the first light source 1 is firstly started, the total energy of the first light source 1 is regulated through the controller 13, so that the first light source can write a lattice structure at a focal plane, and then the energy of each writing point is regulated by utilizing the corresponding relation between each subarea and each writing point on the DMD through precise measurement of the writing lattice structure, so that the energy in the writing lattice is kept uniform.
According to the test chart of the special suppression phenomenon of the suppression beam to the excitation beam in the dual-beam super-resolution writing method shown in fig. 4, it can be found that when the excitation light energy is fixed, the writing structure gradually disappears along with the enhancement of the suppression beam, and then gradually enhances. Therefore, the energy (promoting part) of the corresponding area at the lower left part in the graph is selected, the energy of the first light source 1 and the energy of the second light source 2 are optimized, then the switch of the micro mirror (70 x 70) at the corresponding area on the DMD and the displacement condition of the three-dimensional sample table 12 are simultaneously controlled according to the required three-dimensional structure to write, the parallel writing of 4900 dot matrix (independent switch between dots) can be simultaneously realized, and further the high-flux and super-resolution writing of any three-dimensional nano structure on the double-beam photoresist can be realized.
FIG. 5 is a diagram of an electron microscope comparing the writing effect of the present application with that of a single beam. Wherein, the upper left graph is a three-dimensional structure (inscription under the single beam condition) directly inscribed by using the first light source 1 (excitation beam), and the axial period is 220 nm; it can be seen from the oblique view that the lines in the axial direction are already difficult to distinguish, as shown in the upper right diagram, whereby it can be seen that a single light source cannot achieve inscription in the axial direction of 220 nm cycles. When the second light source 2 (beam suppression) is added, the energy of the first light source 1 is unchanged, the second light source 2 correspondingly selects the energy of the lower left promotion part in fig. 4, the writing result is shown in the lower left diagram in fig. 5, the magnifying electron microscope image (lower right diagram) on the side surface can clearly find that the axial line can be resolved, so that the super-resolution writing capability is improved, and the writing of 220 nm axial period is realized.
Example 2
In this example, the photoinitiator material of the dual beam photoresist used was selected to be spiro [1, 3-trimethylindole- (6' -nitrobenzodihydropyran) ], with the remainder remaining consistent with example 1.
It should be noted that, for the photoinitiator material of the dual beam photoresist used in the present method and the present system, any one suitable photoinitiator material or a combination of photoinitiator materials such as benzophenone, diacetyl, 7-diethylamino-3-thenoylcoumarin, 2-isopropylthioxanthone, etc. may be selected according to practical requirements, in addition to benzil used in example 1 and spiro [1, 3-trimethylindole- (6' -nitrobenzodihydropyran) ] used in example 2.
Example 3
In this embodiment, the wavelength of the excitation beam is 600nm and is a femtosecond beam; the wavelength of the suppression beam used was still 600nm and was picosecond, the others remaining the same as in example 1.
It should be noted that, for the excitation light beam and the suppression light beam used in the method and the system, the wavelengths of the excitation light beam and the suppression light beam can be selected from 400-800nm, and the wavelengths can be the same wavelength or different wavelengths, preferably, the excitation light beam and the suppression light beam with the same wavelength are adopted, so that the influence caused by chromatic aberration (chromatic aberration can cause the center of a focusing light spot to be misaligned) is fully avoided; the excitation beam is only recommended to use a femtosecond laser beam, while the suppression beam may select a continuous laser beam (example 1), a picosecond laser beam (example 3), or also a nanolaser beam according to actual environment, equipment conditions, and experimental needs.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present application. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present application is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present application.
Claims (10)
1. A high-flux super-resolution three-dimensional inscription method based on double light beams is characterized in that combined light is parallelly incident to a digital micro-mirror device and is reflected by the digital micro-mirror device and then is incident to a micro-lens array, a focusing lattice is formed at the focal plane of the micro-lens array, the focusing lattice is imaged on the surface of double-light-beam photoresist to form an inscription lattice with excitation light beams coincident with inhibition light beams, and the double-light-beam photoresist is exposed;
the beam combination light is obtained by combining an excitation beam and a suppression beam;
the suppression beam has special suppression phenomenon on the excitation beam: the inhibition effect is enhanced firstly along with the inhibition of the photo-resist polymerization enhancement, then the inhibition effect is weakened, and then the phenomenon is converted into the promotion phenomenon, so that the photo-resist polymerization promotion phenomenon occurs in the three-dimensional central area of the two focused light beams, and the photo-resist polymerization inhibition phenomenon occurs in the peripheral area;
each point in the inscription lattice consists of a focusing point of an excitation beam and a focusing point of an inhibition beam, the energy distribution of the excitation beam and the energy distribution of the inhibition beam coincide in space, and the light intensity distribution of a single point is Gaussian distribution;
the energy of each point in the inscription lattice is regulated and controlled by regulating the on-off state of the micro mirror in the digital micro mirror device area;
by adjusting the energy of the inhibition beam, each point in the inscription lattice forms photoresist polymerization promotion in the central area and photoresist polymerization inhibition in the peripheral area.
2. The high-flux super-resolution three-dimensional writing method based on double beams according to claim 1, wherein the excitation beam is a femtosecond laser beam with the wavelength range of 400-800nm; the inhibition beam is any one of a continuous laser beam, a picosecond laser beam and a nanometer laser beam, and the wavelength range is 400-800nm.
3. The method of claim 2, wherein the excitation beam and the suppression beam have the same wavelength.
4. The method for three-dimensional writing with high throughput and super resolution based on double light beams as claimed in claim 1, wherein the photoinitiator material in the double light beam photoresist is any one of benzil, benzophenone, diacetyl, spiro [1, 3-trimethylindole- (6' -nitrobenzodihydropyran) ], 7-diethylamino-3-thiophenecarboxyl coumarin and 2-isopropyl thioxanthone.
5. A system of a high-flux super-resolution three-dimensional inscription method based on double light beams, which is characterized in that the method as claimed in any one of claims 1 to 4 is adopted for three-dimensional inscription;
the system comprises a light source, a beam combination module (3), a digital micro-mirror device (5), a micro-lens array (9), an objective lens (11) and a three-dimensional sample stage (12);
the light source emits an excitation light beam and a suppression light beam respectively;
the beam combination module (3) combines the excitation beam and the inhibition beam from the light source and then enters the digital micro-mirror device (5), the digital micro-mirror device (5) reflects the combined beam and enables the combined beam to enter the micro-lens array (9), the micro-lens array (9) forms a focusing lattice at a focal plane, and the focusing lattice is imaged on the three-dimensional sample stage (12) through the objective lens (11) to form a writing lattice;
the dual beam photoresist is disposed on a three-dimensional sample stage (12).
6. The system of the high-throughput super-resolution three-dimensional inscription method based on double beams according to claim 5, wherein said beam combination module (3) comprises a first half glass slide (14), a polarization splitting prism (15), a second half glass slide (16) and a second reflecting mirror (17);
the first half glass slide (14) carries out polarization state modulation on a first laser beam emitted by a light source, so that all energy is transmitted after the first laser beam passes through the polarization splitting prism (15);
the second half glass slide (15) carries out polarization state modulation on a second laser beam emitted by the light source, so that all energy is reflected after the second laser beam passes through the second reflecting mirror (17) and enters the polarization splitting prism (15).
7. The system of the dual-beam-based high-throughput super-resolution three-dimensional inscription method according to claim 5, further comprising a beam expanding module (4) disposed between the beam combining module (3) and the digital micromirror device (5), so that the combined beam is expanded to match with the effective active area of the digital micromirror device (5);
the beam expanding module (4) comprises a fourth lens (18), an aperture (19) and a fifth lens (20); the small hole (19) is arranged at the focal plane between the fourth lens (18) and the fifth lens (20) and is used for filtering the combined beam, and the magnification formed by the fourth lens (18) and the fifth lens (20) is larger than 1 and is used for expanding the combined beam.
8. The system of the dual-beam-based high-throughput super-resolution three-dimensional inscription method according to claim 5, wherein a first lens (6) and a second lens (7) are further arranged between the digital micromirror device (5) and the microlens array (9) in sequence, and the digital micromirror device (5), the first lens (6), the second lens (7) and the microlens array (9) form a 4F imaging relationship.
9. The system of the high-flux super-resolution three-dimensional inscription method based on double light beams according to claim 8, wherein a first reflecting mirror (8) is further arranged between the second lens (7) and the micro lens array (9).
10. The system of the dual-beam-based high-throughput super-resolution three-dimensional inscription method according to claim 5, wherein a third lens (10) is further disposed between said microlens array (9) and said objective lens (11), and a focal plane of the microlens array (9), the third lens (10), the objective lens (11) and the three-dimensional sample stage (12) form a 4F imaging relationship.
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| WO2022100751A1 (en) * | 2020-11-16 | 2022-05-19 | 香港大学 | Laser interference lithography device and method |
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