CN114779591A - Super-resolution photoetching method based on double-color double-step absorption effect - Google Patents
Super-resolution photoetching method based on double-color double-step absorption effect Download PDFInfo
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- CN114779591A CN114779591A CN202210717492.0A CN202210717492A CN114779591A CN 114779591 A CN114779591 A CN 114779591A CN 202210717492 A CN202210717492 A CN 202210717492A CN 114779591 A CN114779591 A CN 114779591A
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- 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
- G03F7/70216—Mask projection systems
- G03F7/70325—Resolution enhancement techniques not otherwise provided for, e.g. darkfield imaging, interfering beams, spatial frequency multiplication, nearfield lenses or solid immersion lenses
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Abstract
The invention discloses a super-resolution lithography method based on a bicolor two-step absorption effect, which is based on the spectral absorption characteristics of a basic state and a triplet state of a benzil photoinitiator, utilizes a laser beam with the wavelength of the basic state absorption range of one material and a laser beam with the wavelength of the triplet state absorption range of the other material to jointly act in the material, realizes the bicolor two-step absorption effect by controlling the energy of the two, and combines the relative displacement control of the two to obtain the writing line width smaller than the diffraction limit. The invention provides a super-resolution nanometer laser direct writing method with sub-hundred nanometer precision writing precision and fast writing capability, so that the three-dimensional photoetching direct writing technology has the advantages of high speed, super-resolution and complex structure writing capability.
Description
Technical Field
The invention belongs to the field of super-resolution laser nanometer direct writing lithography, and particularly relates to a super-resolution lithography method based on a two-color two-step absorption effect.
Background
"the industry wants to improve the performance of the product, and the micro-nano manufacturing technology is taken as the basis of the high-end manufacturing industry of the country, can highlight the industrial development level of the country, plays an important role in promoting scientific and technological progress, promoting industrial development, improving national defense strength and the like, and is a key for the country to gain advantages among international competition. However, at present, domestic high-end micro-nano manufacturing technologies such as high-end industrial lithography machines for manufacturing microelectronic chips and high-end electron beam lithography equipment for scientific research are monopolized by foreign related companies, and the industry and scientific research institutions in China need to spend a large amount of expenses for the high-end processing equipment every year. Therefore, the research and development of the micro-nano processing equipment technology in China are short plates for scientific research and industrial manufacturing, and particularly, the nano processing equipment is monopolized abroad for a long time and is called the field of 'neck clamping'.
The technology represented by photoetching is a main method for carrying out micro-nano processing, and the direct-writing photoetching technology represented by two-photon direct writing has the advantages of 3D processing capability, capability of directly processing a structure designed at a computer end (self-defined structure), no limitation of the structure to a mask plate unlike the exposure photoetching technology, and capability of being a micro-nano processing technology which is urgently needed in emerging fields such as silicon optical chips, novel sensors, artificial intelligence, novel materials and the like. However, the two-photon lithography technology depends on a femtosecond laser source or a picosecond laser source, and devices such as optical lenses and pulse broadening correction which need to be matched for high-energy pulses are very expensive, and the cost of the system is also greatly increased.
A Wegener subject group of the German Karlshire Rigie institute of technology proposes a method for realizing 3D processing capability by using a conventional light source, the preparation of a three-dimensional structure is realized by using a benzil photoinitiator and combining a conventional continuous light source with the wavelength of 405nm, the characteristic line width can reach below hundred nanometers, but the defect is that the writing speed is very slow, and the further popularization and application of the technology are hindered.
Disclosure of Invention
The invention aims to provide a high-precision and rapid nanometer writing method aiming at the defects of the prior art.
The purpose of the invention is realized by the following technical scheme:
a super-resolution photoetching method based on a double-color double-step absorption effect comprises the following steps:
(1) coating photoresist on a glass substrate or a silicon substrate, and placing the glass substrate or the silicon substrate at the focal plane of an objective lens of a photoetching system;
(2) turning on the first absorbed beam to adjust its optical power density
Incident into the photoresist; the wavelength range of the first absorption light beam is 100 nm-450 nm;
(3) then the second absorption beam is turned on to adjust its optical power density
The second absorption beam is incident into the photoresist, and the focusing center of the second absorption beam is adjusted to coincide with the focusing center of the first absorption beam; the wavelength range of the second absorption light beam is 400 nm-800 nm;
(4) relatively moving the focusing centers of the first absorption light beam and the second absorption light beam to form a writing light spot with a super-diffraction limit; and controlling the photoetching system to carry out the carving of any nano structure, and developing in an acetone solvent after the carving is finished to obtain a carved structure.
Specifically, the photoresist material in step (1) is benzil, bis (2,2,6, 6-tetramethyl-4-piperidyl-1-oxy) sebacate (BTPOS), and pentaerythritol triacrylate (PETA), wherein the mass fraction of benzil is 1.7 wt%, and the mass fraction of bis (2,2,6, 6-tetramethyl-4-piperidyl-1-oxy) sebacate is 2.1 wt%;
specifically, the wavelength of the first absorption beam in step (2) is preferably 405 nm; the wavelength of the second absorption light beam in the step (3) is preferably 488 nm;
specifically, the writing speed in the step (4) is controlled to be 10 um/s-1 m/s.
In addition, the range of the relative movement in the step (4) is within a half of the sum of the wavelengths of the first absorption beam and the second absorption beam.
The invention has the following beneficial effects:
based on the spectral absorption characteristics of the ground state and the triplet state of the benzil photoinitiator, the laser beam with the wavelength in the absorption range of the ground state of one material and the laser beam with the wavelength in the absorption range of the triplet state of the other material act on the material together, the two-color two-step absorption effect is realized by controlling the energy of the two laser beams, and the relative displacement control of the two laser beams is combined, so that the scribing line width smaller than the diffraction limit is obtained. Compared with the technology mentioned in the background document, the invention can improve the writing speed by controlling the energy and the energy ratio of the first absorption beam and the second absorption beam, and regulate and control the positions of the centers of the two beams, thereby reducing the laser action area and further reducing the line width of the writing characteristic. The super-diffraction limit 3D writing capability realized by the method 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 schematic diagram of a super-resolution lithography method based on a two-color two-step absorption effect according to the present invention;
FIG. 2 is a graph showing the absorption of the ground state and triplet state of the inventive azo-photoinitiator at different wavelengths;
FIG. 3 is a diagram showing the arrangement of the center positions of two color spots in writing according to an embodiment of the present invention;
FIG. 4 is a graph of the result of the imaging of the writing lines under an electron microscope in the example of the invention.
Description of reference numerals: 1-a first absorption beam, 2-a second absorption beam, 3-an equivalent writing spot, 4-a photoinitiator original state, 5-a photoinitiator intermediate state, 6-a photoinitiator excited state, 7-a first absorption beam, and 8-a second absorption beam.
Detailed Description
The present invention is further illustrated by the following examples and figures, but should not be construed as being limited thereby.
A super-resolution lithography method based on a two-color two-step absorption effect, as shown in FIG. 1, comprises the following steps:
(1) coating photoresist containing benzil photoinitiator on a glass substrate or a silicon substrate, and placing the photoresist at the focal plane of an objective lens of a photoetching system;
(2) turning on the first absorbed beam to adjust its optical power density
Incident into the photoresist;
(3) turning on the second absorption beam to adjust its optical power density
The second absorption beam is incident into the photoresist, and the focusing center of the second absorption beam is adjusted to coincide with the focusing center of the first absorption beam;
(4) relatively moving the focusing centers of the first absorption light beam and the second absorption light beam in a certain range to form a writing light spot exceeding the diffraction limit; and controlling the photoetching system to carry out the carving of any nano structure, and developing after the carving is finished to obtain the carved structure.
In the examples, the photoresist material formulations were benzil, bis (2,2,6, 6-tetramethyl-4-piperidyl-1-oxy) sebacate (BTPOS) and pentaerythritol triacrylate (PETA), wherein the mass fraction of benzil was 1.7 wt% and the mass fraction of bis (2,2,6, 6-tetramethyl-4-piperidyl-1-oxy) sebacate was 2.1 wt%. The absorption of the ground state and the triplet state at different wavelengths is shown in fig. 2, in which the extinction coefficient of the triplet state is uniformly divided by 100.
Placing the configured photoresist in a laser writing system, wherein the wavelength range of the first absorption light beam is 100 nm-450 nm; the wavelength range of the second absorption light beam is 400 nm-800 nm;
specifically, the writing speed is controlled to be 10 um/s-1 m/s.
The system uses a first absorbing beam with a laser wavelength of 405nm and a second absorbing beam with a laser wavelength of 488nm and has been adjusted to completely coincide the centers of the two beams. The objective lens adopts an oil lens with NA of 1.4, and the moving platform is a piezoelectric moving platform.
Before the start of writing, the photoinitiator was in the original state, and the optical power density of the first absorbed beam was set to 6.7X 108W/m2Setting the optical power density of the second absorption beam to be 9.1 × 108W/m2And the center positions of the two-color light spots are staggered by a certain distance (about 20 nm) along the X-axis 45-degree angle direction of the writing coordinate axis as shown in figure 3 during writing, namely, the two-color light spots relatively move to form a writing light spot with super diffraction limit. The range of the relative movement is within half of the sum of the wavelengths of the first absorption beam and the second absorption beam.
In the example the writing speed is set to 10um/s and the writing structure is chosen to be a grating structure with a period of about 200 nm. When the photo-initiator is exposed to the first absorption beam and the second absorption beam at the beginning of writing, the photo-initiator firstly absorbs the first absorption beam, as shown in fig. 1, the photo-initiator changes to an intermediate state, at this time, electrons complete the ground state absorption, if the second absorption beam does not act, the photo-initiator also can initiate a series of photochemical reactions, which are expressed as a common single photon absorption phenomenon, and the line width of writing can not exceed the diffraction limit. In this example, after the photoinitiator absorbs the first absorption light, electrons in the photoinitiator continue to complete triplet absorption under the action of the second absorption light, a series of photochemical reactions are randomly initiated, a double-step absorption effect is completed, a two-photon absorption effect similar to that in femtosecond writing is realized, and super-resolution writing is further completed. After the writing and the developing, the obtained writing structure is placed in a scanning electron microscope for imaging observation, an imaging graph is shown in fig. 4, the line width of the grating stripe can be observed to be about 85nm (less than 100 nm), the super-resolution nanometer writing capability is realized, the height is about 300nm through measurement, the super-resolution nanometer writing capability is realized, the super-resolution nanometer writing structure has a very good depth-to-width ratio, and the ratio of the height to the width of the grating stripe with the depth-to-width ratio is also shown in the figure.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the scope of the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
The above embodiments are only used for illustrating the design idea and features of the present invention, and the purpose of the present invention is to enable those skilled in the art to understand the content of the present invention and implement it accordingly, and the protection scope of the present invention is not limited to the above embodiments. Therefore, all equivalent changes or modifications based on the principles and design concepts disclosed herein are intended to be included within the scope of the present invention.
Claims (6)
1. A super-resolution photoetching method based on a double-color double-step absorption effect is characterized by comprising the following steps:
(1) coating photoresist on a glass substrate or a silicon substrate, and placing the glass substrate or the silicon substrate at the focal plane of an objective lens of a photoetching system;
(2) turning on the first absorption beam to adjust its optical power density
Incident into the photoresist; the wavelength range of the first absorption light beam is 100 nm-450 nm;
(3) then the second absorption beam is turned on to adjust its optical power density
The second absorption beam is incident into the photoresist, and the focusing center of the second absorption beam is adjusted to coincide with the focusing center of the first absorption beam; the wavelength range of the second absorption light beam is 400 nm-800 nm;
(4) relatively moving the focusing centers of the first absorption light beam and the second absorption light beam to form a writing light spot with a super-diffraction limit; and controlling the photoetching system to carry out the writing of any nano structure, and developing in an acetone solvent after the writing is finished to obtain the written structure.
2. The method according to claim 1, wherein the photoresist material in step (1) is selected from the group consisting of benzil, bis (2,2,6, 6-tetramethyl-4-piperidyl-1-oxy) sebacate, and pentaerythritol triacrylate, wherein the mass fraction of benzil is 1.7 wt%, the mass fraction of bis (2,2,6, 6-tetramethyl-4-piperidyl-1-oxy) sebacate is 2.1 wt%, and the mass fraction of pentaerythritol triacrylate is 96.2 wt%.
3. The method according to claim 1, wherein the first absorption beam in step (2) has a wavelength of 405 nm.
4. The method according to claim 1, wherein the second absorption beam in step (3) has a wavelength of 488 nm.
5. The method according to claim 1, wherein the writing speed in step (4) is controlled to be 10 um/s-1 m/s.
6. The method according to claim 1, wherein the relative shift in step (4) is within a half of the sum of the wavelengths of the first and second absorption beams.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1556451A (en) * | 1976-06-10 | 1979-11-28 | Formigraphic Engine Corp | Methods and apparatus for producing three dimensional objects and patterns |
| CN1692313A (en) * | 2002-10-02 | 2005-11-02 | 3M创新有限公司 | Multiphoton photosensitization method |
| US20100123889A1 (en) * | 2008-11-20 | 2010-05-20 | Korea Research Institute Of Standards And Science | Super-resolution lithography apparatus and method based on multi light exposure method |
| CN102955360A (en) * | 2011-08-23 | 2013-03-06 | Jsr株式会社 | Photosensitive composition, method for manufacturing molded article, molded article and semiconductor device |
| US20200356004A1 (en) * | 2019-05-08 | 2020-11-12 | Boise State University | Photo-resist for super-resolution optical lithography |
| CN113156773A (en) * | 2021-03-31 | 2021-07-23 | 华中科技大学 | Cooperative absorption double-beam super-resolution lithography system and method |
| US20220055290A1 (en) * | 2018-12-17 | 2022-02-24 | Karlsruher Institut für Technologie | Parallelized 3D Lithography Using Multi-Beam, Multi-Color Light-Induced Polymerization |
| CN114527629A (en) * | 2022-04-21 | 2022-05-24 | 之江实验室 | Super-resolution photoetching method based on double dark spot combined inhibition and photoresist |
-
2022
- 2022-06-23 CN CN202210717492.0A patent/CN114779591B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1556451A (en) * | 1976-06-10 | 1979-11-28 | Formigraphic Engine Corp | Methods and apparatus for producing three dimensional objects and patterns |
| CN1692313A (en) * | 2002-10-02 | 2005-11-02 | 3M创新有限公司 | Multiphoton photosensitization method |
| US20100123889A1 (en) * | 2008-11-20 | 2010-05-20 | Korea Research Institute Of Standards And Science | Super-resolution lithography apparatus and method based on multi light exposure method |
| CN102955360A (en) * | 2011-08-23 | 2013-03-06 | Jsr株式会社 | Photosensitive composition, method for manufacturing molded article, molded article and semiconductor device |
| US20220055290A1 (en) * | 2018-12-17 | 2022-02-24 | Karlsruher Institut für Technologie | Parallelized 3D Lithography Using Multi-Beam, Multi-Color Light-Induced Polymerization |
| US20200356004A1 (en) * | 2019-05-08 | 2020-11-12 | Boise State University | Photo-resist for super-resolution optical lithography |
| CN113156773A (en) * | 2021-03-31 | 2021-07-23 | 华中科技大学 | Cooperative absorption double-beam super-resolution lithography system and method |
| CN114527629A (en) * | 2022-04-21 | 2022-05-24 | 之江实验室 | Super-resolution photoetching method based on double dark spot combined inhibition and photoresist |
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