CN115028759A - Laser manufacturing method based on triplet state up-conversion and application thereof - Google Patents
Laser manufacturing method based on triplet state up-conversion and application thereof Download PDFInfo
- Publication number
- CN115028759A CN115028759A CN202210743675.XA CN202210743675A CN115028759A CN 115028759 A CN115028759 A CN 115028759A CN 202210743675 A CN202210743675 A CN 202210743675A CN 115028759 A CN115028759 A CN 115028759A
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- Prior art keywords
- triplet
- annihilator
- sensitizer
- conversion
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- MPIAGWXWVAHQBB-UHFFFAOYSA-N [3-prop-2-enoyloxy-2-[[3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propoxy]methyl]-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C MPIAGWXWVAHQBB-UHFFFAOYSA-N 0.000 claims description 2
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/02—Positioning or observing the workpiece, e.g. with respect to the point of impact; Aligning, aiming or focusing the laser beam
- B23K26/06—Shaping the laser beam, e.g. by masks or multi-focusing
- B23K26/064—Shaping the laser beam, e.g. by masks or multi-focusing by means of optical elements, e.g. lenses, mirrors or prisms
- B23K26/0643—Shaping the laser beam, e.g. by masks or multi-focusing by means of optical elements, e.g. lenses, mirrors or prisms comprising mirrors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/02—Positioning or observing the workpiece, e.g. with respect to the point of impact; Aligning, aiming or focusing the laser beam
- B23K26/06—Shaping the laser beam, e.g. by masks or multi-focusing
- B23K26/064—Shaping the laser beam, e.g. by masks or multi-focusing by means of optical elements, e.g. lenses, mirrors or prisms
- B23K26/0648—Shaping the laser beam, e.g. by masks or multi-focusing by means of optical elements, e.g. lenses, mirrors or prisms comprising lenses
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/02—Positioning or observing the workpiece, e.g. with respect to the point of impact; Aligning, aiming or focusing the laser beam
- B23K26/06—Shaping the laser beam, e.g. by masks or multi-focusing
- B23K26/067—Dividing the beam into multiple beams, e.g. multifocusing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- 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
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
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- G—PHYSICS
- G11—INFORMATION STORAGE
- G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
- G11B7/00—Recording or reproducing by optical means, e.g. recording using a thermal beam of optical radiation by modifying optical properties or the physical structure, reproducing using an optical beam at lower power by sensing optical properties; Record carriers therefor
- G11B2007/0003—Recording, reproducing or erasing systems characterised by the structure or type of the carrier
- G11B2007/0016—Recording, reproducing or erasing systems characterised by the structure or type of the carrier for carriers adapted to have label information written on the non-data side by the optical head used for data recording, e.g. lightscribe, labelflash
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/52—PV systems with concentrators
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- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Plasma & Fusion (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
Abstract
The invention discloses a laser manufacturing method based on triplet state up-conversion and application thereof. The method comprises the following steps: preparing a photosensitive material according to the selected sensitizer, annihilator, photoinitiator and polymerization monomer; according to a processing file of the micro-nano structure, irradiating the photosensitive material by using exciting light according to a preset moving track, and processing to obtain all growth structures required by the micro-nano structure; under the irradiation of excitation light at each moving track point, sensitizer molecules absorb light energy emitted by excitation light and transition to a triplet state, annihilator molecules absorb energy of triplet sensitizer molecules and then undergo energy level transition to the triplet state, annihilator molecules in the triplet state collide with each other to undergo annihilation, photoinitiator molecules are used for absorbing annihilation energy and then transition to the triplet state, and photoinitiator molecules in the triplet state are cracked to generate active substances which interact with polymerization monomers to initiate monomer curing. The invention can realize the micro-nano structure processing with low power, low cost and high precision.
Description
Technical Field
The invention belongs to the technical field of laser manufacturing, and particularly relates to a laser manufacturing method based on triplet state up-conversion and application thereof.
Background
The laser micro-nano processing is an important laser application, can realize the preparation of micro-structures at micron or nanometer level, and is widely applied to the fields of optical imaging, optical chips, optical storage, optical communication and the like. Laser direct writing lithography is an important method for realizing micro-nano processing, and the optical principle of the method is mainly high-power femtosecond laser-induced two-photon polymerization. In addition, according to an Abbe diffraction limit formula, a laser with a shorter wavelength is needed to be used as a processing light source for preparing a micro-nano structure with high precision and small size. Short wavelength (especially ultraviolet band) lasers are very expensive, limiting the large-scale application of laser direct writing technology in the field of micro-nano processing.
Therefore, a new laser manufacturing method needs to be researched to realize the preparation of the micro-nano structure with low power, low cost and high precision.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a laser manufacturing method based on triplet state up-conversion and application thereof, which can realize low-power, low-cost and high-precision micro-nano structure processing.
In order to achieve the aim, the invention provides a laser manufacturing method based on triplet state up-conversion, which is used for processing a micro-nano structure and comprises the following steps:
(1) selecting a photo-polymerization material and a triplet up-conversion material with an optical up-conversion characteristic based on triplet-triplet annihilation, and preparing a photosensitive material according to the photo-polymerization material and the triplet up-conversion material; the triplet up-conversion material comprises a sensitizer and an annihilator, and the photopolymerization material comprises a photoinitiator and a polymerization monomer;
(2) according to the processing file of the micro-nano structure, the power density is less than 100 mW-cm -1 Excitation light of (2) according to presetIrradiating the photosensitive material by the moving track, and processing to obtain all growth structures required by the micro-nano structure;
under the irradiation effect of the excitation light at each moving track point, the sensitizer molecule is used for absorbing light energy emitted by the excitation light and transits to an excited state, and then transits to a triplet state in an intersystem crossing mode; the annihilator molecules are used for absorbing energy of triplet sensitizer molecules, then energy level transition is carried out to the triplet state, and annihilator molecules in the triplet state collide with each other to carry out annihilation; the photoinitiator molecules are used for absorbing annihilation energy and then jump to an excited state, and then jump to a triplet state through intersystem crossing, and the photoinitiator molecules in the triplet state are cracked to generate active substances; the active substance interacts with the polymerization monomer to initiate the polymerization monomer to be solidified, and the processing of the growth structure of the micro-nano structure is completed.
In one embodiment, the sensitizer is selected to have a molar extinction coefficient greater than 10 4 L·mol -1 ·cm -1 The absorption waveband is matched with the wavelength of the excitation light, the intersystem crossing efficiency is more than 95%, the service life is more than microsecond magnitude, and the triplet state energy is higher than that of the annihilator molecule.
In one embodiment, the annihilator is selected from a material having a lifetime on the order of greater than microseconds, a fluorescence quantum yield greater than 95%, and a singlet excited state energy less than twice its triplet energy.
In one embodiment, the annihilator employs a fused ring aromatic hydrocarbon that includes naphthalene and its derivatives, biphenyl and its derivatives, and terphenyl and its derivatives.
In one embodiment, the combination of the sensitizer and the annihilator is in the form of:
when the sensitizer adopts zinc tetraphenylbenzoporphyrin, zinc tetraphenylporphyrin or platinum tetraphenylbenzoporphyrin, perylene is adopted as the annihilator; when the sensitizer employs trinitroanthracene porphyrin palladium or meso-tetraphenyl-tetraphenylporphyrin palladium complex, the annihilator employs rubrene; when the sensitizer adopts octaethylporphyrin palladium, octaethylporphyrin platinum, octaethylporphyrin zinc or tetraphenylporphyrin palladium, the annihilator adopts 9,10 diphenylanthracene; when the sensitizer adopts meso-tetraphenyl-tetraphenylporphyrin palladium complex, tetraphenylbenzoporphyrin palladium or tetraphenylbenzoporphyrin platinum, the annihilator adopts 9, 10-di (phenylethynyl) anthracene; when the sensitizer adopts 2, 3-butanedione, the annihilator adopts 2, 5-diphenyl oxazole; when the sensitizer adopts tris [ 2-phenylpyridine-C2, N ] iridium (III), the annihilating agent adopts pyrene; when the sensitizer adopts zinc tetraphenylbenzoporphyrin, the annihilator adopts 2-chloro-9, 10-bis (phenylethynyl) anthracene; when the sensitizer is zinc tetraphenylporphyrin, the annihilator is coumarin 343.
In one embodiment, the photoinitiator is a material with an absorption band matched to the emission band of the annihilator and a system cross-over efficiency greater than 95%.
In one embodiment, the photoinitiator is 1-hydroxycyclohexyl phenyl ketone, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinobenzyl) butanone, phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, bis (1- (2, 4-difluorophenyl) -3-pyrrolyl) titanocene, benzophenone, photoinitiator 500, 4' -ethoxyacetophenone, 4-hydroxybenzophenone, or 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide.
In one embodiment, the polymerized monomer is selected from liquid monomers and oligomers having a reactive group number greater than 3, and the polymerized monomer is selected from dipentaerythritol pentaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, 1, 6-hexanediol diacrylate, 2-phenoxyethyl acrylate, (2) -ethoxylated bisphenol A dimethacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, tris- (2-hydroxyethyl) isocyanurate triacrylate, or dipentaerythritol hexaacrylate.
In one embodiment, the excitation light is a pulsed laser, a continuous laser, or an LED light source.
In a second aspect, the present invention provides an application of the above-mentioned triplet up-conversion-based laser manufacturing method in the fields of 3D printing, lithography and optical storage.
According to the laser manufacturing method and application based on triplet state up-conversion, the photosensitive material with the characteristics of two material systems is prepared, the optical up-conversion based on triplet state-triplet state annihilation and photopolymerization are combined, and high-energy light can be emitted only by absorbing low-energy excitation light, so that the photopolymerization material is cured, the micro-nano structure is further processed, and the laser manufacturing method and application have the characteristics of low-power excitation and low cost; and corresponding to the processing of micro-nano structures with different structures and performance characteristics, the high-precision micro-nano structure can be prepared only by selecting a triplet up-conversion material consisting of appropriate materials and adjusting the light energy emitted by the triplet up-conversion material.
Drawings
FIG. 1 is a flow chart of a method for triplet up-conversion based laser fabrication according to an embodiment of the present invention;
FIG. 2 is a laser fabrication schematic diagram of the triplet up-conversion based laser fabrication method of FIG. 1;
FIG. 3 is a schematic diagram of a projection system for laser manufacturing according to an embodiment of the present invention;
FIG. 4 is a schematic diagram of a dual-beam laser manufacturing system according to an embodiment of the present invention;
FIG. 5 is a schematic diagram of a laser-based direct write system according to an embodiment of the present invention;
FIG. 6 is a schematic structural diagram of a projection type optical data storage mask according to an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a laser manufacturing method based on triplet state up-conversion, aiming at realizing the preparation of a micro-nano structure with low power, low cost and high precision. The laser manufacturing method mainly includes that photosensitive materials selected according to actual requirements change in material performance under irradiation of corresponding exciting light, and a micro-nano structure growth structure is formed through solidification.
Fig. 1 is a flowchart of a laser manufacturing method based on triplet up-conversion according to an embodiment of the present invention, and as shown in fig. 1, the laser manufacturing method is used for processing a micro-nano structure, and includes steps S10 and S20, which are detailed as follows:
s10, selecting a photo-polymerization material and a triplet up-conversion material with triplet-triplet annihilation optical up-conversion characteristics, and preparing the photosensitive material according to the photo-polymerization material and the triplet up-conversion material. The triplet up-conversion material comprises a sensitizer and an annihilator, and the photopolymerization material comprises a photoinitiator and a polymerization monomer.
Specifically, when the photosensitive material is prepared, the sensitizer and the annihilating agent used in the triplet state up-conversion material are mixed and stirred uniformly with the photoinitiator and the polymerization monomer in the photopolymerization material. The photosensitive material prepared by the embodiment consists of a triplet up-conversion material system and a photopolymerization material system, and can have the characteristics of two material systems.
In this embodiment, the triplet up-conversion material system includes a sensitizer and an annihilator, and has the characteristic of optical up-conversion based on triplet-triplet annihilation (TTA), and can absorb excitation light with long wavelength (low energy), and the TTA reaction occurs to emit light with short wavelength (high energy) (anti-stokes emission). Compared with the traditional laser manufacturing method adopting two-photon absorption up-conversion, the required excitation light energy is lower (the power density is less than 100mW cm) -1 ) The method has the characteristics of low power excitation and low cost, and can select proper sensitizing agent and annihilation agent materials in the system to regulate and control the wavelength of excitation light and the wavelength of emitted light.
The photopolymerization material system comprises a photoinitiator and a polymerization monomer, has photopolymerization characteristics, is combined with the TTA-based optical upconversion characteristics in the triplet upconversion material system, can absorb short-wavelength (high-energy) light emitted by the triplet upconversion material, performs photopolymerization reaction, and is cured to form a micro-nano structure-growth structure.
In order to realize the processing of all the growth structures of the micro-nano structure with different structures (two-dimensional structures or three-dimensional structures) and different functional characteristics, the method comprises the following specific steps:
s20, adopting a power density of less than 100mW cm according to the processing file of the micro-nano structure -1 The exciting light irradiates the photosensitive material according to a preset moving track, and all growth structures required by the micro-nano structure are obtained through processing. Specifically, the exciting light can adopt pulse laser, continuous laser or an LED light source, and the requirement of material polymerization energy can be met.
Under the action of excitation light irradiation at each moving locus point, as shown in fig. 2, the sensitizer molecule can absorb light energy emitted by the excitation light and jump to an excited state, and then jump to a triplet state by means of intersystem crossing (ISC); the triplet sensitizer molecules and the annihilator molecules are subjected to energy transfer, the annihilator molecules can absorb the energy of the triplet sensitizer molecules and then generate energy level transition to the triplet state, the annihilator molecules in the triplet state collide with each other to generate an annihilation process, one triplet annihilator molecule is transited to the ground state and transfers the energy to the other triplet annihilator molecule to make the triplet annihilator molecule transit to the singlet excited state, and the annihilator molecules in the singlet excited state release the energy while returning to the ground state. The photoinitiator molecules can absorb energy released when the annihilator returns to a ground state, then jump to an excited state, then jump to a triplet state through intersystem crossing, the photoinitiator molecules in the triplet state are cracked to generate active substances such as free radicals or cations, and the like, the active substances can interact with active groups in the polymerization monomers to initiate the polymerization monomers to be cured, and the processing of a growth structure of a micro-nano structure is completed.
According to the laser manufacturing method based on triplet state up-conversion, the photosensitive material with the characteristics of two material systems is prepared, optical up-conversion based on triplet state-triplet state annihilation and photopolymerization are combined, high-energy light can be emitted only by absorbing low-energy excitation light, so that the photopolymerization material is cured, the micro-nano structure is further processed, and the laser manufacturing method based on triplet state up-conversion has the characteristics of low-power excitation and low cost; and corresponding to the processing of micro-nano structures with different structures and performance characteristics, the high-precision micro-nano structure can be prepared by only selecting a triplet state up-conversion material consisting of appropriate materials and adjusting the light energy emitted by the triplet state up-conversion material.
Further, as can be seen from the analysis of the functional characteristics of the triplet up-conversion material and the photopolymerizable material provided in the above embodiments, the triplet up-conversion material and the photopolymerizable material provided in this embodiment need to satisfy the following material characteristics:
for the sensitizers in the triplet state up-conversion material, one of the sensitizers is used as a molecule for absorbing excitation light energy and needs to be sensitive to the excitation light, and the selected sensitizer needs to be higher than 10 4 L·mol -1 ·cm -1 The material with the molar extinction coefficient can be sensitive to exciting light, so that the material has strong light absorption capability in visible light and infrared light bands. Secondly, the sensitizer molecule can be ensured to absorb the light energy emitted by the excitation light to jump to the excited state only when the absorption waveband of the sensitizer molecule is within the wavelength range of the excitation light. Third, the sensitizer material should have a high probability of intersystem crossing (ISC) transition to triplet state, and the intersystem crossing efficiency of the selected sensitizer material should be greater than 95%. And fourthly, the selected sensitizer material needs to transfer the energy of the three linear molecules to the annihilator molecules efficiently, and the selected sensitizer material also needs to have the service life of more than microsecond magnitude. Fifthly, the selected sensitizer needs to have the characteristic that the triplet state molecular energy of the sensitizer is higher than that of the annihilator molecules, so that the energy transfer between the triplet state sensitizer molecules and the annihilator molecules can be realized, and the larger the energy difference is, the larger the driving force of the energy transfer is.
For the annihilator in the triplet up-conversion material, the selected annihilator material has the characteristics of longer service life than microsecond and higher than 95% fluorescence quantum yield, and meanwhile, the energy of singlet excited molecules of the annihilator material is ensured not to be higher than twice that of triplet molecules, so that the effective occurrence of the triplet-triplet annihilation process can be ensured.
In general, the annihilator provided in this embodiment can be selected from fused ring aromatic hydrocarbon materials, and the fused ring aromatic hydrocarbon materials include naphthalene and derivatives thereof, biphenyl and derivatives thereof, and terphenyl and derivatives thereof.
Specifically, the present embodiment provides a combination of sensitizer and annihilator materials in a triplet up-conversion material including, but not limited to, the combinations of materials listed in table 1.
TABLE 1
The combination of the sensitizer and the annihilator materials selected by numbers 18-22 in table 1 can be prepared and obtained by referring to the following documents: benchmark-triple association photonic upconversion schemes [ J ]. Physical Chemistry Chemical Physics,2018,20(17): 12182-. The combination of the sensitizer and the annihilator selected by the numbers 23-26 can be prepared and obtained by referring to the following documents: photon upconversion from a two-Photon absorption (TPA) to a triple-triple analysis (TTA) [ J ] Physical Chemistry Chemical Physics,2016,18(16): 10818-. The combination of sensitizers and annihilator materials selected by serial numbers 27-35 can be obtained by reference to the following references: photon inversion based on sensory triplets-triplets organization [ J ]. Coordination Chemistry Reviews,2010,254(21-22): 2560-.
For the photoinitiator in the photopolymerization material, one selected photoinitiator material needs to meet the condition that the absorption waveband of the photoinitiator material is matched with the emission band of annihilator molecules, so that the efficient transfer of annihilation energy can be realized. Secondly, the photoinitiator needs to have a high probability of intersystem crossing (ISC) transition to a triplet state, and the selected photoinitiator material also needs to have the characteristic that the intersystem crossing efficiency is more than 95%, so that the initiation efficiency is high.
Specifically, the photoinitiators provided in this example include, but are not limited to, all of the materials listed in table 2.
TABLE 2
For the polymerizable monomer in the photopolymerizable material, liquid monomers and oligomers having chemical reactivity may be used, and the molecular structure of the liquid monomers and oligomers is generally unsaturated, cyclic or contains a plurality of reactive groups (e.g., vinyl group, acryl group, etc.), and the larger the number of reactive groups (greater than 3), the more reactive the monomer, the faster the photocuring speed.
Specifically, the monomers provided in this example include, but are not limited to, all of the materials listed in table 3.
TABLE 3
The laser manufacturing method based on triplet state up-conversion provided by the invention is suitable for the fields of but not limited to photoetching, optical storage, 3D printing and the like.
The following examples are given in more detail.
Example 1
The invention is applicable to integrated circuit lithography, including mask fabrication. The photosensitive material undergoes a photo-physical chemical reaction under the action of the irradiation light, thereby changing the properties of the irradiated portion of the photosensitive material. The photosensitive material of the non-irradiated portion is left as it is, and the pattern of the previously designed non-irradiated portion is left on the substrate by the development treatment, thereby completing the transfer processing of the designed pattern. For the projection lithography, a laser manufacturing system is shown in fig. 3, and includes a laser, a lens, a filtering aperture, a photoelectric switch, a reflector, a dichroic mirror, a mask, an objective lens, a camera, a filter, a displacement stage (PI piezoelectric stage), an illumination source, a device controller, a computer, and the like. The laser, the photoelectric switch, the lens, the filtering small hole, the reflecting mirror, the dichroic mirror, the mask, the objective lens and the displacement table are sequentially arranged along the same light path, the photosensitive material is arranged on the displacement table and located between the objective lens and the displacement table, and the camera, the filter, the lens, the dichroic mirror, the objective lens, the displacement table and the illumination light source are sequentially arranged along the same light path.
The light beam is reflected by the dichroic mirror and then irradiates the mask, the light-transmitting part of the light beam passes through the mask, the light-non-transmitting part of the light beam is shielded, and then the light beam is focused inside the photosensitive material through the objective lens, so that the target pattern can be engraved at one time.
Example 2
The invention is suitable for the double-beam laser manufacturing technology. A two-beam laser manufacturing system is shown in fig. 4. In addition to the manufacturing light, a secondary light is added. The auxiliary light is also subjected to beam expanding and filtering, then is subjected to beam combining by a dichroic mirror and a light-producing beam, and is irradiated on the photosensitive material by a focusing objective lens after beam combining.
The manufacturing light and the auxiliary light contained in the dual-beam laser manufacturing system act on the photosensitive material together, so that the purpose of reducing the characteristic size of the processing structure can be achieved. The manufacturing light is focused into a material to be irradiated and processed through shaping and beam expanding, and a Gaussian-shaped light spot is generally formed; in order to realize the reduction of the characteristic size by single-point direct writing on a focusing plane, auxiliary light is subjected to beam expanding and filtering and then is modulated and focused into a material to be irradiated and processed by a 2 pi vortex phase plate or a space optical phase modulator with equivalent function, and a doughnut-shaped hollow light spot with zero central position intensity is generally formed; the two light spot centers are superposed in space and act on the material mentioned in the invention, so that the characteristic size can be reduced by single-point direct writing on a focusing plane.
Example 3
The invention is applicable to optical storage technology. The data store may be a single point of storage or a multi-point of storage. The single-point storage can be used for selecting a laser manufacturing direct writing system to complete data writing, and the multi-point storage can be used for selecting a laser manufacturing projection system (shown in figure 3) to complete data writing.
As shown in fig. 5, the laser manufacturing direct writing system includes a laser, a lens, a small filtering hole, a photoelectric switch, a reflector, a dichroic mirror, an objective lens, a CCD camera, a filter, a displacement stage (PI piezoelectric stage), an illumination light source, a device controller, a computer, and the like. The laser, the photoelectric switch, the lens, the small filtering hole, the reflecting mirror, the dichroic mirror, the objective lens and the displacement table are sequentially arranged along the same optical path, the photosensitive material is arranged on the displacement table and located between the objective lens and the displacement table, and the light beams sequentially pass through the optical elements and then are emitted into the photosensitive material. The camera, the filter, the lens, the dichroic mirror, the objective lens, the displacement table and the illumination light source are sequentially arranged along the same light path.
For single-point storage, taking a 10 × 10 data dot matrix format as an example, if the data dot matrix is written by using the laser manufacturing projection system of the present invention, the data dot matrix is divided into 100 steps, a single data point is written once, 100 data points are written in sequence according to the data dot matrix distribution, and the data dot matrix is generated after 100 steps of writing. The direct writing method is suitable for the condition that the data point array is small, and the projection method is suitable for writing the three-dimensional large data array if the data point array needs to be written.
For multi-point storage, taking the format of 10 × 10 data dot matrix as an example, if the data dot matrix is written by using the write-through system of the present invention, all data can be written at one time. By selecting a mask adapted to the data format, such as the projective optical data storage mask shown in fig. 6, writing of 100 data points is completed on the storage medium at one time.
Example 4
The invention is suitable for 3D printing. A beam of light is focused on a photosensitive material to form a single focused light spot, the light spot irradiates the photosensitive material, so that the photosensitive material is rapidly subjected to physical and chemical changes in a short time, and the performance of the same photosensitive material after being irradiated by the light is changed in the common 3D printing process.
It will be understood by those skilled in the art that the foregoing is only an exemplary embodiment of the present invention, and is not intended to limit the invention to the particular forms disclosed, since various modifications, substitutions and improvements within the spirit and scope of the invention are possible and within the scope of the appended claims.
Claims (10)
1. A laser manufacturing method based on triplet state up-conversion is used for micro-nano structure processing and is characterized by comprising the following steps:
(1) selecting a photo-polymerization material and a triplet up-conversion material with an optical up-conversion characteristic based on triplet-triplet annihilation, and preparing a photosensitive material according to the photo-polymerization material and the triplet up-conversion material; the triplet up-conversion material comprises a sensitizer and an annihilator, and the photopolymerization material comprises a photoinitiator and a polymerization monomer;
(2) according to the processing file of the micro-nano structure, the power density is less than 100mW cm -1 Irradiating the photosensitive material by the exciting light according to a preset moving track, and processing to obtain all growth structures required by the micro-nano structure;
under the irradiation effect of the excitation light at each moving track point, the sensitizer molecule is used for absorbing light energy emitted by the excitation light and transits to an excited state, and then transits to a triplet state in an intersystem crossing mode; the annihilator molecules are used for absorbing energy of triplet sensitizer molecules, then energy level transition is carried out to the triplet state, and annihilator molecules in the triplet state collide with each other to carry out annihilation; the photoinitiator molecules are used for absorbing annihilation energy and then transited to an excited state, then transited to a triplet state through intersystem crossing, and the photoinitiator molecules in the triplet state are cracked to generate active substances; the active substance interacts with the polymerization monomer to initiate the polymerization monomer to be solidified, and the processing of the growth structure of the micro-nano structure is completed.
2. The triplet up-conversion based laser fabrication method of claim 1 wherein the sensitizer is selected for use with a molar extinction coefficient greater than 10 4 L·mol -1 ·cm -1 The absorption waveband is matched with the wavelength of the excitation light, the intersystem crossing efficiency is more than 95%, the service life is more than microsecond magnitude, and the triplet state energy is higher than that of the annihilator molecule.
3. The triplet up-conversion based laser fabrication method according to claim 2, wherein the annihilating agent is selected from a material with lifetime greater than microsecond, fluorescence quantum yield greater than 95%, and singlet excited state energy less than twice its triplet energy.
4. The triplet up-conversion based laser fabrication method of claim 3 wherein the annihilator employs a fused ring aromatic hydrocarbon comprising naphthalene and its derivatives, biphenyl and its derivatives, and terphenyl and its derivatives.
5. The triplet up-conversion based laser fabrication method according to claim 3 wherein the sensitizer and the annihilating agent are in combination:
when the sensitizer adopts zinc tetraphenylbenzoporphyrin, zinc tetraphenylporphyrin or platinum tetraphenylbenzoporphyrin, perylene is adopted as the annihilator; when the sensitizer employs trinitroanthracene porphyrin palladium or meso-tetraphenyl-tetraphenylporphyrin palladium complex, the annihilator employs rubrene; when the sensitizer adopts octaethylporphyrin palladium, octaethylporphyrin platinum, octaethylporphyrin zinc or tetraphenylporphyrin palladium, the annihilator adopts 9,10 diphenylanthracene; when the sensitizer employs meso-tetraphenyl-tetraphenylporphyrin palladium complex, tetraphenylbenzoporphyrin palladium or tetraphenylbenzoporphyrin platinum, the annihilating agent employs 9, 10-bis (phenylethynyl) anthracene; when the sensitizer adopts 2, 3-butanedione, the annihilator adopts 2, 5-diphenyl oxazole; when the sensitizer adopts tris [ 2-phenylpyridine-C2, N ] iridium (III), the annihilating agent adopts pyrene; when the sensitizer adopts zinc tetraphenylbenzoporphyrin, the annihilator adopts 2-chloro-9, 10-bis (phenylethynyl) anthracene; when the sensitizer is zinc tetraphenylporphyrin, the annihilator is coumarin 343.
6. The triplet up-conversion based laser fabrication method according to claim 1, wherein the photo-initiator is a material with absorption band matching the emission band of the annihilator and intersystem crossing efficiency greater than 95%.
7. The triplet up-conversion based laser fabrication method according to claim 6 wherein the photo-initiator is 1-hydroxycyclohexyl phenyl ketone, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinobenzyl phenyl) butanone, phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide, bis (1- (2, 4-difluorophenyl) -3-pyrrolyl) titanocene, benzophenone, photo-initiator 500, 4' -ethoxyacetophenone, 4-hydroxybenzophenone or 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide.
8. The triplet up-conversion based laser manufacturing method according to claim 1, wherein the polymerization monomer is liquid monomers and oligomers having a reactive group number of more than 3, and the polymerization monomer is dipentaerythritol pentaacrylate, pentaerythritol tetraacrylate, pentaerythritol triacrylate, 1, 6-hexanediol diacrylate, 2-phenoxyethyl acrylate, (2) -ethoxylated bisphenol a dimethacrylate, trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, tris- (2-hydroxyethyl) isocyanurate triacrylate or dipentaerythritol hexaacrylate.
9. The triplet up-conversion based laser fabrication method of claim 1, wherein the excitation light is pulsed laser, continuous laser, or LED light source.
10. Use of the triplet up-conversion based laser fabrication method of any of claims 1 to 9 in the fields of 3D printing, lithography and optical storage.
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| CN113166638A (en) * | 2018-11-27 | 2021-07-23 | 哈佛学院院长及董事 | Photonic up-conversion nanocapsules for 3D printing and other applications |
| CN110554577A (en) * | 2019-07-19 | 2019-12-10 | 暨南大学 | System and method for laser direct writing micro-nano structure based on single wavelength and double light beams |
| CN112198146A (en) * | 2020-09-30 | 2021-01-08 | 华中科技大学 | Up-conversion optical microcavity and application thereof |
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