WO2020080945A1 - Photochimie à grande vitesse pour lithographie 3d - Google Patents

Photochimie à grande vitesse pour lithographie 3d Download PDF

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WO2020080945A1
WO2020080945A1 PCT/NL2019/050688 NL2019050688W WO2020080945A1 WO 2020080945 A1 WO2020080945 A1 WO 2020080945A1 NL 2019050688 W NL2019050688 W NL 2019050688W WO 2020080945 A1 WO2020080945 A1 WO 2020080945A1
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photo
photosensitizer
curable composition
group
composition according
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PCT/NL2019/050688
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Inventor
Arjen Boersma
Beniamino SCIACCA
Yunqi Wang
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Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno
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Publication of WO2020080945A1 publication Critical patent/WO2020080945A1/fr

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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
    • G03F7/20—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
    • 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
    • G03F7/0037—Production of three-dimensional images
    • 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
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • 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
    • G03F7/70375—Multiphoton lithography or multiphoton photopolymerization; Imaging systems comprising means for converting one type of radiation into another type of radiation
    • 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
    • G03F7/70383—Direct write, i.e. pattern is written directly without the use of a mask by one or multiple beams
    • 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

Definitions

  • the invention relates to a photo-curable composition for direct laser writing. Further, the invention relates to a method for direct laser writing below the diffraction limit.
  • Maskless lithography is a valuable technique for the fabrication of, for example, computer chips, optical components or photonic circuitries. It enables the writing of a pattern into a substrate using a focused beam without needing a photomask to protect area’s of the substrate that should not be affected. Typically a focused beam is scanned across a substrate which solubility properties are changed as a result of the irradiation. Areas exposed, or not exposed according to the nature of the substrate, can be subsequently washed away, leaving behind a specific pattern, typically a micropattern or nanopattern. A much used group of substrates is formed by resins.
  • Irradiation of the substrate can be achieved using an electron or photon beam.
  • the resolution of the system is physically limited by the wavelength of the source of radiation, also known as the Abbe diffraction limit (equation 1).
  • d is the diameter of the beam
  • l is the wavelength of the radiation source
  • n is the refraction index of the medium
  • Q is the half- angle of the cone of the beam.
  • High resolution of up to -10-20 nm can be achieved with electron beam lithography, because accelerated electrons are characterized by a small De Broglie wavelength.
  • electron beam lithography is limited to writing through the full thickness of a resin layer, due to the linear response of the resin to the radiation intensity, which is homogeneous throughout the resin layer (Gan, Z., Cao, Y., Evans, R.A., Gu, M., Nature Comm., 2013, 4:2061).
  • conventional (one photon) UV optical lithography is used. This technique is also limited to 2D, but is associated with a much lower resolution (>100 nm) as the wavelength of photons is generally larger than that of electrons.
  • 3D structures can be derived by writing these layer by layer, as is being done in, e.g., stereolithographic additive manufacturing techniques.
  • Direct writing of 3D structures in resins requires a non linear behavior of the resin.
  • the resin solidifies, where as in places with lower intensities (out of focus) the resin is not affected.
  • the photoactive composition that is being irradiated is a photoresist.
  • This composition is a light-sensitive material that becomes soluble (positive resist) or insoluble (negative resist) upon irradiation.
  • Positive photoresists typically generate hydrophilic functional groups upon irradiation thereby increasing their solubility in water, opposed to negative photoresists which form polymers or become crosslinked, thereby rendering an insoluble product.
  • a conventional photoresist typically comprises at least two components: a resin that is polymerized, degraded or has otherwise undergone a structural change upon irradiation and a photo-initiator.
  • the photo-initiator forms, upon excitation with light of a specific wavelength, a reactive species, such as a radical, which can initiate a structural change of the resin.
  • a reactive species such as a radical
  • radical formation occurs upon excitation from the ground state (So) to an excited state (Si or Si * ), followed by intersystem crossing (ISC) to the longer lived triplet state (Ti).
  • radicals are generated, for example through homolytic cleavage of a bond, which radicals can initiate a polymerization or cross-linking reaction of the monomers (Eliseev, S.P., Korolkov, A.E., Vitukhnovsky, A.G., Chubich, D.A., Sychev, V.V., Nanotechnologies in Russia, 2016, 11 (3-4), 200-217).
  • suitable photo-initiators are molecules comprising a conjugated n-system.
  • a conjugated n-system is a system of connected n-orbitals with delocalized electrons.
  • a n-system is connected if the electrons are delocalized, i.e. they can move freely from one atom or bond to the other. This delocalization lowers their overall energy and thereby the energy difference between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO).
  • HOMO highest occupied molecular orbital
  • LUMO lowest unoccupied molecular orbital
  • 2PL typically two photon lithography
  • 2PL is a type of optical lithography wherein the photo-initiator is excited by absorption of two photons rather than one: for example two photons in the red to near-infrared light may be absorbed instead of one photon in the ultraviolet light.
  • 2 PL allows for the creation of a non-linear process, i.e. the photo initiator that is located at the focal point of the laser is excited, whereas the surrounding molecules are remained unaffected. Hence, allowing for direct laser writing in 3D.
  • diaryliodonium hexafluoroantimonate initializes cationic (co-)polymerization reactions rather than radical-induced polymerization reactions.
  • a breakthrough in improving the resolution of optical lithography was the discovery that a second laser may be employed to quench part of the excited states of the photo-initiator before a reaction with the resin can occur.
  • This method called stimrdated emission depletion (STED) allows for the direct laser writing (in 3D) beyond the diffraction limit.
  • STED employs two lasers having different wavelengths.
  • One laser excites the photo -initiator into an excited state, whereas the second laser depletes part of the excited states (typically those excited states located at the border of the excited area, so that the diameter of the spot becomes smaller) through stimulated emission, before the excited states undergo ISC and subsequently generate radicals to initiate polymerization of the polymerizable compound.
  • the second laser depletes part of the excited states (typically those excited states located at the border of the excited area, so that the diameter of the spot becomes smaller) through stimulated emission, before the excited states undergo ISC and subsequently generate radicals to initiate polymerization of the polymerizable compound.
  • DETC 7-diethylamino-3-thenoylcoumarin
  • PETTA viscous monomer pentaerythritol tetraacrylate
  • excitation can be achieved using a two-photon laser in the 800 nm range such as Tksapphire oscillator lasers or frequency- doubled Er-doped fiber oscillators.
  • depletion can be achieved using frequency-doubled Nd or Yb lasers at 532 nm (Fischer, J., Wegener, M., Laser Photonics Rev., 2013, 7 (1), 22-44; Fischer, J. et ah, Exploring the Mechanisms in STED-Enhanced Direct laser Writing, Adv. Optical Mater., 2014).
  • the use of coumarins, including DETC, for STED is associated with a number of drawbacks.
  • the difference between one photon absorbance and emission maximum is rather small (e.g. for DETC the difference is only 60 nm). Consequently, the laser wavelength of the depletion laser approaching the wavelength of the absorption peak, results in the unwanted excitation of the photo-initiator by the depletion laser, hence lowering the overall resolution.
  • the invention relates to a photo-curable composition for direct laser writing, comprising
  • -a photosensitizer having a conjugated n-system of at least 11 atoms and which photosensitizer is excitable upon two-photon absorption at a wavelength in the range of 700-900 nm;
  • the photo-curable composition is a negative photoresist.
  • the invention further relates to the use of a photo-curable composition according to the invention in (photo) lithography, in particular in direct laser writing.
  • the composition is thus typically employable in maskless lithography.
  • the photosensitizer is a molecule that absorbs one or more photons and generates an exited state that can be quenched by energy transfer to another molecule or into light (fluorescence).
  • the photosensitizer is usually present in an amount of about 0.05 wt% or more of the total photo-curable composition.
  • the photosensitizer is usually present in an amount of about 5 wt% or less of the total photo-curable composition.
  • the photosensitizer content is 0.1 wt.% to 1 wt.% of the total composition, more preferably 0.2-0.5 wt.% of the total composition.
  • the photo-curable composition preferably comprises a photosensitizer which excitable upon two-photon absorption at a wavelength in the range of 700- 900 nm, more preferably at a wavelength in the range of 750-850 nm.
  • the skilled person will be able to determine, based on common general knowledge and the information disclosed herein whether a photosensitizer is excitable at a wavelength in the stated range, respectively has an excitation maximum in the claimed range. Pmsed on the properties of the photosensitizer the skilled person can determine a suitable excitation wavelength and excitation laser.
  • a femtosecond laser is used in a method according to the invention or to determine the excitation maximum.
  • the photosensitizer can be depleted with light of a wavelength in the range of 600-700 nm.
  • the photosensitizer has a conjugated n-system of at least 11 atoms (i.e.
  • the photosensitizer generally has a conjugated n-system of 100 atoms or less, preferably 200 atoms or less, more preferably 150 atoms or les, in particular 100 atoms or less, more in particular 50 atoms or less, more in particular 45 or less.
  • This conjugated system allows for an efficient photon absorption, due to a large two photon absorption cross section, usually of at least 100 cm 4 s molecules 1 photon 1 (GM).
  • the upper value is not critical; e.g.
  • the two photon absorption cross section may be 10000 GM or more. In practice, the two photon absorption cross section is usually 2000 or less. Preferably, the two photon absorption cross section is at least 100 GM, more preferably at least 150 GM, in particular at least 200 GM. Usually, the two photon absorption cross section is at most 1000 GM, in particular at most 750 GM, more in particular at most 500 GM.
  • a more efficient absorption means a lower intensity laser may be employed and hence the risk of inducing photobleaching of the photo-initiator is significantly decreased.
  • the two photon cross section of a molecule can be determined by Femtosecond Z- Scan Spectrometry, according to e.g. Sheik-Bahae et al. [IEEE Journal of Quantum Electronics, 26(4), 760-769, 1990]
  • the photosensitizer has a Stokes shift, i.e. the difference in wavelength between the absorption and emission maximum, of at least 40 nm .
  • the photosensitizer has a Stokes shift, of at least 80 nm, preferably at least 90 nm, more preferably at least 120 nm.
  • the practical maximum can be ⁇ determined taking into consideration the depletion wavelength of the method for which the composition is intended to be used.
  • the Stokes shift is at most 250 nm, preferably at most 200 run, in particular at most 150 nm.
  • the photosensitizer can advantageously be used in a method according to the invention wherein the wavelength of the depletion laser used to induce stimulated emission is high, with the proviso that the wavelength of the depletion laser is below the wavelength of the excitation laser.
  • the use of a depletion laser with a high wavelength significantly reduces the risk of undesired one photon absorption of the photosensitizer by the depletion laser.
  • a residual absorption at the depletion wavelength of less than 150/M/cm, preferably less than 100/M/cm was observed.
  • residual absorption of at least 50/M/cm, more preferably 0/M/cm of residual absorption is observed.
  • the photosensitizer has a molecular weight of at least 400 g/mol, preferably at least 450 g/mol, more preferably at least 500 g/mol, more preferably at least 600 g/mol, in particular of at least 800 g/mol, more in particular of at least 1000 g/mol.
  • the photosensitizer preferably has a molecular weight of at most 5.000 g/mol, more preferably at most 2.000 g/mol.
  • a high molecular weight further reduces the mobility of the photosensitizer in the photo-curable composition to prevent spreading of the polymerization process across the boundaries of the excited areas, which reduces the resolution.
  • symmetry of the molecular structure also advantageously influences the properties of the photosensitizer.
  • Symmetrical molecules are molecules having at least one symmetry element selected from the group consisting of rotational axis Cn, plane of symmetry, center of inversion and rotation reflection axis.
  • symmetrical molecules often exhibit an efficient two-photon absorption. Molecules exhibiting symmetry are therefore particularly suitable for the present invention.
  • The‘n’ in Cn is an integer having a value of at least 2, preferably 2, 3 or 4. Particularly good results have been achieved with a
  • n 2 or 3.
  • the photo -initiation process is influenced by functional groups that may be present on the conjugated n-system of the photosensitizer.
  • Electron- donating groups enrich the delocalized n-system, which typically leads to a HOMO that is higher in energy, i.e. closer to the LUMO.
  • Electron-withdrawing groups deplete the conjugated system and typically lower the energy level of the LUMO.
  • the photosensitizer is a molecule having an electron-accepting heterocyclic core. Particularly good results have been achieved with a photosensitizer having a 1,3,5-triazine core.
  • the triazine core is 2,4,6- trisubstituted and comprises three (equal) groups, each comprising a n-conjugated system and a terminal donor group selected from the group consisting of tertiary amines, secondary amines, primary amines, amides, phenoxide, phenol, esters and ethers.
  • the n-conjugated system may be substituted with suitable side-groups.
  • the invention relates to a photo-curable composition according to the invention, wherein the photosensitizer is a substituted 1,3,5-triazine, wherein the triazine is substituted on the 2,4 and 6 position with a group that comprises at least 4 n-conjugated bonds and one terminal electron- donating group.
  • this substituted 1,3,5-triazine has a C3 rotational axis.
  • a preferred group of photosensitizers according to the invention is represented by Lormula I.
  • each Q may be any functional group that can be chemically substituted on the p-bond, usually Q is H or a hydrocarbon, typically having 1-24 carbon atoms, each Q may be the same or different groups, with the proviso that most preferably the symmetry C3 rotational axis is maintained; and each A is an electron- donating group, preferably selected from the group consisting of tertiary amines, secondary amines, primary amines, amides, phenoxide, phenol, esters and ethers. Most preferably each A is the same, in order to maintain C3 rotational axis symmetry.
  • the electron- donating groups A may comprise one or more carbons. If present, the number of carbon is usually up to 24, in particular 2-12 carbons.
  • n is an integer of 1 or higher, preferably 4 or higher. Usually, n is 10 or less.
  • the three side-groups of the photosensitizer are aromatic.
  • the invention further relates to a photo-curable composition according to the invention, wherein the photosensitizer is a substituted 1,3,5- triazine, wherein the triazine is substituted on the 2,4 and 6 position with an aryl group, comprising an electron- donating group on the 4-position and wherein most preferably the wherein the photosensitizer comprises a C3 rotational axis.
  • a preferred group of aromatic photosensitizers according to the invention is represented by Formula II.
  • each Q may be any functional group that can be chemically substituted to the aromatic group, usually Q is H or a hydrocarbon, typically having 1-24 carbon atoms, each Q may be the same group or different groups, with the proviso that most preferably the symmetry C3 rotational axis is maintained.
  • Each A is an electron- donating group, preferably selected from the group consisting of tertiary amines, secondary amines, primary amines, amides, phenoxide, phenol, esters and ethers. Most preferably each A is the same.
  • the electron- donating groups A may comprise one or more carbons. If present, the number of carbon is usually up to 24, in particular 2-12.
  • n is an integer of 1 or higher, preferably 2 or higher.
  • n is 6 or less.
  • functional group Q may also be a group connecting the two aromatic rings in order that a biaryl moiety is obtained, for example a fluorene or phenanthrene moiety.
  • one or more carbon atoms of one or more aromatic group are substituted with a heteroatom, preferably nitrogen.
  • A may be any group and Q is an aliphatic or aromatic group or H.
  • Q is H or a hydrocarbon, typically having 1-24 carbon atoms
  • each Q may be the same group or different groups, with the proviso that most preferably the symmetry C3 rotational axis is maintained.
  • each A has 0-24 carbons, in particular 2-12 carbons. Most preferably each A is the same, to maintain C3 rotational axis symmetry.
  • the invention also relates to photo-curable composition according to the invention, wherein the photosensitizer is a substituted triazine, wherein the triazine is substituted on the 2,4,6-position with a fluorene, comprising an electron donating group on the 2 -position and wherein the photosensitizer comprises a C3 rotational axis.
  • the photosensitizer is a substituted triazine, wherein the triazine is substituted on the 2,4,6-position with a fluorene, comprising an electron donating group on the 2 -position and wherein the photosensitizer comprises a C3 rotational axis.
  • photosensitizers are molecules comprising a fluorene group, preferably 9-dialkyl fluorene.
  • a general scaffold is shown in
  • R2 is the core unit and is selected from the groups amine and 1,3,5-triazine.
  • R2 typically contains three substitution groups.
  • the molecule from Formula IV preferably comprises a symmetry element, typically a C2 or C3 rotational axis.
  • n is usually 2 or 3, but, in some cases may also be 1.
  • R2 may be connected directly onto the fluorene group, or may be bridged by at least one phenyl group m maybe be any integer van 0-10, preferably 0-5, in particular 0-2.
  • R may in principle be any group, but usually is an alkyl group having between 0-24 carbons, in particular 12-22 carbons. Most preferably each A is the same group, in order to keep, if present, the C2 or C3 symmetry.
  • R1 is an electron- donating or electron-accepting group, depending on the nature of the R2. It is preferred that if R1 is electron-donating that R2 is electron- accepting or vice versa. If R2 is an electron- donating group, it is preferably selected from the group consisting of tertiary amines, secondary amines, primary amines, amides, phenoxide, phenol, esters and ethers. Particularly good results have been obtained when R1 is a diphenyl amine. If R2 is an electron-withdrawing group, it is preferably selected from electron-accepting heterocycles such as thiazole, triazine, pyrimidine, pyridine, pyrazine, quinolone, isoquinoline. Alternatively, suitable groups include
  • quaternary amines nitro groups, sulfonates, nitrile groups, triflyl groups, trihalides, carboxylic acids, acyl chlorides, aldehydes, ketones and anhydrides.
  • the photosensitizer has a diyne core and, most preferably a C2 rotational axis.
  • the diyne core is 1,4-substituted with two (equal) groups (R, R’) comprising a n-conjugated system. It can thus be represented by the general formula:
  • Said groups comprising a n-conjugated system typically have a terminal accepting group selected from the group consisting of quaternary amines, nitro groups, sulfonates, nitrile groups, trifyl groups, trihalides, carboxylic acids, acyl chlorides, aldehydes, ketones and anhydrides.
  • the n-conjugated system may be substituted with suitable side-groups.
  • the photo-curable composition according to the invention comprises a photosensitizer which is a disubstituted 1,3 diyne, wherein the diyne is substituted on the 1-position and thed-position with a group that comprises at least 3 n-conjugated bonds and one terminal electron- withdrawing group and wherein the photosensitizer comprises a C2 rotational axis.
  • Q may be any functional that can be chemically substituted to the n-bond, usually Q is H or a hydrocarbon, typically having 1-24 carbon atoms, each Q may be the same group or different groups with the proviso that most preferably the symmetry C2 rotational axis is maintained.
  • Each A is an electron- accepting group, preferably selected from the group consisting of quaternary amines, nitro groups, sulfonates, nitrile groups, trifyl groups, trihalides, carboxylates, acyl chlorides, aldehydes, ketones and anhydrides. Most preferably each A is the same, to maintain C2 rotational axis symmetry.
  • the electron- accepting group A has 0-24 carbons, in particular 1-12 carbons and n is an integer of 2 or higher, preferably 4 or higher. Usually, n is 10 or less.
  • the side groups comprise aromatic groups.
  • the invention further relates to a photo-curable composition according to the invention, wherein the photosensitizer is a l,4-bis(4- ⁇ 2-(iV-methyl)pyridine-l-iumyl]ethenyl ⁇ phenyl)-butadiyne.
  • the photosensitizer is a l,4-bis(4- ⁇ 2-(iV-methyl)pyridine-l-iumyl]ethenyl ⁇ phenyl)-butadiyne.
  • R may be any functional group that can be chemically substituted to the n-bond, usually R is H or a hydrocarbon, typically having 1-24 carbon atoms, or an aromatic group, either linked or fused to the aromatic core.
  • R may be the same group or different groups, with the proviso that most preferably the symmetry C2 rotational axis is maintained.
  • Q may be a carbon or nitrogen atom.
  • each A is an electron donating group, most preferably each A is the same, to maintain the C2 rotational axis symmetry.
  • the electron -donating group has 0-24 carbons, in particular 1-12 carbons.
  • a counter ion is present to balance the positive charge of the pyridinium ion.
  • Particularly suitable counter ions include, chloride, bromide, iodide, sulfonates such as triflate.
  • the A group may also be absent.
  • the squiggly bond represents an unsaturated carbon-carbon bond and can either be a double or triple bond.
  • two additional R- groups are may be any functional group that can be chemically substituted to the p-bond present to fulfill the octet rule on the carbon atoms.
  • These R groups may be any functional group that can be chemically substituted to the p-bond and may be the same group or different groups, with the proviso that most preferably the symmetry C2 rotational axis is maintained.
  • Q is a carbon atom and A is an electron-donating group, preferably selected from the group consisting of tertiary amines, secondary amines, primary amines, amides, phenoxide, phenol, esters and ethers.
  • A is the same group, to maintain the C2 rotational axis symmetry.
  • the photosensitizer is selected from the group consisting of AF455, AF450, AF457, AF350, AF380, AF459-2, AF50, AF287, AF295, AF389, AF240, AF250, AF270, Butadiyne-1 and Butadiyne-2. Particularly good results have been achieved with AF455.
  • AF450 is also known as (2,4,6-tris[7-(diphenylamino)-9,9-didecylfluoren- 2-yl]-l,3,5-triazine)
  • AF455 is also known as (2,4,6-tris[9,9-bis(3,7-dimethyloctyl)-7- (diphenylamino)-fluoren-2yl]-l,3,5-triazine)
  • AF457 is also known as (2,4,6-tris[(7- (diphenylamino)-9,9-diprop-2-enylfluoren-2-yl]-l,3,5-triazine)
  • AF350 is also known as (N, N,N-tris[4- ⁇ 7-(2-benzothiazolyl)-9, 9-die thylfluoren-2-yl ⁇ phenyl] amine)
  • AF380 is also known as (N,N, , - tri
  • AF240 is also known as (N-, [ 7-(2- benzothiazolyl)-9,9-diethylfluoren-2-yl] N,N, -diphenyl amine)
  • AF270 is also known as (N,-[4- ⁇ 7-(2-benzothiazolyl)-9,9-diethylfluoren-2-yl ⁇ phenyl] N,N, -diphenyl amine)
  • AF295 is also known as (N,, N,, -Bis[4- ⁇ 7-(2-henzothiazolyl)-9,9-diethylfluoren-2- yljphenyl] N, -phenyl amine)
  • AF389 is also known as 2,5,-bis[(7-(diphenylamino)- 9,9-diethylfluoren-2-yl]-3a,6a-dihydro[l,3]thiazolo
  • AF455 also known as 7,7',7”-(l,3,5- triazine-2,4,6-triyl)tris[9,9-didecyl-N,N-diphenyl 9ii-Fluoren-2-amine, is a symmetrical chromophore, composed of an electron- accepting core with three arms that comprise a n-conjugated system terminated with an electron- donating group.
  • AF455 has a one photon absorption wavelength of 445 nm and a two photon absorption wavelength of 784 nm. Two photon absorption proceeds at higher energy than one photon absorption, which is due to the parity selection rules for molecules having a center of inversion: two-photon transitions from the ground state to an excited state with the same parity (gerade 1925) are allowed whereas one-photon transitions from the ground to excited state with opposite parity are allowed (gerade— > unger ade). Furthermore, AF455 exhibits fluorescence at a wavelength of 580 nm, i.e. a difference with the absorption peak of 135 nm.
  • AF455 advantageously has a two photon cross section of 400 GM.
  • AF455 is particularly suitable for use according to the invention.
  • l,4-bis ⁇ 2,5-dimethoxy-4-[2-(4- pyridyl)ethenyl]phenyl ⁇ butadiyne (Butadiyne- 1)
  • l,4-bis(4- ⁇ 2-(7V- methyl)pyridine-l-iumyl]ethenyl ⁇ phenyl)-butadiyne triflate (Butadiyne-2) are symmetrical, two -ah sorption chromophores containing a diacetylene moiety as the central n-bridge.
  • Butadiyne- 1 and Butadiyne-2 have a one photon absorption of 430 and 410 nm and a two photon cross section of 200 and 300 GM respectively. Furthermore, the emission wavelength of Butadiyne- 1 and Butadiyne is 463 and 515 nm respectively, corresponding to a stokes shift of respectively 33 nm and 105 nm.
  • the photosensitizer suitable for the invention generally does not form radicals or other reactive species upon excitation, but instead transfers its energy onto a co-initiator.
  • the co-initiator then forms radicals to initiate the
  • An advantage of using a photosensitizer absorbing light, which is transferred to a co-initiator that forms radicals is that the photosensitizer itself exhibits a higher photostability and is therefore less prone to photobleaching.
  • Suitable co-initiators are molecules which are able to form radicals after a triplet-triplet energy transfer from the sensitizer to the co-initiator.
  • the co-initiator preferably is a relatively small molecule with sufficient mobility in the photo-curable composition to reach the polymerizable compound, to initiate the polymerization.
  • the co-initiators should not possess substantial absorption of the wavelengths of either the excitation or the depletion laser.
  • the co-initiator comprises at least one hexaarylbiimidazole (HABI) and/or at least one he tero- aromatic thiol.
  • HABI hexaarylbiimidazole
  • Preferred hetero-aromatic thiols are mercaptobenzoxazole (MBO), mercaptobenzimidazole (MBI), mercaptobenzothiazole (MBT). Of these thiols, particularly good results have been achieved with MBO.
  • a preferred HABI is 2,2 , -bis(2-chlorophenyl)-4,4’,5,5’-tetrapenyl-l,2’-biimidazole (o- Cl HABI).
  • o-Cl HABI can be readily photocleaved to form a pair of lophyl radicals, which is a poor polymerization initiator but an excellent hydrogen abstractor. It can subsequently cleave the weak S-H bond to form a thiyl radical which in turn may initiate polymerization of the polymerizable compound.
  • a combination of o-Cl HABI and MBO is present.
  • excitation of o-Cl HABI proceeds at a wavelength of 355 nm, which is well below the wavelengths of the excitation and depletion lasers used in the method according to the invention. Hence, risk of direct excitation of the co-initiator with the excitation laser is minimized.
  • the co-initiator content is usually at least bout 0.1 wt.%.
  • the co initiator content is usually about 5 wt.% or less.
  • the co-initiator content preferably is 0.5 wt.% to 2.0 wt.% of the total photo-curable composition, more preferably 0.8- 1.5 wt.% of the total composition.
  • the photo-curable composition according to the invention comprises a polymerizable compound, such as a monomer, or a pre-polymer. Upon irradiation, this polymerizable compound undergoes radical-induced
  • every monomer or other polymerizable compound is suitable that is able to undergo radical-chain polymerization reactions.
  • the type of monomer or other polymerizable compound which is used can influence the photoinitation process
  • the polymerizable compound or mixture of compounds that is used determines the dielectric environment of the photoinitiator.
  • the absorption and stimulated emission characteristics of the photoinitiator are determined by the polarity (i.e. dielectric constant) of the environment. So, changing the
  • polymerizable compound or mixture of compounds from polar into apolar can shift absorption peaks by many tens of nm’s.
  • the polarity influences the solubility of the polymerizable compound and polymer and thereby promotes precipitation of the polymer.
  • the properties of the obtained polymer influence the functional characteristics of the final device it is used for.
  • a transparent polymer can be used for optical purposes, for example when light needs to be refracted by the polymer.
  • the mechanical properties of the polymer may be chosen by selecting a particular monomer. Hence, the polymer can he more mechanically strong, more rigid or more flexible depending on its final use.
  • the monomer in a photocurable composition according to the invention is selected from the group consisting of acrylates, metacrylates, acrylamides and metacrylamides.
  • the monomers can comprise monofunctional monomers, such as acrylate, metacrylate, ethylacrylate, acryloylmorpholine, fluoro acrylate or aryl acrylate.
  • the monomers can comprise bifunctional
  • monomers such as ethylene glycol diacrylate, hexanedioldiacrylate, or can comprise multifunctional monomers, such as pentaerythritol tetraacrylate
  • PETTA trimethylol triacrylate
  • TMPTA trimethylol triacrylate
  • IsoTA 2-hydroxy ethylisocyanurate
  • Multifunctional monomers contribute to high mechanical strength of the photocured composition, due to their high crosslink density.
  • a pre-polymer may be present. These are preferably oligomers of one or more of the preferred monomers.
  • the polymerizable compound is preferably present in an amount of 95.0 wt.% to 99.5 wt.% of the total composition, more preferably in an amount of 97.0- 99.0 wt.% of the total composition. If more than one type of monomers is used, the mixing ratio of different monomers determine the optical, electric and mechanical properties of the polymer. The skilled person will be able to choose suitable mixing ratio ’ s, dependent on the intended purpose of the obtained structure, based on common general knowledge and the information disclosed herein.
  • the invention further relates to a method for direct laser writing beyond the diffraction limit, comprising
  • any laser may be used that is able to excite the photosensitizer.
  • Preferred lasers include femtosecond lasers. Examples of preferred lasers include Thsapphire oscillator lasers and frequency-doubled Er-doped fiber oscillator.
  • the excitation laser preferably has a pulse rate of between 50-100 MHz, more preferably about 80 MHz.
  • the depletion laser employed in the method according to the invention may be any laser suitable inducing stimulated emission of the photosensitizer.
  • the wavelength of the depletion laser is at least 400 nm.
  • the wavelength of the depletion laser is below 1000 nm.
  • the wavelength of the depletion laser is in the range of 500 - 800 nm, more preferably in the range of 600 - 700 nm.
  • a typical laser set up comprises an excitation and depletion laser which are focused and phased using appropriate lenses and directed using mirrors.
  • the focused beams might be filtered and then put onto a substrate.
  • the set-up may further comprise resonating scanners, x, y, z stages and polarizers.
  • An advantage of the method for direct laser writing according to the invention is that high writing speeds, typically of at least 0.1 m/s, preferably of about 1 m/s or more are achieved.
  • the maximum writing speed is at most 10 m/s, in particular at most 5 m/s, more in particular at most 2.0, m/s.
  • the exposure time of the substrate by the laser influences the probability of absorption and thereby the writing speed.
  • highly absorbing photo-initiators allow for the reduction of the exposure time and thereby enhance the writing speed.
  • High absorption is further depending on a large cross section of the photo-initiator.
  • energy transfer of the photo-initiator to the co-initiator and the polymerization rate play a role. Efficient energy transfer of the photo-initiator to the co-initiator may improve the writing speed. Likewise, a higher reaction rate of the radical-chain polymerization improves writing speed.
  • the time that is needed for the stimulated emission needs to be short, in order for a fast repetition of excitation pulses.
  • the invention further relates to a method for making a photonic integrated circuit, comprising
  • radicals are formed from the co-initiator and this polymerizable compound undergoes radical-induced polymerization, thereby forming a cured (solid) material.
  • the cured material is insoluble in the photo-curable composition (and solvent of the photo-curable composition, if any).
  • the depletion laser can be used to quench part of the excited states of the photo-initiator before a reaction with the resin occurs or to suppress proceeding of the reaction.
  • the invention thus in particular extends to stimulated emission depletion (STED) lithography, allowing for direct laser writing.
  • STED stimulated emission depletion
  • the solid support that is used may be any suitable material to which the photo-curable composition after hardening adheres.
  • silicon, glass, polymer, metal, semiconductor materials such as Indium Phosphate, Gallium Arsenide (GaAs), Germanium.
  • GaAs Gallium Arsenide
  • Germanium Germanium.
  • a layer of liquid photoresist (the photo-curable composition) is applied to the solid support material in any suitable way known in the art, the skilled person will know how to do this.
  • the cured resist material After irradiation, the cured resist material is washed to remove soluble residues of the photo-curable composition. Any solvent that is suitable for removing the residual unreacted photo-curable composition according to the invention may be used.
  • the cured material preferably is transparent in the wavelength range of 1000-1600 nm, having an attenuation of lower than 1 dB/m.
  • the invention also relates to a photonic integrated circuit, waveguide or large area patterned substrate comprising a polymer and the photosensitizer having a conjugated n-system of at least 11 atoms as defined in any of the claims.
  • a photonic integrated circuit, waveguide or large area patterned substrate comprising a polymer and the photosensitizer having a conjugated n-system of at least 11 atoms as defined in any of the claims.
  • Such product is obtainable by photo-curing a composition according to the invention Typically in a method according to the invention.
  • the co-initiator has typically fully or partially reacted away. In some embodiments co-initiator is still detectable, in others not.
  • the polymerisable compound will typically at least substantially have been converted to a cured polymer.
  • direct laser writing beyond the diffraction limit is achieved which allows for a different product, distinguished from the present art.
  • the voxel size is smaller than for two-photon lithography. This
  • the invention thus also relates to a photonic integrated circuit obtainable by the method of the invention.
  • the invention also relates to 3D photonic structures, such as photonic crystals, mirrors, waveguides and tapers, obtainable by the method of the invention.
  • the invention also relates to (large area) patterned substrates, such as flat panel displays and thin film transistors, obtainable by the method of the invention.
  • the invention further relates to a photonic integrated circuit, comprising a support material and a photo-cured composition according to the invention.
  • a photonic integrated circuit comprising a support material and a photo-cured composition according to the invention.
  • a photonic integrated circuit according to the invention usually has a photo-cured polymer, wherein the polymer is transparent in the wavelength range of 1000- 1600 nm.
  • a typical photonic integrated circuit according to the invention is comprised of a silicon wafer covered with a polymer, obtained by radical-induced polymerization of the monomers, or photoresist, used in the method.
  • the feature size in the integrated circuit may be very small, i.e. 100 nm to 10 mhi.
  • the integrated circuits have many applications, for example they may be applied in electronic and photonic devices such as optical transmitters and receivers (or transceivers), silicon photonic chips, integrated waveguides and sensors.
  • Example 2 composition comprising substituted triazine (AF455)
  • a photo-initiator system consisting of 0.25 wt% of a substituted tri azine photosensitizer (AF455) as photosensitizer, and 1 wt% 2,2’-bis(2- chlorophenyl)-4,4’,5,5’-tetrapenyl-l,2 ’ -biimidazole (o-Cl HABI) and 1 wt% mercaptobenzoxazole (MBO) as co-initiators were dissolved in the monomer polyethylene glycol) diacrylate (PEG), to provide a photocurable composition according to the invention.
  • AF455 substituted tri azine photosensitizer
  • MBO mercaptobenzoxazole
  • the photocurable composition was drop-cast onto a glass slide and excited with 780 nm ultrashort laser pulse, 60 fs pulse duration, 100 MHz repetition rate.
  • the pulse energy was controlled by means of an acousto-optic modulator (AOM).
  • AOM acousto-optic modulator
  • NA 1.46.
  • the objective lens was translated along the optical axis (z-direction) using a piezo stage with a positioning step size of 20 nm.
  • the sample was translated laterally (x, y-directions) using a linear stage with a horizontal working range from 0.1 x 0.1 mm2 to 5 x 5 mm 2 .
  • Figure 2 shows a 45 x 45 pm 2 woodpile structure lithographically constructed at a scan speed of 1 mni/s by excitation laser. Each rod (1.8 pm) comprises 3 prints and rod spacing is 7 pm. Pile layer in z-direction spaced at 1.4 pm.
  • This Example supports in particular the suitablity of a composition comprising a substituted triazine (such as represented by the general formula I) according to the invention in direct laser writing.
  • Example 3 composition comprising DETC (comparative example)
  • the photo-initiator system consisted of 0.25 wt% 7-diethylamino-3- thenoylcoumarin (DETC) instead of AF455 . It was dissolved in the monomer polyethylene glycol) diacrylate (PEG), to provide a comparative photocurable composition. It was used to perform two-photon laser writing. DETC is widely considered as present best photo-initiator for use in 3D STED direct laser writing. Using the same laser parameters as that of Example 2, a line with a length of 100 pm and width of 1 pm was lithographically written at a scan speed of 100 pm/s.
  • a composition (comprising AF455). as described in Example 2 was used Compared to Example 2, a depletion laser (at 638 nm, continuous wave) was added and aligned with the excitation laser beam through a dichroic mirror, as shown in Figure 4. Both beams were focused through an oil immersion objective lens.
  • AF455 photo-initiator system cf.
  • Example 2 with both excitation beam and depletion beam on, no written structure showed. This indicates it is possible to effectively completely suppress the formation of the structure by the depletion beam, where desired.

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  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention concerne une composition photodurcissable pour l'écriture laser directe, en particulier l'écriture laser directe en 3D, comprenant : un photosensibilisateur ayant un système conjugué d'au moins 11 atomes et lequel photosensibilisateur peut être excité lors d'une absorption à deux photons à une longueur d'onde dans la plage de 700 à 900 nm, et lequel photosensibilisateur est appauvri à une longueur d'onde dans la plage de 600 à 700 nm ; au moins un co-initiateur capable de former des radicaux ; et un composé polymérisable, en particulier un monomère, qui est polymérisable par polymérisation induite par des radicaux.
PCT/NL2019/050688 2018-10-19 2019-10-18 Photochimie à grande vitesse pour lithographie 3d WO2020080945A1 (fr)

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CN116300310B (zh) * 2023-01-06 2024-04-16 之江实验室 一种利用光引发剂实现超分辨刻写与成像的方法和装置

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