CN102768466A - Chemical amplification type positive photoresist, preparation method and application thereof in two-photon fine processing - Google Patents
Chemical amplification type positive photoresist, preparation method and application thereof in two-photon fine processing Download PDFInfo
- Publication number
- CN102768466A CN102768466A CN2011101147635A CN201110114763A CN102768466A CN 102768466 A CN102768466 A CN 102768466A CN 2011101147635 A CN2011101147635 A CN 2011101147635A CN 201110114763 A CN201110114763 A CN 201110114763A CN 102768466 A CN102768466 A CN 102768466A
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- China
- Prior art keywords
- photon
- acid
- chemical amplification
- positive photoresist
- type positive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
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- 238000003199 nucleic acid amplification method Methods 0.000 title claims abstract description 83
- 238000012545 processing Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002253 acid Substances 0.000 claims abstract description 81
- 239000011347 resin Substances 0.000 claims abstract description 56
- 229920005989 resin Polymers 0.000 claims abstract description 56
- 238000010521 absorption reaction Methods 0.000 claims abstract description 23
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- 238000004090 dissolution Methods 0.000 claims abstract description 16
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- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 claims description 20
- 229910052594 sapphire Inorganic materials 0.000 claims description 16
- 239000010980 sapphire Substances 0.000 claims description 16
- 238000013519 translation Methods 0.000 claims description 16
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- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 5
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- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 4
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 claims description 4
- JHKFHQVAHFWDRE-UHFFFAOYSA-N C(F)(F)F.C1(=CC=CC=C1)[S](C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound C(F)(F)F.C1(=CC=CC=C1)[S](C1=CC=CC=C1)C1=CC=CC=C1 JHKFHQVAHFWDRE-UHFFFAOYSA-N 0.000 claims description 4
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- 125000006267 biphenyl group Chemical group 0.000 claims description 4
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- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 claims description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
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- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 3
- SVONRAPFKPVNKG-UHFFFAOYSA-N 2-ethoxyethyl acetate Chemical compound CCOCCOC(C)=O SVONRAPFKPVNKG-UHFFFAOYSA-N 0.000 claims description 3
- HXDLWJWIAHWIKI-UHFFFAOYSA-N 2-hydroxyethyl acetate Chemical compound CC(=O)OCCO HXDLWJWIAHWIKI-UHFFFAOYSA-N 0.000 claims description 3
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- JKYIVMKKKADFGC-UHFFFAOYSA-N diphenyliodanium;fluoroform Chemical compound FC(F)F.C=1C=CC=CC=1[I+]C1=CC=CC=C1 JKYIVMKKKADFGC-UHFFFAOYSA-N 0.000 claims description 3
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- TVODIPKBEMSROH-UHFFFAOYSA-N ethyl 3-methoxy-2-methylpropanoate Chemical compound CCOC(=O)C(C)COC TVODIPKBEMSROH-UHFFFAOYSA-N 0.000 claims description 3
- 229940057867 methyl lactate Drugs 0.000 claims description 3
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- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
Abstract
The invention discloses a chemical amplification type positive photoresist which comprises the following raw materials in parts by weight: 0.0001-2 parts of photosensitive dye; 0.005-10 parts of a photoacid generator; 5-80 parts of acid-degradable resin; 0-60 parts of a dissolution inhibitor; 20-90 parts of an organic solvent. The invention also discloses a preparation method and application of the photoresist. The invention has the characteristics that the sensitized acid-producing system has simple composition, convenient preparation and reliable acid-producing effect under the excitation of two photons; the sensitizer has large two-photon absorption cross section, simple synthesis and low cost; the photoresist prepared by the sensitized acid-producing system has high processing resolution and low processing energy threshold.
Description
Technical field
The invention belongs to chemical amplification type positive photoresist field, particularly relate to a kind of chemical amplification type positive photoresist, preparation method and the application in the two-photon retrofit thereof.
Background technology
The two-photon process technology has the material penetrability by force, and the advantage that spatial resolution is high has a wide range of applications at the trickle manufacture field of 3 D super precision.And the preparation of corresponding photoresist is the key content of two-photon Processing Technology Development.At present, the material that is applied to the two-photon working research mainly is: the 1) negative photoresist of commercialization, and like the radical polymerization mould assembly photoresist SCR500 of Japan Synthetic Rubber Co. Ltd, the cationic polymerization type photoresist SU-8 of U.S. MicroChem company.Because the initiation component in these materials absorbs all at ultraviolet band, the near-infrared region two photon absorption cross section is very little, causes the process energy very high, and speed is very slow, and the volumetric contraction that the monomer polymerization process takes place has also limited the raising of material discrimination rate.2) two-photon dye sensitization negative photoresist is referring to article (Opt.Express, 2001, vol.8; 517-584, Chem.Phys.Lett., 2001, vol.340; 444-448, J.Photochem.Photobiol.A, 2009, vol.203; 211-215), its mechanism is to utilize the commercial photo-acid agent of the dye sensitization with big two photon absorption cross section, the efficent electronic transfer reaction takes place between the two under two-photon excitation generate Bronsted acid or radical cation, causes free radical or cationic polymerization.Yet,, can't be used to prepare chemical amplification type positive photoresist based on acid catalysis mechanism owing to all contain alkaline nitrogen-containing group in the molecular structure of dye in the above-mentioned article as electron donor.3) utilize the commercialization dye sensitization to give birth to the chemical amplification type positive photoresist of acid system preparation.Utilize commercial initiating agent ITX sensitization photo-acid agent to prepare the chemical amplification type positive photoresist and carried out the little processing of double photon three dimension like Lee etc.(J.Am.Chem.Soc.，2009，vol.131，11294-11295)。But because the two photon absorption cross section of common commercialization dyestuff is all very little, the energy that two-photon adds the needs in man-hour is very big, and process velocity is very slow.4) utilization has the chemical amplification type positive photoresist of the photo-acid agent preparation of big two photon absorption cross section.As the people such as Marder of U.S. Georgia Institute of Technology utilize synthetic molecule with big two photon absorption cross section contain the photo-acid agent preparation of arylsulfonium salts structure the chemical amplification type positive photoresist (Science, 2002, vol.296,1106-1109); The arylsulfonium salts class photo-acid agent with big two photon absorption cross section that the people such as Belfield of university of U.S. Florida synthesize (Chem.Commun., 2009,827-829, DOI:10.1039/b815831b); The chemical amplification positive photoresist of the living sour agent preparation of the two-photon with N-hydroxyl dicarboximide ester structure that utilizations such as the Ober of Cornell Univ USA are synthetic (J.Mater.Chem., 2009, Vol.19,505-513).Yet, more than the single component two-photon that uses in these systems give birth to the restriction that sour agent structural design receives the livings acid groups in the molecule, be difficult to improve two photon absorption cross section, and synthesis step is many, condition is harsh, is difficult to the input practical application.
In sum, also do not have ripe commercialization two-photon processing to use the chemical amplification type positive photoresist at present in the world, this mainly is because of difficult, with high costs with the synthetic preparation of the living acid system of two-photon absorption process coupling.
Summary of the invention
First technical matters that the present invention will solve is to provide a kind of chemical amplification type positive photoresist; This photoresist contains the two-photon sensitization and gives birth to acid system; Giving birth to acid system, acid-degeneration type resin, dissolution inhibitor, solvent etc. by the two-photon sensitization forms according to a certain ratio; Have the high and low characteristics of machining energy threshold value of machining resolution; Can solve the chemical amplification type positive photoresist preparation difficulty that is used for two-photon processing at present; Machining energy is too high, the problem that speed is slow excessively.The present invention gives birth to sour agent with sensitizer and commercialization and forms the living acid system of sensitization, and sensitization is given birth to acid system and under the two-photon excitation condition, produced acid, the degraded of catalysis acid sensitive resin, thus prepare the chemical amplification type positive photoresist that is applicable to two-photon processing; Characteristics of the present invention are that sensitization product acid system is formed simply, and preparation is convenient, and the sour effect of product is infallible under two-photon excitation; The sensitizer two photon absorption cross section is big, and is synthetic simple, with low cost; The photoresist of preparing with this sensitization product acid system has very high machining resolution and very low machining energy threshold value.
Second technical matters that the present invention will solve is to provide a kind of preparation method of chemical amplification type positive photoresist.
The 3rd technical matters that the present invention will solve is to provide the application of a kind of chemical amplification type positive photoresist in the two-photon retrofit; This photoresist has strong two-photon absorption at the Visible-to-Near InfaRed wave band, has the high and low characteristics of machining energy threshold value of machining resolution, can be applicable to the little manufacture field of two-photon.
For solving above-mentioned first technical matters, a kind of chemical amplification type positive photoresist of the present invention, it contains the two-photon sensitization and gives birth to acid system.
Further, the living acid system of said two-photon sensitization comprises: 0.0001～2 part of light-sensitive coloring agent; 0.005～10 part of photo-acid agent.This life acid system is made up of by certain proportioning light-sensitive coloring agent with big two photon absorption cross section and the commercialization photo-acid agent that can directly buy; Solved the single component two-photon and given birth to the restriction that sour agent structural design receives the living acid groups in the molecule, be difficult to improve two photon absorption cross section, and synthesis step has been many, the problem that condition is harsh.This system has strong two-photon absorption at the Visible-to-Near InfaRed wave band, can produce Bronsted acid efficiently, can be used for preparation and have low machining energy threshold value, high-resolution two-photon chemical amplification type positive photoresist.
Further, a kind of chemical amplification type positive photoresist of the present invention comprises the raw material of following parts by weight:
0.0001～2 part of light-sensitive coloring agent;
0.005～10 part of photo-acid agent;
5～80 parts of acid-degeneration type resins;
0～60 part of dissolution inhibitor;
20～90 parts of organic solvents.
Further, described light-sensitive coloring agent be with the triphenylamine be electron donor straight chain or many types benzal cyclanone two-photon dyestuff or be the straight chain of electron donor or the benzal alkane ketone two-photon dyestuff of many types with the triphenylamine.Such dyestuff has big two photon absorption cross section at Visible-to-Near InfaRed, and is synthetic simple and easy, and economical and efficient can be given birth to acid system with the two-photon sensitization efficiently of the composite composition of multiple commercial photo-acid agent, selects widely, and compatibility is flexible.
Further, said is that the straight chain of electron donor or the benzal cyclanone two-photon dyestuff of many types are the compounds with molecular structure with the triphenylamine:
Further, said is that the straight chain of electron donor or the benzal alkane ketone two-photon dyestuff of many types are the compounds with molecular structure with the triphenylamine:
In above-mentioned general molecular formula M1～M6: A1, A2, A3, A4 are halogen atom, hydrogen atom, alkyl, alkoxy or nitro; Be preferably hydrogen atom, alkyl or alkoxy; A1, A2, A3, A4 can be identical or different substituted radical; A5, A6 are hydrogen atom or alkyl; A5, A6 can be identical or different substituted radical;
is cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone or cyclooctanone.
Further, described halogen atom is meant fluorine atom, chlorine atom, bromine atoms or iodine atom;
Further, what described alkyl was a carbon number less than in 15 the alkyl is a kind of, for example methyl, ethyl, propyl group, isopropyl, normal-butyl, isobutyl, the tert-butyl group etc.
Further, what described alkoxy was a carbon number less than in 15 the alkoxy is a kind of, for example methoxyl, ethoxy, propoxyl group, isopropoxy, n-butoxy, isobutoxy, tert-butoxy etc.
Further, described acid-degeneration type resin can be that any under acid catalysis, degraded generates the photoetching resin of alkali solubility group.The limiting examples of acid-degeneration type resin include but not limited to part methyl methyl acrylate and metering system tert-butyl acrylate multipolymer, t-BOC (tertbutyloxycarbonyl) protection gather 4-hydroxy styrenes, methyl methacrylate and methacrylic acid dihydropyrane ester copolymer, and other common acid catalytic degradation type photoetching resins.
Further, said dissolution inhibitor can be that any under acid catalysis, degraded produces micromolecule benzene, biphenyl, the fused-ring derivatives of alkali solubility group.The limiting examples of dissolution inhibitor include but not limited to t-BOC protection phenol, t-BOC protection to 1 of biphenol, t-BOC protection; 3; 1,2 of 5-trisphenol, t-BOC protection, 2 of the adjacent trisphenol of 3-, t-BOC protection; 2 of 6-dinitrophenol, t-BOC protection, the polyhydroxy substituted benzenes such as bisphenol-A of 6-dihydroxy nitrobenzene, t-BOC protection, and other common chemical amplification positive photoresists use dissolution inhibitor.
Further, said photo-acid agent can be any acidic photo-induced acid agent of under illumination, decomposing, and the limiting examples of photo-acid agent comprises N-hydroxyphthalimide ester, N-hydroxyl naphthalimide ester, triazine, sulfosalt, salt compounded of iodine etc.Special; Photo-acid agent is selected from N-hydroxyphthalimide triflate, N-hydroxyl-1; 8-naphthalimide triflate, N-hydroxyphthalimide methane sulfonate, N-hydroxyl-1; The set that 8-naphthalimide methane sulfonate, N-hydroxyphthalimide p-methyl benzenesulfonic acid ester, N-hydroxyl-1,8-naphthalimide p-methyl benzenesulfonic acid ester, triazine derivative, dinitro benzyl p-toluenesulfonic esters etc. are formed; In addition, photo-acid agent can be selected from diphenyl iodonium fluoroform sulphonate, diphenyl iodonium perfluoro butyl sulfosalt, diphenyl iodonium hexafluorophosphate, diphenyl iodonium hexafluoro antimonate, diphenyl iodonium hexafluoro arsenate, the two pairs of methylbenzene iodine fluoroform sulphonates, the two pairs of methylbenzene iodine perfluoro butyl sulfosalts, the two pairs of methylbenzene iodine hexafluorophosphates, the two pairs of methylbenzene iodine hexafluoro antimonates, the two pairs of methylbenzene iodine hexafluoro arsenates, diphenyl p-methoxyphenyl sulphur fluoroform sulphonate, diphenyl p-methylphenyl sulphur fluoroform sulphonate, triphenyl sulphur fluoroform sulphonate, three (to tert-butyl-phenyl) sulphur fluoroform sulphonate, diphenyl p-methoxyphenyl sulphur perfluoro butyl sulfosalt, diphenyl p-methylphenyl base sulphur perfluoro butyl sulfosalt, diphenyl to tert-butyl-phenyl sulphur perfluoro butyl sulfosalt, the diphenyl potpourri to one or more arbitrary proportions in isobutyl phenenyl sulphur perfluoro butyl sulfosalt, triphenyl sulphur perfluoro butyl sulfosalt, three (to tert-butyl-phenyl) sulphur perfluoro butyl sulfosalt, triphenyl sulphur hexafluoro arsenate, triphenyl sulphur hexafluoro antimonate, triphenyl sulphur hexafluorophosphate and triphenyl sulphur fluoroform sulphonate, the 4-thiophenyl phenyl diphenyl sulphur hexafluorophosphate.
Further, said organic solvent is for being used in the conventional various organic solvents of photoetching compositions.The limiting examples of organic solvent includes but not limited to glycol monoethyl ether, glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol acetate, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, acetate EGME, propylene glycol methyl ether acetate, propylene glycol, propylene glycol monoacetate, MEK, methyl isoamyl ketone, cyclohexanone 、 diox, methyl lactate, ethyl lactate, methyl pyruvate, ethyl pyruvate, methoxypropionic acid methyl esters, ethoxyl ethyl propionate, N; Dinethylformamide, N-N-methyl-2-2-pyrrolidone N-, 3-ethoxyl ethyl propionate, 2-heptanone, gamma-butyrolacton, 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-2-methyl ethyl propionate, ethoxyethyl acetate(EA), acetate hydroxyl ethyl ester, 2-hydroxy-3-methyl methyl butyrate, 3-methoxyl-2 Methylpropionic acid methyl esters, 3-ethoxyl ethyl propionate, 3-methoxyl-2 Methylpropionic acid ethyl ester, ethyl acetate, butyl acetate, pentyl acetate, toluene, xylene or dimethyl sulfoxide (DMSO).
Above-mentioned chemical amplification type positive photoresist can make with conventional method, still, in order to reach better technique effect, adopts following method preparation.
For solving above-mentioned second technical matters, the preparation method of chemical amplification type positive photoresist of the present invention comprises the steps:
Under the lucifuge condition; The photo-acid agent of 0.0001～2 part two-photon sensitizer and 0.005～10 part is dissolved in 20～90 parts the organic solvent; After treating dissolving fully; Acid-degeneration type resin and 0～60 part of dissolution inhibitor to wherein continuing 5～80 parts of addings stir, and promptly obtain two-photon chemical amplification type positive photoresist.
For solving above-mentioned the 3rd technical matters, the chemical amplification type positive photoresist that contains the living acid system of two-photon sensitization according to the invention is applicable to the two-photon retrofit, comprises the steps:
To coat pretreated glass or silicon chip surface by the two-photon chemical amplification type positive photoresist of the present invention preparation, treat solvent evaporates after, form the photoresist film that is applicable to two-photon photoetching processing; The glass sheet that scribbles two-photon chemical amplification positive photoresist film is placed by on the little translation stage of computer-controlled three-dimensional; With the Ti-Sapphire femto-second laser is light source; Laser beam focuses on the two-photon chemical amplification positive photoresist film through a microcobjective; Sensitization is given birth to sour agent and is given birth to acid after the two-photon sensitizing dyestuff generation two-photon absorption at laser spot place, catalysis glued membrane generation acid degradation reaction, thus carry out three-dimensional little processing; Glass sheet after will machining then places the baking of baking oven back, and the back baking is accomplished to be placed in the developer solution and developed, and the part that flush away has been degraded just can obtain little graphics processing.
Give birth to acid system and have following significant advantage with two-photon sensitization of the present invention with it two-photon chemical amplification type positive photoresist for preparing:
1) two-photon sensitization of the present invention is given birth in the acid system, and sensitizer has big two photon absorption cross section in the 700-900nm scope, and is synthetic simple and easy; Economical and efficient; And can give birth to acid system with the sensitization of the composite composition two-photon of multiple commercial photo-acid agent, and to select widely, compatibility is flexible.
2) trianilino group in the benzal of straight chain among the present invention or many types (ring) the alkane ketone two-photon dyestuff has good electron donation as electron donor.
3) trianilino group in the benzal of straight chain among the present invention or many types (ring) the alkane ketone two-photon dyestuff can not produce acid catalyzed chemical amplification process and suppress.
4) benzal of straight chain among the present invention or many types (ring) alkane ketone two-photon dyestuff has big two photon absorption cross section and sensitization efficient.
5) the two-photon chemical amplification type positive photoresist among the present invention has very low machining energy threshold value.Two-photon chemical amplification type positive photoresist among the present invention has very high machining resolution.
Description of drawings
Shown in Figure 1 is the two photon absorption cross section spectrogram that dyestuff S1 utilizes the up-conversion fluorescence method to record in acetonitrile in the embodiment of the invention 1;
Shown in Figure 2 is the two photon absorption cross section spectrogram that dyestuff S6 utilizes the up-conversion fluorescence method to record in acetonitrile in the embodiment of the invention 7;
Shown in Figure 3 for according to the photoresist film of the embodiment of the invention 1 formulated through attenuated total reflection fluorescent absorption test collection of illustrative plates behind the femtosecond laser pre-irradiation (variation of carbonyl absorption peak on the t-BOC group of the acid-sensitive sense in 1735cm-1 place is shown);
The microcosmic two dimension groove stereoscan photograph that obtains of processing for the embodiment of the invention 1 shown in Figure 4;
The stereoscan photograph of processing the three-dimensional little processing structure that obtains for the embodiment of the invention 12 shown in Figure 5.
Embodiment
Below in conjunction with specific embodiment the present invention is described further, but the present invention is not limited to following examples.
Embodiment 1
A kind ofly contain the chemical amplification type positive photoresist that acid system is given birth in the two-photon sensitization, comprise the raw material of following parts by weight:
In the formula M 1; A1, A2, A3, A4 are hydrogen atom,
be that the dyestuff S1 of cyclopentanone is as the two-photon sensitizer;
Under the lucifuge condition, 20mg S1 and 120mg N-hydroxyphthalimide triflate are dissolved in 15g N, the N dimethyl formamide; After treating dissolving fully; What add 4g part t-BOC protection gathers the 4-hydroxy styrenes, lucifuge condition held 4h, and stir.The two-photon polymerized resin for preparing is applied on the glass sheet, and 90 ℃ of bakings were removed dissolvent residual in 5 minutes, utilized the Ti-Sapphire femtosecond as LASER Light Source; Pulse width 80 femtoseconds, repetition frequency 80MHz, wavelength 780nm; Output power 0.35mw, laser beam is 100x through an enlargement factor, the micro-oily mirror in resin aperture 1.45 focuses in the two-photon chemical amplification positive photoresist film; The glass sheet that scribbles resin places by processing on the little translation stage of computer-controlled three-dimensional; Machine the back and after 110 ℃, dried by the fire 1 minute, in the tetramethylammonium hydroxide aqueous solution of 0.26N (N), develop then, promptly obtain the retrofit figure.
Embodiment 2
A kind ofly contain the chemical amplification type positive photoresist that acid system is given birth in the two-photon sensitization, comprise the raw material of following parts by weight:
In the formula M 1; A1, A2 are hydrogen atom; A3, A4 are methyl,
be that the dyestuff S2 of cyclobutanone is as the two-photon sensitizer;
Under the lucifuge condition; 10mg S2 and 100mg N-hydroxyphthalimide triflate are dissolved in the 15g diethylene glycol dimethyl ether, treat dissolving fully after, what add 4g part t-BOC protection gathers the 4-hydroxy styrenes; Lucifuge condition held 4h, and stir.The two-photon polymerized resin for preparing is applied on the glass sheet, and 90 ℃ of bakings were removed dissolvent residual in 5 minutes, utilized the Ti-Sapphire femtosecond as LASER Light Source; Pulse width 80 femtoseconds, repetition frequency 80MHz, wavelength 750nm; Output power 0.5mw, laser beam is 100x through an enlargement factor, the micro-oily mirror in resin aperture 1.45 focuses in the two-photon chemical amplification positive photoresist film; The glass sheet that scribbles resin places by processing on the little translation stage of computer-controlled three-dimensional; Machine the back and after 110 ℃, dried by the fire 1 minute, in the tetramethylammonium hydroxide aqueous solution of 0.26N (N), develop then, promptly obtain the retrofit figure.
Embodiment 3
A kind ofly contain the chemical amplification type positive photoresist that acid system is given birth in the two-photon sensitization, comprise the raw material of following parts by weight:
In the formula M 2; A1, A2 are methyl; A3 is a hydrogen atom,
be that the dyestuff S3 of cyclobutanone is as the two-photon sensitizer;
Under the lucifuge condition, 15mg S3 and 60mg two (trichloromethyl) triazine are dissolved in 15g acetate EGME, treat dissolving fully after, what add 5g part t-BOC protection gathers the 4-hydroxy styrenes, lucifuge condition held 4h, and stirring.The two-photon polymerized resin for preparing is applied on the glass sheet, and 90 ℃ of bakings were removed dissolvent residual in 5 minutes, utilized the Ti-Sapphire femtosecond as LASER Light Source; Pulse width 80 femtoseconds, repetition frequency 80MHz, wavelength 800nm; Output power 0.30mw, laser beam is 100x through an enlargement factor, the micro-oily mirror in resin aperture 1.45 focuses in the two-photon chemical amplification positive photoresist film; The glass sheet that scribbles resin places by processing on the little translation stage of computer-controlled three-dimensional; Machine the back and after 110 ℃, dried by the fire 1 minute, in the tetramethylammonium hydroxide aqueous solution of 0.26N (N), develop then, promptly obtain the retrofit figure.
Embodiment 4
A kind ofly contain the chemical amplification type positive photoresist that acid system is given birth in the two-photon sensitization, comprise the raw material of following parts by weight:
In the formula M 3; A1, A2 are ethoxy,
be that the dyestuff S4 of cyclohexanone is as the two-photon sensitizer;
Under the lucifuge condition; 10mg S4 and 100mg N-hydroxyphthalimide triflate are dissolved in the 15g diethylene glycol dimethyl ether, treat dissolving fully after, what add 4g part t-BOC protection gathers the 4-hydroxy styrenes; Lucifuge condition held 4h, and stir.The two-photon polymerized resin for preparing is applied on the glass sheet, and 90 ℃ of bakings were removed dissolvent residual in 5 minutes, utilized the Ti-Sapphire femtosecond as LASER Light Source; Pulse width 80 femtoseconds, repetition frequency 80MHz, wavelength 760nm; Output power 0.25mw, laser beam is 100x through an enlargement factor, the micro-oily mirror in resin aperture 1.45 focuses in the two-photon chemical amplification positive photoresist film; The glass sheet that scribbles resin places by processing on the little translation stage of computer-controlled three-dimensional; Machine the back and after 110 ℃, dried by the fire 1 minute, in the tetramethylammonium hydroxide aqueous solution of 0.26N (N), develop then, promptly obtain the retrofit figure.
A kind ofly contain the chemical amplification type positive photoresist that acid system is given birth in the two-photon sensitization, comprise the raw material of following parts by weight:
In the formula M 1; A1, A2, A 3, A4 are hydrogen atom,
be that the dyestuff S1 of cyclopentanone is as the two-photon sensitizer
Under the lucifuge condition, 10mg S1 and 90mg N-hydroxyl-1,8-naphthalimide triflate are dissolved in the 15g diethylene glycol dimethyl ether; After treating dissolving fully; What add 4g part t-BOC protection gathers the 4-hydroxy styrenes, lucifuge condition held 4h, and stir.The two-photon polymerized resin for preparing is applied on the glass sheet, and 90 ℃ of bakings were removed dissolvent residual in 5 minutes, utilized the Ti-Sapphire femtosecond as LASER Light Source; Pulse width 80 femtoseconds, repetition frequency 80MHz, wavelength 780nm; Output power 0.35mw, laser beam is 100x through an enlargement factor, the micro-oily mirror in resin aperture 1.45 focuses in the two-photon chemical amplification positive photoresist film; The glass sheet that scribbles resin places by processing on the little translation stage of computer-controlled three-dimensional; Machine the back and after 110 ℃, dried by the fire 1 minute, in the tetramethylammonium hydroxide aqueous solution of 0.26N (N), develop then, promptly obtain the retrofit figure.
Embodiment 6
A kind ofly contain the chemical amplification type positive photoresist that acid system is given birth in the two-photon sensitization, comprise the raw material of following parts by weight:
In the formula M 1; A1, A2, A3, A4 are hydrogen atom,
be that the dyestuff S5 of cyclobutanone is as the two-photon sensitizer;
Under the lucifuge condition; 15mg S5 and 80mg two (4-aminomethyl phenyl) iodine hexafluorophosphate are dissolved in the 15g gamma-butyrolacton, treat dissolving fully after, add 6g methyl methacrylate, methacrylic acid dihydropyrane ester copolymer; Lucifuge condition held 4h, and stir.The two-photon polymerized resin for preparing is applied on the glass sheet, and 70 ℃ of bakings were removed dissolvent residual in 10 minutes, utilized the Ti-Sapphire femtosecond as LASER Light Source; Pulse width 80 femtoseconds, repetition frequency 80MHz, wavelength 800nm; Output power 0.5mw, laser beam is 100x through an enlargement factor, the micro-oily mirror in resin aperture 1.45 focuses in the two-photon chemical amplification positive photoresist film; The glass sheet that scribbles resin places by processing on the little translation stage of computer-controlled three-dimensional; Machine the back and after 90 ℃, dried by the fire 1 minute, in the tetramethylammonium hydroxide aqueous solution of 0.26N (N), develop then, promptly obtain the retrofit figure.
Embodiment 7
A kind ofly contain the chemical amplification type positive photoresist that acid system is given birth in the two-photon sensitization, comprise the raw material of following parts by weight:
In the formula M 4, A1, A2, A3, A4, A5 and A6 are the dyestuff S6 of hydrogen atom as the two-photon sensitizer;
Under the lucifuge condition; 10mg S6 and 60mg two (4-aminomethyl phenyl) iodine hexafluorophosphate are dissolved in the 20g ethylene glycol diethyl ether, treat dissolving fully after, add 8g methyl methacrylate, metering system tert-butyl acrylate multipolymer; Lucifuge condition held 4h, and stir.The two-photon polymerized resin for preparing is applied on the glass sheet, and 90 ℃ of bakings were removed dissolvent residual in 5 minutes, utilized the Ti-Sapphire femtosecond as LASER Light Source; Pulse width 80 femtoseconds, repetition frequency 80MHz, wavelength 760nm; Output power 0.5mw, laser beam is 100x through an enlargement factor, the micro-oily mirror in resin aperture 1.45 focuses in the two-photon chemical amplification positive photoresist film; The glass sheet that scribbles resin places by processing on the little translation stage of computer-controlled three-dimensional; Machine the back and after 110 ℃, dried by the fire 1 minute, in the tetramethylammonium hydroxide aqueous solution of 0.26N (N), develop then, promptly obtain the retrofit figure.
A kind ofly contain the chemical amplification type positive photoresist that acid system is given birth in the two-photon sensitization, comprise the raw material of following parts by weight:
In the formula M 4, A1, A3, A4 and A5 are hydrogen atom, and A6 is that the dyestuff S7 of n-hexyl is as the two-photon sensitizer;
Under the lucifuge condition, 8mg S7 and 64mg two (4-aminomethyl phenyl) iodine hexafluorophosphate are dissolved in the 12g ethylene glycol diethyl ether, treat dissolving fully after, what add 5g part t-BOC protection gathers the 4-hydroxy styrenes, lucifuge condition held 5h, and stirring.The two-photon polymerized resin for preparing is applied on the glass sheet, and 90 ℃ of bakings were removed dissolvent residual in 5 minutes, utilized the Ti-Sapphire femtosecond as LASER Light Source; Pulse width 80 femtoseconds, repetition frequency 80MHz, wavelength 760nm; Output power 0.4mw, laser beam is 100x through an enlargement factor, the micro-oily mirror in resin aperture 1.45 focuses in the two-photon chemical amplification positive photoresist film; The glass sheet that scribbles resin places by processing on the little translation stage of computer-controlled three-dimensional; Machine the back and after 110 ℃, dried by the fire 1 minute, in the tetramethylammonium hydroxide aqueous solution of 0.26N (N), develop then, promptly obtain the retrofit figure.
Embodiment 9
A kind ofly contain the chemical amplification type positive photoresist that acid system is given birth in the two-photon sensitization, comprise the raw material of following parts by weight:
In the formula M 4, A1, A2, A3 and A4 are hydrogen atom, and A5, A6 are that the dyestuff S8 of normal-butyl is as the two-photon sensitizer;
Under the lucifuge condition, 10mg S8 and 50mg two (4-aminomethyl phenyl) iodine hexafluorophosphate are dissolved in the 12g diethylene glycol dimethyl ether, treat dissolving fully after, what add 6g part t-BOC protection gathers the 4-hydroxy styrenes, lucifuge condition held 5h, and stirring.The two-photon polymerized resin for preparing is applied on the glass sheet, and 90 ℃ of bakings were removed dissolvent residual in 5 minutes, utilized the Ti-Sapphire femtosecond as LASER Light Source; Pulse width 80 femtoseconds, repetition frequency 80MHz, wavelength 760nm; Output power 0.4mw, laser beam is 100x through an enlargement factor, the micro-oily mirror in resin aperture 1.45 focuses in the two-photon chemical amplification positive photoresist film; The glass sheet that scribbles resin places by processing on the little translation stage of computer-controlled three-dimensional; Machine the back and after 110 ℃, dried by the fire 1 minute, in the tetramethylammonium hydroxide aqueous solution of 0.26N (N), develop then, promptly obtain the retrofit figure.
Embodiment 10
A kind ofly contain the chemical amplification type positive photoresist that acid system is given birth in the two-photon sensitization, comprise the raw material of following parts by weight:
In the formula M 4, A1, A2, A3 and A4 are hydrogen atom, and A5 and A6 are the dyestuff S9 of methyl as the two-photon sensitizer;
Under the lucifuge condition, 10mg S9 and 100mg N-hydroxyphthalimide methanesulfonates are dissolved in the 12g diethylene glycol dimethyl ether, treat dissolving fully after, what add 6g part t-BOC protection gathers the 4-hydroxy styrenes, lucifuge condition held 5h, and stirring.The two-photon polymerized resin for preparing is applied on the glass sheet, and 90 ℃ of bakings were removed dissolvent residual in 5 minutes, utilized the Ti-Sapphire femtosecond as LASER Light Source; Pulse width 80 femtoseconds, repetition frequency 80MHz, wavelength 760nm; Output power 1.0mw, laser beam is 100x through an enlargement factor, the micro-oily mirror in resin aperture 1.45 focuses in the two-photon chemical amplification positive photoresist film; The glass sheet that scribbles resin places by processing on the little translation stage of computer-controlled three-dimensional; Machine the back and after 110 ℃, dried by the fire 1 minute, in the tetramethylammonium hydroxide aqueous solution of 0.26N (N), develop then, promptly obtain the retrofit figure.
Embodiment 11
A kind ofly contain the chemical amplification type positive photoresist that acid system is given birth in the two-photon sensitization, comprise the raw material of following parts by weight:
In the formula M 5, A1, A2, A3, A5 and A6 are the dyestuff S10 of hydrogen atom as the two-photon sensitizer;
Under the lucifuge condition; 10mg S10 and 100mg N-hydroxyphthalimide methanesulfonates are dissolved in the 15g gamma-butyrolacton, treat dissolving fully after, add 6g methyl methacrylate, methacrylic acid dihydropyrane ester copolymer; Lucifuge condition held 5h, and stir.The two-photon polymerized resin for preparing is applied on the glass sheet, and 80 ℃ of bakings were removed dissolvent residual in 5 minutes, utilized the Ti-Sapphire femtosecond as LASER Light Source; Pulse width 80 femtoseconds, repetition frequency 80MHz, wavelength 800nm; Output power 0.8mw, laser beam is 100x through an enlargement factor, the micro-oily mirror in resin aperture 1.45 focuses in the two-photon chemical amplification positive photoresist film; The glass sheet that scribbles resin places by processing on the little translation stage of computer-controlled three-dimensional; Machine the back and after 90 ℃, dried by the fire 1 minute, in the tetramethylammonium hydroxide aqueous solution of 0.26N (N), develop then, promptly obtain the retrofit figure.
Embodiment 12
Contain the two-photon sensitization and give birth to the chemical amplification type positive photoresist of acid system, comprise the raw material of following parts by weight:
In the formula M 6, A1, A2, A5 and A6 are the dyestuff S11 of hydrogen atom as the two-photon sensitizer;
Under the lucifuge condition; 10mg S10 and 90mg N-hydroxyphthalimide methanesulfonates are dissolved in the 15g gamma-butyrolacton, treat dissolving fully after, add 6g methyl methacrylate, methacrylic acid dihydropyrane ester copolymer; Lucifuge condition held 5h, and stir.The two-photon polymerized resin for preparing is applied on the glass sheet, and 80 ℃ of bakings were removed dissolvent residual in 5 minutes, utilized the Ti-Sapphire femtosecond as LASER Light Source; Pulse width 80 femtoseconds, repetition frequency 80MHz, wavelength 800nm; Output power 0.8mw, laser beam is 100x through an enlargement factor, the micro-oily mirror in resin aperture 1.45 focuses in the two-photon chemical amplification positive photoresist film; The glass sheet that scribbles resin places by processing on the little translation stage of computer-controlled three-dimensional; Machine the back and after 90 ℃, dried by the fire 1 minute, in the tetramethylammonium hydroxide aqueous solution of 0.26N (N), develop then, promptly obtain the retrofit figure.
Embodiment 13
A kind ofly contain the chemical amplification type positive photoresist that acid system is given birth in the two-photon sensitization, comprise the raw material of following parts by weight:
In the formula M 4, A1, A2, A3, A4, A5 and A6 are the dyestuff S6 of hydrogen atom as the two-photon sensitizer;
Under the lucifuge condition; 10mg S6 and 60mg two (4-aminomethyl phenyl) iodine hexafluorophosphate are dissolved in the 20g ethylene glycol diethyl ether; After treating dissolving fully, add the bisphenol-A of 1g t-BOC protection, add 8g methyl methacrylate, metering system tert-butyl acrylate multipolymer behind the 1h; Lucifuge condition held 4h, and stir.The two-photon polymerized resin for preparing is applied on the glass sheet, and 90 ℃ of bakings were removed dissolvent residual in 5 minutes, utilized the Ti-Sapphire femtosecond as LASER Light Source; Pulse width 80 femtoseconds, repetition frequency 80MHz, wavelength 760nm; Output power 0.5mw, laser beam is 100x through an enlargement factor, the micro-oily mirror in resin aperture 1.45 focuses in the two-photon chemical amplification positive photoresist film; The glass sheet that scribbles resin places by processing on the little translation stage of computer-controlled three-dimensional; Machine the back and after 110 ℃, dried by the fire 1 minute, in the tetramethylammonium hydroxide aqueous solution of 0.26N (N), develop then, promptly obtain the retrofit figure.
Embodiment 14
A kind ofly contain the chemical amplification type positive photoresist that acid system is given birth in the two-photon sensitization, comprise the raw material of following parts by weight:
In the formula M 4, A1, A2, A3 and A4 are hydrogen atom, and A5, A6 are that the dyestuff S8 of normal-butyl is as the two-photon sensitizer;
Under the lucifuge condition; 10mg S8 and 50mg two (4-aminomethyl phenyl) iodine hexafluorophosphate are dissolved in the 12g diethylene glycol dimethyl ether; After treating dissolving fully, add the p-dihydroxy-benzene of 1g t-BOC protection, what add 5g part t-BOC protection behind the 1h again gathers the 4-hydroxy styrenes; Lucifuge condition held 5h, and stir.The two-photon polymerized resin for preparing is applied on the glass sheet, and 90 ℃ of bakings were removed dissolvent residual in 5 minutes, utilized the Ti-Sapphire femtosecond as LASER Light Source; Pulse width 80 femtoseconds, repetition frequency 80MHz, wavelength 760nm; Output power 0.4mw, laser beam is 100x through an enlargement factor, the micro-oily mirror in resin aperture 1.45 focuses in the two-photon chemical amplification positive photoresist film; The glass sheet that scribbles resin places by processing on the little translation stage of computer-controlled three-dimensional; Machine the back and after 110 ℃, dried by the fire 1 minute, in the tetramethylammonium hydroxide aqueous solution of 0.26N (N), develop then, promptly obtain the retrofit figure.
Embodiment 15
A kind of is the preparation method of benzal cyclanone two-photon dyestuff of straight chain or many types of electron donor with the triphenylamine:
In the formula M 1; A1, A2, A3, A4 are hydrogen atom,
be that the synthetic method of dyestuff S1 of cyclopentanone is following:
In the 100ml there-necked flask, add the 20ml absolute ethyl alcohol; Stir down and add 2.73g (0.01mol) diphenylamine benzaldehyde, 0.42g (0.005mol) cyclopentanone and 0.06g NaOH; 60 ℃ are reacted 3h down, and solution changes redness into by yellow gradually, and has a large amount of red crystals to separate out; Cross and filter thick product 2.9g, get S1 2.7g (productive rate 86%) through the absolute ethyl alcohol recrystallization.
Ultimate analysis calculated value (C43H34N2O): C, 86.84; H, 5.76; N, 4.71; O, 2.69
Measured value: C, 86.80; H, 5.80; N, 4.71; O, 2.71
Mass spectrum EI-MS:m/z 594.27
Embodiment 16
A kind of is the preparation method of benzal cyclanone two-photon dyestuff of straight chain or many types of electron donor with the triphenylamine:
In the formula M 2; A1, A2 and A 3 are hydrogen atom,
be that the synthetic method of dyestuff S12 of cyclobutanone is following:
In the 100ml there-necked flask, add the 15ml absolute ethyl alcohol; Stir down and add 2.73g (0.01mol) diphenylamine benzaldehyde, 1.4g (0.02mol) cyclobutanone and 0.05g NaOH; Room temperature reaction 8h filters out orange deposition, does eluent with volume fraction 0.3% ethanol/dichloro; Silica stationary is carried out chromatographic resolution mutually, gets pure substance 2-(4-hexichol amido benzal) cyclobutanone (ml) 2.75g (productive rate 80%).
Intermediate product m1 2.6g (0.008mol), two formailide base benzene 1.2g (0.004mol) and 0.06gNaOH are added in the 25ml absolute ethyl alcohol; Heat back and heat up in a steamer 3h; System reddens gradually and has red precipitate to generate, and the system cooled and filtered is done eluent with the crude product that filters out with the ethanol/dichloro of volume fraction 0.5%; Silica gel column chromatography separates, and gets red pure article 2.5g (productive rate 65%).
Ultimate analysis calculated value (C66H49N3O2): C, 86.53; H, 5.39; N, 4.59; O, 3.49
Measured value: C, 86.53; H, 5.40; N, 4.60; O, 3.50
Mass spectrum EI-MS:m/z 915.38
Embodiment 17
A kind of is the preparation method of benzal cyclanone two-photon dyestuff of straight chain or many types of electron donor with the triphenylamine:
In the formula M 3; A1, A2 are hydrogen atom,
be that the synthetic method of dyestuff S13 of cyclopentanone is following:
In the 100ml there-necked flask, add the 15ml absolute ethyl alcohol; Stir down and add 2.73g (0.01mol) diphenylamine benzaldehyde, 1.6g (0.02mol) cyclopentanone and 0.05g NaOH; Room temperature reaction 8h filters out orange deposition, does eluent with volume fraction 0.3% ethanol/dichloro; Silica stationary is carried out chromatographic resolution mutually, gets pure substance 2-(4-hexichol amido benzal) cyclopentanone (m2) 2.6g (productive rate 73%).
Intermediate product m2 2.0g (0.006mol), three formailide 0.65g (0.002mol) and 0.06gNaOH are added in the 25ml absolute ethyl alcohol; Heat back and heat up in a steamer 3h; System reddens gradually and has the peony deposition to generate, and the system cooled and filtered is done eluent with the crude product that filters out with the ethanol/dichloro of volume fraction 0.5%; Silica gel column chromatography separates, and gets red pure article 1.1g. (productive rate 42%).
Ultimate analysis calculated value (C93H72N4O3): C, 86.35; H, 5.61; N, 4.33; O, 3.71
Measured value: C, 86.34; H, 5.60; N, 4.33; O, 3.70
Mass spectrum EI-MS:m/z 1293.56
Embodiment 18
A kind of is the preparation method of benzal alkane ketone two-photon dyestuff of straight chain or many types of electron donor with the triphenylamine:
In the formula M 4, the synthetic method that A1, A2, A3, A4, A5 and A6 are hydrogen atom dyestuff S6 is following:
In the 100ml there-necked flask, add the 20ml absolute ethyl alcohol, add 2.73g (0.01mol) to diphenylamine benzaldehyde, 0.29g (0.005mol) acetone and 0.06g NaOH under stirring, normal temperature is reaction 3h down; Solution changes redness into by yellow gradually; And have a large amount of yellowish red color crystal to separate out, and to cross and filter thick product 2.7g, crude product is done eluent with the ethanol/dichloro of volume fraction 0.5%; Silica gel column chromatography separates, and gets S6 2.2g (productive rate 73%) through the absolute ethyl alcohol recrystallization again
Ultimate analysis calculated value (C41H32N2O): C, 86.59; H, 5.67; N, 4.93; O, 2.81
Measured value: C, 86.60; H, 5.65; N, 4.94; O, 2.82
Mass spectrum EI-MS:m/z 568.25
Embodiment 19
A kind of is the preparation method of benzal alkane ketone two-photon dyestuff of straight chain or many types of electron donor with the triphenylamine:
In the formula M 5, A1, A2 and A3 are hydrogen atom, and A5 and A6 are dyestuff S14 synthetic of ethyl:
In the 100ml there-necked flask, add the 15ml absolute ethyl alcohol; Stir down and add 2.73g (0.01mol) diphenylamine benzaldehyde, 2.28g (0.02mol) 4-heptanone and 0.05g NaOH; Room temperature reaction 8h filters out orange deposition, does eluent with volume fraction 0.3% ethanol/dichloro; Silica stationary is carried out chromatographic resolution mutually, gets pure substance 3-(4-hexichol amido benzal)-4-heptanone (m3) 2.4g (productive rate 62%)
In 2.21g (0.006mol) m3 and two formailide base benzene 0.9g (0.003mol) and 0.06gNaOH adding 25ml absolute ethyl alcohol; Heat back and heat up in a steamer 3h; System reddens gradually and has red precipitate to generate, and the system cooled and filtered is done eluent with the crude product that filters out with the ethanol/dichloro of volume fraction 0.5%; Silica gel column chromatography separates, and gets red pure article 2.1g. (productive rate 67%)
Ultimate analysis calculated value (C72H65N3O2): C, 86.11; H, 6.52; N, 4.18; O, 3.19
Measured value: C, 86.11; H, 6.53; N, 4.19; O, 3.20
Mass spectrum EI-MS:m/z 1003.51
Embodiment 20
A kind of is the preparation method of benzal alkane ketone two-photon dyestuff of straight chain or many types of electron donor with the triphenylamine:
In the formula M 6, A1, A2 and A5 are hydrogen atom, and A6 is that the synthetic method of dyestuff S15 of ethyl is following:
In the 100ml there-necked flask, add the 15ml absolute ethyl alcohol, add 2.73g (0.01mol) to diphenylamine benzaldehyde, 1.72g (0.02mol) 2 pentanone and 0.05g NaOH under stirring, room temperature reaction 8h; Filter out orange deposition; Do eluent with volume fraction 0.3% ethanol/dichloro, silica stationary is carried out chromatographic resolution mutually, gets pure substance 3-(4-hexichol amido benzal)-2 pentanone (m4) 0.94g (productive rate 26%; Other has 1-(4-hexichol amido benzal)-2 pentanone, productive rate 32%)
In 0.94g (0.0027mol) m4 and three formailide 0.3g (0.0009mol) and 0.06g NaOH adding 25ml absolute ethyl alcohol; Heat back and heat up in a steamer 3h; System reddens gradually and has red precipitate to generate, and the system cooled and filtered is done eluent with the crude product that filters out with the ethanol/dichloro of volume fraction 0.5%; Silica gel column chromatography separates, and gets red pure article 0.5g. (productive rate 41%)
Ultimate analysis calculated value (C93H78N4O3): C, 85.95; H, 6.05; N, 4.31; O, 3.69
Measured value: C, 85.95; H, 6.05; N, 4.32; O, 3.70
Mass spectrum EI-MS:m/z 1299.61
Embodiment 21
Repeat embodiment 1; Its difference only is that said
is cycloheptanone; Said photo-acid agent is N-hydroxyl-1,8-naphthalimide methane sulfonate; Said organic solvent is a glycol monoethyl ether.
Embodiment 22
Repeat embodiment 1; Its difference only is that said
is cyclooctanone; Said photo-acid agent is a N-hydroxyphthalimide p-methyl benzenesulfonic acid ester; Said organic solvent is an ethylene glycol monoethyl ether.
Embodiment 23
Repeat embodiment 2, its difference only is that in the formula M 1, A1, A2 are hydrogen atom, and A3, A4 are propyl group; Said photo-acid agent is N-hydroxyl-1,8-naphthalimide p-methyl benzenesulfonic acid ester; Said organic solvent is an ethylene glycol acetate.
Embodiment 24
Repeat embodiment 2, its difference only is that in the formula M 1, A1, A2 are hydrogen atom, and A3, A4 are isopropyl; Said photo-acid agent is a dinitro benzyl p-toluenesulfonic esters; Said organic solvent is a diethylene glycol.
Embodiment 25
Repeat embodiment 2, its difference only is that in the formula M 1, A1, A2 are hydrogen atom, and A3, A4 are isobutyl; Said photo-acid agent is the diphenyl iodonium fluoroform sulphonate; Said organic solvent is a propylene glycol methyl ether acetate.
Embodiment 26
Repeat embodiment 2, its difference only is that in the formula M 1, A1, A2 are hydrogen atom, and A3, A4 are the tert-butyl group; Said photo-acid agent is the diphenyl iodonium perfluoro butyl sulfosalt; Said organic solvent is the propylene glycol monoacetate.
Embodiment 27
Embodiment 28
Repeat embodiment 6, its difference only is that in the formula M 1, A1 is a hydrogen atom, and A2 is a propoxyl group, and A3 is a n-butoxy, the A4 tert-butoxy; Said photo-acid agent is two pairs of methylbenzene iodine hexafluorophosphates; Said organic solvent Shi diox.
Embodiment 29
Repeat embodiment 6, its difference only is that in the formula M 1, A1, A2 are hydrogen atom, and A3, A4 are nitro; Said photo-acid agent is a diphenyl p-methoxyphenyl sulphur fluoroform sulphonate; Said organic solvent is a methyl lactate.
Embodiment 30
Repeat embodiment 2, its difference only is that in the formula M 1, A1, A2 are hydrogen atom, and A3, A4 are fluorine atom; Said photo-acid agent is three (to tert-butyl-phenyl) sulphur fluoroform sulphonate; Said organic solvent is a methyl pyruvate.
Embodiment 30
Repeat embodiment 2, its difference only is that in the formula M 1, A1, A2 are hydrogen atom, and A3, A4 are the chlorine atom.Said photo-acid agent is two pairs of methylbenzene iodine hexafluoro arsenates; Said organic solvent is a 2-hydroxy-2-methyl ethyl propionate.
Embodiment 31
Repeat embodiment 2, its difference only is that in the formula M 1, A1, A2 are hydrogen atom, and A3, A4 are bromine atoms; Said photo-acid agent is a diphenyl p-methoxyphenyl sulphur perfluoro butyl sulfosalt; Said organic solvent is an ethoxyethyl acetate(EA).
Embodiment 32
Repeat embodiment 2, its difference only is that in the formula M 1, A1, A2 are hydrogen atom, and A3, A4 are the iodine atom; Said photo-acid agent is a triphenyl sulphur perfluoro butyl sulfosalt; Said organic solvent is 3-methoxyl-2 Methylpropionic acid ethyl ester.
Embodiment 33
Repeat embodiment 13, its difference only is that said dissolution inhibitor is the phenol of t-BOC protection.
Embodiment 34
Repeat embodiment 13, its difference only is that said dissolution inhibitor is 1,3 of t-BOC protection, the 5-trisphenol.
Embodiment 35
Repeat embodiment 13, its difference only is that said dissolution inhibitor is 1,2 of t-BOC protection, the adjacent trisphenol of 3-.
Embodiment 36
Repeat embodiment 14, its difference only is that said dissolution inhibitor is 2 of t-BOC protection, the 6-dinitrophenol.
Embodiment 37
Repeat embodiment 14, its difference only is that said dissolution inhibitor is 2 of t-BOC protection, 6-dihydroxy nitrobenzene.
Embodiment 38
Repeat embodiment 1, its difference only is:
Embodiment 39
Repeat embodiment 1, its difference only is:
Embodiment 40
Repeat embodiment 1, its difference only is:
Obviously, the above embodiment of the present invention only be for clearly the present invention is described and is done for example, and be not to be qualification to embodiment of the present invention.For the those of ordinary skill in affiliated field, on the basis of above-mentioned explanation, can also make other multi-form variation or change.Here can't give exhaustive to all embodiments.Everyly belong to the row that conspicuous variation that technical scheme of the present invention extends out or change still are in protection scope of the present invention.
Claims (19)
1. the chemical amplification type positive photoresist is characterized in that, it is that to give birth to acid system with the two-photon sensitization be photic product acid constituents.
2. chemical amplification type positive photoresist according to claim 1 is characterized in that, said two-photon sensitization is given birth to acid system and comprised:
0.0001～2 part of light-sensitive coloring agent; 0.005～10 part of photo-acid agent.
3. chemical amplification type positive photoresist according to claim 2 is characterized in that, comprises the raw material of following parts by weight:
0.0001～2 part of light-sensitive coloring agent;
0.005～10 part of photo-acid agent;
5～80 parts of acid-degeneration type resins;
0～60 part of dissolution inhibitor;
20～90 parts of organic solvents.
4. according to claim 2 or 3 described chemical amplification type positive photoresists; It is characterized in that, described light-sensitive coloring agent be with the triphenylamine be electron donor straight chain or many types benzal cyclanone two-photon dyestuff or be the straight chain of electron donor or the benzal alkane ketone two-photon dyestuff of many types with the triphenylamine.
5. chemical amplification type positive photoresist according to claim 4 is characterized in that, said is that the straight chain of electron donor or the benzal cyclanone two-photon dyestuff of many types are the compounds with following molecular structure with the triphenylamine:
6. chemical amplification type positive photoresist according to claim 4 is characterized in that, said is that the straight chain of electron donor or the benzal alkane ketone two-photon dyestuff of many types are the compounds with molecular structure with the triphenylamine:
7. chemical amplification type positive photoresist according to claim 5 is characterized in that:
In general molecular formula M1～M3: A1, A2, A3, A4 are halogen atom, hydrogen atom, alkyl, alkoxy or nitro;
is cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone or cyclooctanone.
8. chemical amplification type positive photoresist according to claim 6 is characterized in that:
In general molecular formula M4～M6: A1, A2, A3, A4 are halogen atom, hydrogen atom, alkyl, alkoxy or nitro; A5, A6 are hydrogen atom or alkyl.
9. according to any described chemical amplification type positive photoresist in the claim 7, it is characterized in that: described halogen atom is meant fluorine atom, chlorine atom, bromine atoms or iodine atom; Described alkyl is a carbon number less than in 15 the alkyl any one; Described alkoxy is a carbon number less than in 15 the alkoxy any one.
According to Claim 8 in any described chemical amplification type positive photoresist, it is characterized in that: described halogen atom is meant fluorine atom, chlorine atom, bromine atoms or iodine atom; Described alkyl is a carbon number less than in 15 the alkyl any one; Described alkoxy is a carbon number less than in 15 the alkoxy any one.
11. chemical amplification type positive photoresist according to claim 3 is characterized in that: described acid-degeneration type resin is that any under acid catalysis, degraded generates the photoetching resin of alkali solubility group.
12. chemical amplification type positive photoresist according to claim 11 is characterized in that: the multipolymer that described acid-degeneration type resin is methyl methacrylate and metering system tert-butyl acrylate, part t-BOC protection gather 4-hydroxy styrenes or methyl methacrylate and methacrylic acid dihydropyrane ester copolymer.
13. chemical amplification type positive photoresist according to claim 3 is characterized in that: said dissolution inhibitor is that any under acid catalysis, degraded produces micromolecule benzene, biphenyl, the fused-ring derivatives of alkali solubility group.
14. chemical amplification type positive photoresist according to claim 13; It is characterized in that: said dissolution inhibitor be t-BOC protection phenol, t-BOC protection to 1,3 of biphenol, t-BOC protection, 1 of 5-trisphenol, t-BOC protection; 2; 2 of the adjacent trisphenol of 3-, t-BOC protection, 2 of 6-dinitrophenol, t-BOC protection, the bisphenol-A of 6-dihydroxy nitrobenzene or t-BOC protection.
15. according to claim 2 or 3 described chemical amplification type positive photoresists, it is characterized in that: said photo-acid agent is one or more the potpourri in N-hydroxyphthalimide ester, N-hydroxyl naphthalimide ester, triazine, sulfosalt, the salt compounded of iodine.
16. chemical amplification type positive photoresist according to claim 15; It is characterized in that: said photo-acid agent is N-hydroxyphthalimide triflate, N-hydroxyl-1; 8-naphthalimide triflate, N-hydroxyphthalimide methane sulfonate, N-hydroxyl-1; 8-naphthalimide methane sulfonate, N-hydroxyphthalimide p-methyl benzenesulfonic acid ester, N-hydroxyl-1,8-naphthalimide p-methyl benzenesulfonic acid ester, triazine derivative, dinitro benzyl p-toluenesulfonic esters, diphenyl iodonium fluoroform sulphonate, diphenyl iodonium perfluoro butyl sulfosalt, diphenyl iodonium hexafluorophosphate, diphenyl iodonium hexafluoro antimonate, diphenyl iodonium hexafluoro arsenate, the two pairs of methylbenzene iodine fluoroform sulphonates, the two pairs of methylbenzene iodine perfluoro butyl sulfosalts, the two pairs of methylbenzene iodine hexafluorophosphates, the two pairs of methylbenzene iodine hexafluoro antimonates, the two pairs of methylbenzene iodine hexafluoro arsenates, diphenyl p-methoxyphenyl sulphur fluoroform sulphonate, diphenyl p-methylphenyl sulphur fluoroform sulphonate, triphenyl sulphur fluoroform sulphonate, three (to tert-butyl-phenyl) sulphur fluoroform sulphonate, diphenyl p-methoxyphenyl sulphur perfluoro butyl sulfosalt, diphenyl p-methylphenyl base sulphur perfluoro butyl sulfosalt, diphenyl are to tert-butyl-phenyl sulphur perfluoro butyl sulfosalt, the diphenyl potpourri to one or more arbitrary proportions in isobutyl phenenyl sulphur perfluoro butyl sulfosalt, triphenyl sulphur perfluoro butyl sulfosalt, three (to tert-butyl-phenyl) sulphur perfluoro butyl sulfosalt, triphenyl sulphur hexafluoro arsenate, triphenyl sulphur hexafluoro antimonate, triphenyl sulphur hexafluorophosphate and the triphenyl sulphur fluoroform sulphonate.
17. chemical amplification type positive photoresist according to claim 3; It is characterized in that: said organic solvent is glycol monoethyl ether, glycol dimethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol acetate, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, acetate EGME, propylene glycol methyl ether acetate, propylene glycol, propylene glycol monoacetate, MEK, methyl isoamyl ketone, cyclohexanone 、 diox, methyl lactate, ethyl lactate, methyl pyruvate, ethyl pyruvate, methoxypropionic acid methyl esters, ethoxyl ethyl propionate, N; Dinethylformamide, N-N-methyl-2-2-pyrrolidone N-, 3-ethoxyl ethyl propionate, 2-heptanone, gamma-butyrolacton, 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-2-methyl ethyl propionate, ethoxyethyl acetate(EA), acetate hydroxyl ethyl ester, 2-hydroxy-3-methyl methyl butyrate, 3-methoxyl-2 Methylpropionic acid methyl esters, 3-ethoxyl ethyl propionate, 3-methoxyl-2 Methylpropionic acid ethyl ester, ethyl acetate, butyl acetate, pentyl acetate, toluene, xylene or dimethyl sulfoxide (DMSO).
18. the preparation method of chemical amplification type positive photoresist as claimed in claim 3 is characterized in that, comprises the steps:
Under the lucifuge condition; The photo-acid agent of 0.0001～2 part two-photon sensitizer and 0.005～10 part is dissolved in 20～90 parts the organic solvent; After treating dissolving fully; Acid-degeneration type resin and 0～60 part of dissolution inhibitor to wherein continuing 5～80 parts of addings stir, and promptly obtain two-photon chemical amplification type positive photoresist.
19. the application of chemical amplification type positive photoresist as claimed in claim 3 in the two-photon retrofit is characterized in that, comprises the steps:
Two-photon chemical amplification type positive photoresist is coated pretreated glass or silicon chip surface, treat solvent evaporates after, form the photoresist film be applicable to two-photon photoetching processing; The glass sheet that scribbles two-photon chemical amplification positive photoresist film is placed by on the little translation stage of computer-controlled three-dimensional; With the Ti-Sapphire femto-second laser is light source; Laser beam focuses on the two-photon chemical amplification positive photoresist film through a microcobjective; Sensitization is given birth to sour agent and is given birth to acid after the two-photon sensitizing dyestuff generation two-photon absorption at laser spot place, catalysis glued membrane generation acid degradation reaction, thus carry out three-dimensional little processing; Glass sheet after will machining then places the baking of baking oven back, and the back baking is accomplished to be placed in the developer solution and developed, and the part that flush away has been degraded just can obtain little graphics processing.
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| WO2019080820A1 (en) * | 2017-10-23 | 2019-05-02 | 上海必修福企业管理有限公司 | Photolithography method, photolithography product and photolithography material |
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