CN114315584A - Photosensitizer and preparation method thereof - Google Patents
Photosensitizer and preparation method thereof Download PDFInfo
- Publication number
- CN114315584A CN114315584A CN202111656548.8A CN202111656548A CN114315584A CN 114315584 A CN114315584 A CN 114315584A CN 202111656548 A CN202111656548 A CN 202111656548A CN 114315584 A CN114315584 A CN 114315584A
- Authority
- CN
- China
- Prior art keywords
- photosensitizer
- hydrogen
- oxygen
- containing sulfur
- butyl
- 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.)
- Pending
Links
- 239000003504 photosensitizing agent Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title abstract description 18
- -1 methoxy, ethoxy, propoxy, isopropoxy, isobutoxy Chemical group 0.000 claims abstract description 54
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 28
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 125000001424 substituent group Chemical group 0.000 claims abstract description 21
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 11
- 239000011737 fluorine Substances 0.000 claims abstract description 11
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 10
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 10
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 10
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 10
- 239000011630 iodine Substances 0.000 claims abstract description 10
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims abstract description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 7
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 7
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 7
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims abstract description 7
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract 4
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 5
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 claims description 3
- MGFYSGNNHQQTJW-UHFFFAOYSA-N iodonium Chemical compound [IH2+] MGFYSGNNHQQTJW-UHFFFAOYSA-N 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- JGTNAGYHADQMCM-UHFFFAOYSA-M 1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-M 0.000 claims description 2
- 229920002120 photoresistant polymer Polymers 0.000 abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- 238000009792 diffusion process Methods 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract 1
- 125000004432 carbon atom Chemical group C* 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 229910052717 sulfur Inorganic materials 0.000 abstract 1
- 239000011593 sulfur Substances 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 6
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 125000004185 ester group Chemical group 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000008213 purified water Substances 0.000 description 4
- 150000003841 chloride salts Chemical class 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000001259 photo etching Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- XVCHIUYEUZSGLB-UHFFFAOYSA-N 4,4-dimethylpent-2-enoyl chloride Chemical compound CC(C)(C)C=CC(Cl)=O XVCHIUYEUZSGLB-UHFFFAOYSA-N 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- OZLBDYMWFAHSOQ-UHFFFAOYSA-N diphenyliodanium Chemical class C=1C=CC=CC=1[I+]C1=CC=CC=C1 OZLBDYMWFAHSOQ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- JGTNAGYHADQMCM-UHFFFAOYSA-N perfluorobutanesulfonic acid Chemical compound OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F JGTNAGYHADQMCM-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002952 polymeric resin Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- MIOPJNTWMNEORI-UHFFFAOYSA-N camphorsulfonic acid Chemical compound C1CC2(CS(O)(=O)=O)C(=O)CC1C2(C)C MIOPJNTWMNEORI-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-M fluorosulfonate Chemical compound [O-]S(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-M 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- LVTHXRLARFLXNR-UHFFFAOYSA-M potassium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [K+].[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LVTHXRLARFLXNR-UHFFFAOYSA-M 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Images
Landscapes
- Materials For Photolithography (AREA)
Abstract
The invention is applicable to the technical field of photosensitizers, and provides a photosensitizer and a preparation method thereof. The structural general formula of the photosensitizer is as follows:
wherein R1 is hydrogen, one of substituents of aromatic hydrocarbon with 1-10 carbon atoms containing sulfur/oxygen/nitrogen heteroatomOr a plurality thereof; r2 is hydrogen, methyl, propyl, isopropyl, n-butyl, tert-butyl, methoxy, ethoxy, propoxy, isopropoxy, isobutoxy or one or more of fluorine, bromine and iodine; the R3 is one or more of hydrogen, C1-10 alkane aromatic hydrocarbon or substituent containing sulfur/oxygen/nitrogen heteroatom; and R4 is one or more of hydrogen, C1-10 alkane aromatic hydrocarbon or substituent containing sulfur/oxygen/nitrogen heteroatom. The photosensitizer and the preparation method thereof provided by the invention can effectively control the computational diffusion range, so that the photoresist has better appearance and line width roughness, and the defects are reduced.
Description
Technical Field
The invention belongs to the technical field of organic matter synthesis, and particularly relates to a photosensitizer and a preparation method thereof.
Background
Photoresist (Photoresist), also called Photoresist, refers to a resist material for etching a thin film, the solubility of which changes by irradiation or radiation of ultraviolet light, electron beam, ion beam, X-ray, etc. Photoresist is one of the key materials for fine pattern processing in microelectronic processing technology, and is a photosensitive film for transferring an image onto a substrate, which is a photosensitive mixed liquid composed of three main components, namely photosensitive resin, sensitizer and solvent, and is commonly used as an anti-corrosion coating material in the process of a photolithography technique. The main components of the photoresist are polymer resin, photosensitizer and corresponding additives. The photosensitizer is an important component in a photoresist system, generates acid (H +) under illumination, and in the baking process after exposure, the acid can be used as a catalyst to enable unstable groups on a polymer to be detached, and generates new acid, so that the characteristics of the polymer are changed, and the photoresist can be dissolved in a developing solution.
However, the photosensitizers in the prior art are all basically diphenyl iodonium salts and have no other modified functional groups, the photosensitizers cannot be uniformly dispersed in a photoresist system, and the performance of the conventional photosensitizers in the photoresist system is weak.
Accordingly, there is a need in the art for improvements.
Disclosure of Invention
The embodiment of the invention provides a photosensitizer and a preparation method thereof, aiming at solving the problems that the photosensitizer in the prior art is basically diphenyl iodonium salt and has no other modified functional groups, the photosensitizer cannot be uniformly dispersed in a photoresist system, and the prior photosensitizer has weaker performance in the photoresist system.
The embodiment of the invention is realized in such a way that the invention provides a photosensitizer, which has a structural general formula as follows:
wherein R1 is one or more of substituents of hydrogen, C1-10 arene containing sulfur/oxygen/nitrogen heteroatom; r2 is hydrogen, methyl, propyl, isopropyl, n-butyl, tert-butyl, methoxy, ethoxy, propoxy, isopropoxy, isobutoxy or one or more of fluorine, bromine and iodine; the R3 is one or more of hydrogen, C1-10 alkane aromatic hydrocarbon or substituent containing sulfur/oxygen/nitrogen heteroatom; and R4 is one or more of hydrogen, C1-10 alkane aromatic hydrocarbon or substituent containing sulfur/oxygen/nitrogen heteroatom.
Still further, the photosensitizer is (4- (methacryloyloxy) phenyl) (p-tolyl) iodonium, which has the formula:
still further, the photosensitizer is (4- (methacryloyloxy) phenyl) (p-tert-butylphenyl) iodonium, which has the chemical formula:
still further, the photosensitizer is (4- ((methacryloyloxy) methyl) phenyl) (p-tolyl) iodonium 1, 1, 2, 2, 3, 3-hexafluoropropane-1, 3-disulfonylimide salt, having the formula:
still further, the photosensitizer is (4- (t-butylacryloxy) phenyl) (p-tolyl) iodonium, which has the formula:
still further, the photosensitizer is (4- (tert-butyl) phenyl) (4- ((3, 3-dimethyl-2-methylenebutyl) oxy) methyl) phenyl) iodonium perfluorobutanesulfonate, having the formula:
the embodiment of the invention also provides a preparation method of the photosensitizer, which has a reaction formula as follows:
wherein R1 is one or more of substituents of hydrogen, C1-10 arene containing sulfur/oxygen/nitrogen heteroatom; r2 is hydrogen, methyl, propyl, isopropyl, n-butyl, tert-butyl, methoxy, ethoxy, propoxy, isopropoxy, isobutoxy or one or more of fluorine, bromine and iodine; the R3 is one or more of hydrogen, C1-10 alkane aromatic hydrocarbon or substituent containing sulfur/oxygen/nitrogen heteroatom; the R4 is one or more of hydrogen, C1-10 alkane aromatic hydrocarbon or substituent containing sulfur/oxygen/nitrogen heteroatom; x is one or more of hydrogen sulfate, sulfate radical, nitrate radical, phosphate radical, sulfonate radical, fluorine, bromine and iodine; the M metal ion.
Further, the reaction formula is:
further, the reaction formula is:
further, the reaction formula is:
has the advantages that: in the invention, an ester group and an acrylic acid system are introduced into a specific functional group on a modified benzene ring, so that photoacid molecules can be better dissolved in a photoresist solution and are uniformly distributed; meanwhile, the newly introduced optical energy group can promote the acid production efficiency of the photoacid generator to be better improved; can generate enough acid strength to generate chemical amplification effect with resin; the photosensitizer can effectively control the calculation diffusion range, so that the photoresist has better appearance and line width roughness, and the defects are reduced. The preparation method provided by the invention has simple steps and can realize preparation of various photosensitizers.
Drawings
FIG. 1 is a general structural formula of a photosensitizer provided by an embodiment of the present invention;
FIG. 2 is a reaction scheme of a method for preparing a photosensitizer provided by an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1 and fig. 2, fig. 1 is a general structural formula of a photosensitizer provided in an embodiment of the present invention, and fig. 2 is a reaction formula of a preparation method of the photosensitizer provided in an embodiment of the present invention.
The invention provides a photosensitizer, which has a structural general formula as follows:
wherein R1 is one or more of substituents of hydrogen, C1-10 arene containing sulfur/oxygen/nitrogen heteroatom; r2 is hydrogen, methyl, propyl, isopropyl, n-butyl, tert-butyl, methoxy, ethoxy, propoxy, isopropoxy, isobutoxy or one or more of fluorine, bromine and iodine; the R3 is one or more of hydrogen, C1-10 alkane aromatic hydrocarbon or substituent containing sulfur/oxygen/nitrogen heteroatom; and R4 is one or more of hydrogen, C1-10 alkane aromatic hydrocarbon or substituent containing sulfur/oxygen/nitrogen heteroatom.
The invention also provides a preparation method of the photosensitizer, which has a reaction formula as follows:
wherein R1 is one or more of substituents of hydrogen, C1-10 arene containing sulfur/oxygen/nitrogen heteroatom; r2 is hydrogen, methyl, propyl, isopropyl, n-butyl, tert-butyl, methoxy, ethoxy, propoxy, isopropoxy, isobutoxy or one or more of fluorine, bromine and iodine; the R3 is one or more of hydrogen, C1-10 alkane aromatic hydrocarbon or substituent containing sulfur/oxygen/nitrogen heteroatom; the R4 is one or more of hydrogen, C1-10 alkane aromatic hydrocarbon or substituent containing sulfur/oxygen/nitrogen heteroatom; x is one or more of hydrogen sulfate, sulfate radical, nitrate radical, phosphate radical, sulfonate radical, fluorine, bromine and iodine; the M metal ion.
Example one
Provided in this example is (4- (methacryloyloxy) phenyl) (p-tolyl) iodonium as a photosensitizer and a method for preparing the same. In the preparation process of this example, 34.66g of 4-hydroxy, 4-methyldiphenyliodonium chloride salt was added to a reaction flask, 150ml of methylene chloride was added, the mixture was dissolved and 11.5g of triethylamine solution was added dropwise. The reaction flask was stirred at room temperature for 0.5h under nitrogen, then cooled to-5 ℃. In another reaction bottle, 11.7g of methacrylic chloride is mixed in advance and dissolved in 30ml of dichloromethane, the dropping speed is slowly controlled, and the methacrylic chloride mixed solution is added, and the temperature is controlled to be-5 ℃. After the addition of the methacrylic chloride mixed solution, the mixture was stirred at-5 ℃ for 1 hour. Stirring at-5 deg.C for 1h, naturally heating to 25 deg.C, and stirring for 2 h. The mixture was filtered, the filter cake was washed with 30ml of dichloromethane, and the filtrate was washed 2 times with 10ml of pure water. The filtrate was concentrated and the temperature controlled at 35 ℃. 36.97g of (4- (methacryloyloxy) phenyl) (p-tolyl) iodonium was finally obtained, which was found to have a yield of 89.3%.
The reaction formula is as follows:
the photosensitizer provided by the invention introduces acrylic groups, so that the overall performance of the photosensitizer is improved, and the photosensitizer is distributed in polymer resin to meet the principle of similar compatibility.
Example two
In this embodiment, the preparation process of the photosensitizer is as follows: 28.9g of 4-hydroxy, 4-tert-butyldiphenyliodonium chloride salt was charged into a reaction flask, 150ml of methylene chloride was added, and then, a solution was dissolved and 11.5g of triethylamine solution was added dropwise. Stirring at room temperature for 0.5h under nitrogen protection, and then cooling to-5 ℃. In another reaction flask, 11.7g of methacryloyl chloride was previously mixed and dissolved in 30ml of methylene chloride. Slowly controlling the dropping speed, adding the methacrylic chloride mixed solution, and controlling the temperature to be-5 ℃. After the addition of the methacrylic chloride mixture, the mixture was stirred at-5 ℃ for 1 h. Stirring at-5 deg.C for 1h, naturally heating to 25 deg.C, and stirring for 2 h. The mixture was filtered, the filter cake was washed with 30ml of dichloromethane, and the filtrate was washed 2 times with 10ml of pure water. The filtrate was concentrated and the temperature was controlled at 35 ℃. 39.1g of (4- (methacryloyloxy) phenyl) (p-tert-butylphenyl) iodonium is obtained in a yield of 85.7%.
The reaction formula is as follows:
EXAMPLE III
In this embodiment, the preparation process of the photosensitizer is as follows: 42.9g of (4- ((methacryloyloxy) methyl) phenyl) (p-tolyl) iodonium was charged into a flask, and a mixture of 200g of purified water and 100ml of methanol was added thereto and dissolved. Another reaction flask was charged with 30g of 1, 1, 2, 2, 3, 3-hexafluoropropane-1, 3-disulfonylimide salt aqueous methanol solution in a clear state. As the dropwise addition proceeded, a white solid precipitated. Stir at room temperature overnight. And (3) desolventizing, adding 250ml of dichloromethane, stirring, washing with 100ml of purified water for 3 times, and desolventizing to obtain 63.8g of (4- ((methacryloyloxy) methyl) phenyl) (p-tolyl) iodonium 1, 1, 2, 2, 3, 3-hexafluoropropane-1, 3-disulfonylimide salt as a target product, wherein the yield is 93.2%.
The reaction formula is as follows:
example four
In this embodiment, the preparation process of the photosensitizer is as follows: 34.66g of 4-hydroxy, 4-methyldiphenyliodonium chloride salt are added to a reaction flask, 150ml of dichloromethane are added, the solution is cleared and triethylamine solution is added dropwise: 11.5 g. Stirring at room temperature for 0.5h under nitrogen protection, and then cooling to-5 ℃. In another reaction flask, 14.6g of t-butylacryloyl chloride was previously mixed and dissolved in 30ml of methylene chloride. Slowly controlling the dropping speed, adding the tert-butyl acryloyl chloride mixed solution, and controlling the temperature to be-5 ℃. After the addition, the mixture was stirred at-5 ℃ for 1 h. Stirring at-5 deg.C for 1h, naturally heating to 25 deg.C, and stirring for 2 h. The mixture was filtered, the filter cake was washed with 30ml of dichloromethane, and the filtrate was washed 2 times with 10ml of pure water. The filtrate was concentrated and the temperature was controlled at 35 ℃. The product (4- (tert-butylacryloxy) phenyl) (p-tolyl) iodonium was obtained.
The reaction formula is as follows:
EXAMPLE five
In this embodiment, the preparation process of the photosensitizer is as follows: 51.3g of (4- (tert-butyl) phenyl) (4- ((3, 3-dimethyl-2-methylenebutyl) oxy) methyl) phenyl) iodonium salt was charged in a flask, and a mixture of 200g of purified water and 100ml of methanol was added to dissolve it clearly. Another reaction flask was charged with 30g of aqueous solution of potassium perfluorobutylsulfonate in methanol to obtain a clear solution. As the dropwise addition proceeded, a white solid precipitated. Stir at room temperature overnight. And (3) desolventizing, adding 250ml of dichloromethane, stirring for 20min, washing with 100ml of purified water for 3 times, and desolventizing to obtain the target product (4- (tert-butyl) phenyl) (4- ((3, 3-dimethyl-2-methylene butyl) oxy) methyl) phenyl) iodonium perfluorobutylsulfonate.
The reaction formula is as follows:
in general, the photosensitizer provided by the invention introduces an ester group and an acrylic acid system by modifying a specific functional group on a benzene ring, so that photoacid molecules can be better dissolved in a photoresist solution and are uniformly distributed; ester groups and acrylic groups are added in the photosensitizer molecules, so that the photosensitizer can be better dispersed in a photoresist resin system, has larger molecular volume and smaller diffusion coefficient, and can improve the photoetching performance, and especially, perfluorobutyl sulfonate, 1, 2, 2, 3, 3-hexafluoropropane-1, 3-disulfonimide salt, tris (trifluoromethanesulfonyl) methyl salt, camphorsulfonate, fluorosulfonate and the like can have enough acid strength, so that the photoetching pattern on the resin has lower edge roughness and higher photoetching image forming quality; meanwhile, ester groups and acrylic acid groups are introduced into hydroxyl dialkyl hydrocarbon cations, so that the stability of the photoacid generator in a photoresist system can be improved, and the line roughness can be better; meanwhile, the newly introduced optical energy group can promote the acid production efficiency of the photoacid generator to be better improved; the anion containing sulfonic acid, especially the anion with fluorine element can generate enough acid strength to generate chemical amplification effect with resin; the photosensitizer can effectively control the calculation diffusion range, so that the photoresist has better appearance and line width roughness, and the defects are reduced. The preparation method provided by the invention has simple steps and can realize preparation of various photosensitizers.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A photosensitizer, characterized in that the structural formula of the photosensitizer is as follows:
wherein R1 is one or more of substituents of hydrogen, C1-10 arene containing sulfur/oxygen/nitrogen heteroatom; r2 is hydrogen, methyl, propyl, isopropyl, n-butyl, tert-butyl, methoxy, ethoxy, propoxy, isopropoxy, isobutoxy or one or more of fluorine, bromine and iodine; the R3 is one or more of hydrogen, C1-10 alkane aromatic hydrocarbon or substituent containing sulfur/oxygen/nitrogen heteroatom; and R4 is one or more of hydrogen, C1-10 alkane aromatic hydrocarbon or substituent containing sulfur/oxygen/nitrogen heteroatom.
2. The photosensitizer of claim 1, wherein the photosensitizer is (4- (methacryloxy) phenyl) (p-tolyl) iodonium, having the formula:
3. the photosensitizer of claim 1, wherein the photosensitizer is (4- (methacryloyloxy) phenyl) (p-tert-butylphenyl) iodonium, having the formula:
4. the photosensitizer of claim 1, wherein said photosensitizer is a (4- ((methacryloyloxy) methyl) phenyl) (p-tolyl) iodonium 1, 1, 2, 2, 3, 3-hexafluoropropane-1, 3-disulfonylimide salt having the formula:
5. the photosensitizer of claim 1, wherein the photosensitizer is (4- (t-butylacryloxy) phenyl) (p-tolyl) iodonium, having the formula:
6. the photosensitizer of claim 1, wherein the photosensitizer is (4- (tert-butyl) phenyl) (4- ((3, 3-dimethyl-2-methylenebutyl) oxy) methyl) phenyl) iodonium perfluorobutanesulfonate having the formula:
7. a process for preparing the photosensitizer of claim 1, wherein the reaction formula is:
wherein R1 is one or more of substituents of hydrogen, C1-10 arene containing sulfur/oxygen/nitrogen heteroatom; r2 is hydrogen, methyl, propyl, isopropyl, n-butyl, tert-butyl, methoxy, ethoxy, propoxy, isopropoxy, isobutoxy or one or more of fluorine, bromine and iodine; the R3 is one or more of hydrogen, C1-10 alkane aromatic hydrocarbon or substituent containing sulfur/oxygen/nitrogen heteroatom; the R4 is one or more of hydrogen, C1-10 alkane aromatic hydrocarbon or substituent containing sulfur/oxygen/nitrogen heteroatom; x is one or more of hydrogen sulfate, sulfate radical, nitrate radical, phosphate radical, sulfonate radical, fluorine, bromine and iodine; the M metal ion.
8. The process for preparing the photosensitizer according to claim 1, wherein the reaction formula is:
9. the process for preparing the photosensitizer according to claim 1, wherein the reaction formula is:
10. the process for preparing the photosensitizer according to claim 1, wherein the reaction formula is:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111656548.8A CN114315584A (en) | 2021-12-30 | 2021-12-30 | Photosensitizer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111656548.8A CN114315584A (en) | 2021-12-30 | 2021-12-30 | Photosensitizer and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114315584A true CN114315584A (en) | 2022-04-12 |
Family
ID=81019480
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111656548.8A Pending CN114315584A (en) | 2021-12-30 | 2021-12-30 | Photosensitizer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114315584A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114805048A (en) * | 2022-04-14 | 2022-07-29 | 乐凯华光印刷科技有限公司 | Iodonium salt initiator, treatment-free thermosensitive plate precursor containing iodonium salt initiator, treatment-free thermosensitive plate and application of treatment-free thermosensitive plate precursor |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1306224A (en) * | 1999-12-21 | 2001-08-01 | 西巴特殊化学品控股有限公司 | Iodonium salt used as potential acid provider |
| CN103525435A (en) * | 2012-07-03 | 2014-01-22 | Jsr株式会社 | Liquid crystal aligning agent, manufacturing method for liquid crystal display device, liquid crystal alignment film, liquid crystal display device, polymer and carboxylic acid |
| CN109503752A (en) * | 2018-10-12 | 2019-03-22 | 珠海雅天科技有限公司 | A kind of low diffusion ArF photoresist polymer photosensitizer PAG and its application |
| CN109796382A (en) * | 2019-02-27 | 2019-05-24 | 江苏南大光电材料股份有限公司 | The salty photo-acid generator of long flexible chain, preparation method and photoetching compositions |
| CN109991811A (en) * | 2019-02-27 | 2019-07-09 | 江苏南大光电材料股份有限公司 | A kind of acid dispersion inhibitor and preparation method thereof and photoetching compositions |
| CN110058489A (en) * | 2019-02-27 | 2019-07-26 | 江苏南大光电材料股份有限公司 | A kind of photoetching compositions and preparation method thereof |
-
2021
- 2021-12-30 CN CN202111656548.8A patent/CN114315584A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1306224A (en) * | 1999-12-21 | 2001-08-01 | 西巴特殊化学品控股有限公司 | Iodonium salt used as potential acid provider |
| CN103525435A (en) * | 2012-07-03 | 2014-01-22 | Jsr株式会社 | Liquid crystal aligning agent, manufacturing method for liquid crystal display device, liquid crystal alignment film, liquid crystal display device, polymer and carboxylic acid |
| CN109503752A (en) * | 2018-10-12 | 2019-03-22 | 珠海雅天科技有限公司 | A kind of low diffusion ArF photoresist polymer photosensitizer PAG and its application |
| CN109796382A (en) * | 2019-02-27 | 2019-05-24 | 江苏南大光电材料股份有限公司 | The salty photo-acid generator of long flexible chain, preparation method and photoetching compositions |
| CN109991811A (en) * | 2019-02-27 | 2019-07-09 | 江苏南大光电材料股份有限公司 | A kind of acid dispersion inhibitor and preparation method thereof and photoetching compositions |
| CN110058489A (en) * | 2019-02-27 | 2019-07-26 | 江苏南大光电材料股份有限公司 | A kind of photoetching compositions and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114805048A (en) * | 2022-04-14 | 2022-07-29 | 乐凯华光印刷科技有限公司 | Iodonium salt initiator, treatment-free thermosensitive plate precursor containing iodonium salt initiator, treatment-free thermosensitive plate and application of treatment-free thermosensitive plate precursor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102289149B (en) | Photoacid generator, method for manufacturing same, and resist composition comprising same | |
| TWI694983B (en) | Positive-type resist composition, method for forming resist pattern, photo-reactive quencher, and polymeric compound | |
| TWI385486B (en) | Acid generating agent for chemically amplified resist compositions | |
| CN101687781B (en) | Compound for photoacid generator and use its anti-corrosion agent composition, pattern formation method | |
| CN101727004B (en) | Photoacid generator containing aromatic ring | |
| TWI798445B (en) | Resist composition, method of forming resist pattern, compound, and acid generator | |
| TW201833150A (en) | Resist composition, method of forming resist pattern, compound, and acid generator | |
| CN101408728B (en) | Resist composition, method of forming resist pattern, novel compound and method of producing the same | |
| TW201708944A (en) | Resist composition, method of forming resist pattern, acid generator, and compound | |
| JPS6326653A (en) | Photoresist material | |
| CN101799629A (en) | Chemical amplifying type photo-corrosion-resisting agent composition and formation method of patterning | |
| JP6299914B2 (en) | Resist composition and salt | |
| JP2009501207A (en) | Photoactive compound | |
| CN102279521A (en) | Photochemical acid generator, manufacturing method thereof and resist composition having the photochemical acid generator | |
| TW202014797A (en) | Resist composition, and method of forming resist pattern | |
| CN111662267B (en) | Photoresist acid-producing resin monomer containing dioxobicyclo [2.2.2] octane dicarboxylic acid ester structure and preparation method thereof | |
| JP5512430B2 (en) | Salt and photoresist composition | |
| CN102675159A (en) | Photoacid generating monomer and precursor thereof | |
| CN114315584A (en) | Photosensitizer and preparation method thereof | |
| TW202004337A (en) | Resist composition and method of forming resist pattern | |
| CN101872116A (en) | Produce the photoresist method of patterning | |
| JP5512431B2 (en) | Polymer, photoresist composition and pattern production method | |
| KR20090075802A (en) | Photoactive compounds | |
| CN102603578A (en) | Method of preparing photoacid-generating monomer | |
| JP5104343B2 (en) | Monomer, resin, resist composition using the resin, and method for manufacturing a semiconductor device using the resist composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220412 |