CN100460999C - 193nm far-ultraviolet photoetching rubber and its preparation method - Google Patents
193nm far-ultraviolet photoetching rubber and its preparation method Download PDFInfo
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- CN100460999C CN100460999C CNB2005100402246A CN200510040224A CN100460999C CN 100460999 C CN100460999 C CN 100460999C CN B2005100402246 A CNB2005100402246 A CN B2005100402246A CN 200510040224 A CN200510040224 A CN 200510040224A CN 100460999 C CN100460999 C CN 100460999C
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Abstract
A method for preparing 193nm far-ultraviolet photoetching includes using four monomers of 3,4-digydropyran, maleic anhydride, methacrylate tert-butyl ester and methacrylate methyl- diamantester to join copolymerization simultaneously; leading alicyclic unit on main chain of macromolecule and leading new suspension group on side chain for obtaining film forming resin being used to prepare photoetching.
Description
Technical field
The present invention relates to make the employed photoresist of VLSI (very large scale integrated circuit) chip, relating in particular to 193nm extreme ultraviolet single beam is photoresist of exposure light source and preparation method thereof, belongs to the microelectronics technical field of chemistry.
Background technology
Photoresist claims photoresist again, is meant the etch resistant membraneous material that solubleness changes under the irradiation of ultraviolet light, electron beam, ion beam, X-ray etc. or radiation.Photoresist is occupying special status aspect the integrated circuit (IC) chip manufacturing process, and the integrated level of integrated circuit is high more, and is also high more to the requirement of photoresist.
Advanced at present integrated circuit production line all adopts the projection exposure stepper, and the lithography process live width is more little, and the wavelength of exposure machine is short more, and different exposure wavelength inevitable requirements is used different photoresists.The 248nm photoresist comes to the ripening period in this field, and the resolution of its exposure machine is about 0.2 μ m; Though and the 193nm far-ultraviolet photoetching has entered the practical stage, still have many problems to need to solve, wherein the structure of film forming polymer (claiming again: film forming agent resin, film-forming resin) plays a decisive role to the performance of 193nm photoresist.
According to the knowledge of the applicant, the film-forming resin structure of 193nm far-ultraviolet photoetching mainly contains following four big classes in the prior art: 1. poly-(methyl) acrylate derivative; 2. cycloolefin-copolymer-maleic anhydride; 3. polynorbornene derivatives; 4. fluoropolymer system.The 1. the class formation synthesis technique is fairly simple, optical transparency height under the 193nm wavelength, and the resolution height, but anti-dry etching is poor; The 2. the class formation polymerization technique is easier, anti-dry etching height, but because main chain is an annular unit, and the polymkeric substance rigidity is big, and the film of formation is more crisp, hydrolysis easily; 3. with the 4. polymerization technique more complicated of class formation, its range of application is restricted.
Along with very large scale integration technology constantly develops, the application prospect of 193nm far-ultraviolet photoetching is very good; On the other hand, than immersing exposure method, the dry method exposure has many-sided advantage.Therefore, how to prepare the 193nm far-ultraviolet photoetching that synthesis technique is fairly simple, resolution is high, anti-dry etching is good, become an important subject of this area already.
Summary of the invention
The objective of the invention is to solve the above-mentioned technical barrier that prior art exists, provide a kind of synthesis technique easier and have resolution height, 193nm far-ultraviolet photoetching that anti-dry etching is good concurrently, and the preparation method of this photoresist.
Purpose of the present invention is achieved through the following technical solutions:
The 193nm far-ultraviolet photoetching comprises film-forming resin, emulsion, adjuvant and solvent, and wherein film-forming resin is the polymkeric substance that contains macromolecular structure shown in the formula I.
The preparation method of above-mentioned 193nm far-ultraviolet photoetching, film-forming resin, emulsion, adjuvant and solvent are carried out stirring and dissolving, performance adjustment, circulating filtration according to common process, be deployed into photoresist, wherein film-forming resin be with these four kinds of materials of formula II, formula III, formula IV and formula V as monomer 1, monomer 2, monomer 3 and monomer 4, be prepared from according to following steps:
1. under inert atmosphere, be solvent, above-mentioned four kinds of monomers are put into reaction vessel with polymerization initiator, stir with methylene chloride, tetrahydrofuran or dioxane;
2. with water-bath or oil bath reaction system is heated to 60～90 ℃, kept 4～8 hours;
3. cool to room temperature, add capacity methyl alcohol or ether, produce a large amount of sediments, filtration, drying get the film-forming resin crude product;
4. crude product is dissolved in organic solvent, with capacity methyl alcohol or ether precipitate once more, filtration, drying, the film-forming resin finished product.
Further, among the preparation method of above-mentioned 193nm far-ultraviolet photoetching, the 1. used polymerization initiator of step is an azoisobutyronitrile, and the 4. used organic solvent of step is N-Methyl pyrrolidone, propylene glycol methyl ether acetate or tetrahydrofuran.
Further, among the preparation method of above-mentioned 193nm far-ultraviolet photoetching, the monomer 1 that 1. step is used, monomer 2, monomer 3 with the weight batching ratio of solvent are: (30～80): (20～60): (20～40): (30～60): (3000～8800).
The present invention catches this technical key point of film-forming resin in the photoresist, designs and synthesizes out a kind of film forming polymer of new construction, and then prepares the photoresist that is applicable to 193nm extreme ultraviolet exposure wavelength.Compared with prior art, its outstanding substantive distinguishing features and obvious improvement is mainly reflected in:
(1) it adopts 3,4-dihydropyrane (monomer 1), maleic anhydride (monomer 2) participate in copolyreaction simultaneously with tert-butyl methacrylate (monomer 3), introduced the alicyclic ring unit on the polymer macromolecule backbone structure that forms, improved the combination property of film forming polymer, the way that changes pendent group on the macromolecular main chain structure in this point and the prior art emphatically is different fully;
(2) it also adopts a kind of methacrylated thing of new adamantane derivative to participate in copolyreaction simultaneously as the 4th monomer, makes the polymer macromolecule main chain introduce new pendent group, has further increased the surface strength of final film forming;
(3) by choosing suitable reaction dissolvent and separating out solvent, make the preparation technology of film-forming resin easier, operating conditions gentleness, product yield height.The film-forming resin molecular weight that obtains is higher, and molecular weight distribution is narrower;
(4) photoresist that adopts this film-forming resin to make has permeability preferably at the 193nm place, supports high resolving power, can realize the live width of 0.1 μ m, can satisfy the making requirement of 1G random access memory;
(5) in addition, photoresist provided by the invention also has higher anti-dry etching ability, better heat-resisting performance and lower ease gas simultaneously, it both had been applicable to the dry method exposure technology, be applicable to the immersed method exposure technology again, and, all can satisfy the strict demand of making large scale integrated chip in the shrinkage and the permeability of film afterwards of exposing.
Description of drawings
Fig. 1 is the electron scanning electromicroscopic photograph after resist exposure provided by the invention develops.
Embodiment
Below in conjunction with specific embodiment technical solution of the present invention is described further.These examples only are some exemplary applications, can not be interpreted as a kind of restriction to claim protection domain of the present invention.
Embodiment one
Under the state that is full of inert gas such as nitrogen, with 3,4-dihydropyrane (monomer 1, structural formula is seen formula II), maleic anhydride (monomer 2, structural formula is seen formula III), tert-butyl methacrylate (monomer 3, structural formula is seen formula IV), the firm ester of methyl methacrylate fund (monomer 4, structural formula is seen formula V) and dioxane, weight ratio according to 50:50:20:50:5400 adds in the reaction bulb, the azoisobutyronitrile (AIBN) that adds amounts of reactants again, fully stir, be heated to 60～70 ℃, keep making it to carry out in 4～5 hours polyreaction with water-bath or oil bath.Cool to room temperature then, add the capacity ether, produce a large amount of sediments, filtration, recovery, drying get film-forming resin crude product shown in the formula I.Then, be solvent with propylene glycol methyl ether acetate (PGMEA), with the film-forming resin dissolving crude product, precipitate once more with capacity methyl alcohol, filtration, drying promptly get the film-forming resin finished product.Use amount according to monomer 1 is calculated, and yield is 50%; Gel chromatography (GPC) records the weight-average molecular weight M of this film-forming resin
wBe 5000～18000, molecular weight distribution is 1.7～2.0.
Embodiment two
Under the state that is full of inert gas such as nitrogen, with 3,4-dihydropyrane (monomer 1), maleic anhydride (monomer 2), tert-butyl methacrylate (monomer 3), the firm ester of methyl methacrylate fund (monomer 4) and methylene chloride, weight ratio according to 60:50:20:40:4600 adds in the reaction bulb, the azoisobutyronitrile (AIBN) that adds amounts of reactants again, fully stir, be heated to 70～80 ℃, keep making it to carry out in 5～6.5 hours polyreaction with water-bath or oil bath.Cool to room temperature then, add the capacity ether, produce a large amount of sediments, filtration, recovery, drying get film-forming resin crude product shown in the formula I.Then, be solvent with N-Methyl pyrrolidone (NMP), with the film-forming resin dissolving crude product, precipitate once more with the capacity ether, filtration, drying promptly get the film-forming resin finished product.Use amount according to monomer 1 is calculated, and yield is 45%; Gel chromatography (GPC) records the weight-average molecular weight M of this film-forming resin
wBe 13000～28000, molecular weight distribution is 1.9～2.4.
Embodiment three
Under the state that is full of inert gas such as nitrogen, with 3,4-dihydropyrane (monomer 1), maleic anhydride (monomer 2), tert-butyl methacrylate (monomer 3), the firm ester of methyl methacrylate fund (monomer 4) and tetrahydrofuran (THF), weight ratio according to 70:50:20:30:4000 adds in the reaction bulb, the azoisobutyronitrile (AIBN) that adds amounts of reactants again, fully stir, be heated to 80～90 ℃, keep making it to carry out in 6.5～8 hours polyreaction with water-bath or oil bath.Cool to room temperature then, add capacity methyl alcohol, produce a large amount of sediments, filtration, recovery, drying get film-forming resin crude product shown in the formula I.Then, be solvent with THF, with the film-forming resin dissolving crude product, precipitate once more with capacity methyl alcohol, filtration, drying promptly get the film-forming resin finished product.Use amount according to monomer 1 is calculated, and yield is 40%; Gel chromatography (GPC) records the weight-average molecular weight M of this film-forming resin
wBe 15000～30000, molecular weight distribution is 2.3～2.8.
Embodiment four
Film-forming resin and photoacid generator [C that embodiment one is prepared
6H
5]
3S-OH-X
-, acid binding agent, surfactant and propylene glycol methyl ether acetate PGMEA, through processing steps such as stirring and dissolving, performance adjustment, circulating filtrations, be deployed into the special-purpose photoresist of 193nm extreme ultraviolet.
When this photoresist is used to make VLSI (very large scale integrated circuit) chip, take the surface and the cross section situation of film after the exposure imaging with the electronics scanning electron microscope, photo as shown in Figure 1.Test condition is: photoresist thickness-2000nm, exposure sources-ASML-1150, NA=0.75,0.90/0.60s offAxis Ilbumination, PAB120 ℃, PEB120 ℃, developer-TMAH (tetramethyl oxyammonia, concentration-2.38%, development time-45 second, spray, Electronic Speculum enlargement factor-110,000 times.
As can be seen from Figure 1, photoresist provided by the invention can be supported the high resolving power level, and lines are wide about 98nm, less than 0.1 μ m.In addition, it is against corrosion that the 193nm photoresist adopts the thickness of 3000～5000nm mostly in the prior art, and the present invention adopts the 2000nm thickness promptly to show very strong opposing dry etching ability.
Claims (5)
1. the 193nm far-ultraviolet photoetching comprises film-forming resin, emulsion, adjuvant and solvent, it is characterized in that: described film-forming resin is the polymkeric substance that contains macromolecular structure shown in the formula I
2. the preparation method of the described 193nm far-ultraviolet photoetching of claim 1, film-forming resin, emulsion, adjuvant and solvent are carried out stirring and dissolving, performance adjustment, circulating filtration according to common process, be deployed into photoresist, it is characterized in that: described film-forming resin be with these four kinds of materials of formula II, formula III, formula IV and formula V as monomer 1, monomer 2, monomer 3 and monomer 4, be prepared from according to following steps:
Formula III
1. under inert atmosphere, be solvent, above-mentioned four kinds of monomers are put into reaction vessel with polymerization initiator, stir with methylene chloride, tetrahydrofuran or dioxane;
2. with water-bath or oil bath reaction system is heated to 60～90 ℃, kept 4～8 hours;
3. cool to room temperature, add capacity methyl alcohol or ether, produce a large amount of sediments, filtration, drying get the film-forming resin crude product;
4. crude product is dissolved in organic solvent, with capacity methyl alcohol or ether precipitate once more, filtration, drying, the film-forming resin finished product.
3. the preparation method of 193nm far-ultraviolet photoetching according to claim 2 is characterized in that: the 1. used polymerization initiator of step is an azoisobutyronitrile.
4. the preparation method of 193nm far-ultraviolet photoetching according to claim 2 is characterized in that: the 4. used organic solvent of step is N-Methyl pyrrolidone, propylene glycol methyl ether acetate or tetrahydrofuran.
5. according to the preparation method of claim 2,3 or 4 described 193nm far-ultraviolet photoetchings, it is characterized in that: the 1. middle monomer 1 of step, monomer 2, monomer 3, monomer 4 with the weight batching ratio of solvent are: (30～80): (20～60): (20～40): (30～60): (3000～8800).
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| CN100460999C true CN100460999C (en) | 2009-02-11 |
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| CN113717314B (en) * | 2021-08-26 | 2023-09-22 | 江苏集萃光敏电子材料研究所有限公司 | Photosensitive film-forming resin, photoresist composition and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5968713A (en) * | 1995-06-28 | 1999-10-19 | Fujitsu Limited | Chemically amplified resist compositions and process for the formation of resist patterns |
| US6517990B1 (en) * | 2000-01-19 | 2003-02-11 | Samsung Electronics Co., Ltd. | Photosensitive polymer including copolymer of alkyl vinyl ether and resist composition containing the same |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5968713A (en) * | 1995-06-28 | 1999-10-19 | Fujitsu Limited | Chemically amplified resist compositions and process for the formation of resist patterns |
| US6517990B1 (en) * | 2000-01-19 | 2003-02-11 | Samsung Electronics Co., Ltd. | Photosensitive polymer including copolymer of alkyl vinyl ether and resist composition containing the same |
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Address after: 215128 Jiangsu city of Suzhou province Wuzhong District Su Li Road No. 81 Patentee after: Ruihong (Suzhou) Electronic Chemicals Co.,Ltd. Address before: 215128 Jiangsu city of Suzhou province Wuzhong District Su Li Road No. 81 Patentee before: SUZHOU RUIHONG ELECTRONIC CHEMICAL CO.,LTD. |
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