CN100468194C - 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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- CN100468194C CN100468194C CNB2005100402250A CN200510040225A CN100468194C CN 100468194 C CN100468194 C CN 100468194C CN B2005100402250 A CNB2005100402250 A CN B2005100402250A CN 200510040225 A CN200510040225 A CN 200510040225A CN 100468194 C CN100468194 C CN 100468194C
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Abstract
A method for preparing 193nm far-ultraviolet photoetching includes using three monomers of 3,4-dihydropyran, maleic anhydride and methacrylate tert-butyl ester to join copolymerization simultaneously; leading alicyclic unit on main chain of macromolecule 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 three kinds of materials of formula II, formula III and formula IV as monomer 1, monomer 2 and monomer 3, be prepared from according to following steps:
1. under inert atmosphere, be solvent, above-mentioned three 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.
(formula II)
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): (30～80): (20～40): (3000～7000).
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 three kinds of monomers of 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) 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;
(3) 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;
(4) in addition, photoresist provided by the invention also has higher anti-dry etching ability, better heat-resisting performance and lower ease gas simultaneously, it is not only applicable to the dry method exposure machine, and, all can satisfy the strict demand of making large scale integrated chip in the anti-contracility energy 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 are seen formula II), maleic anhydride (monomer 2, structural formula is seen formula III), tert-butyl methacrylate (monomer 3, structural formula is seen formula IV) and dioxane, weight ratio according to 50:50:40:3400 adds in the reaction bulb, adds the azoisobutyronitrile (AIBN) of amounts of reactants again, fully stirs, be heated to 60～70 ℃ with water-bath or oil bath, keep making it to carry out in 4～5 hours polyreaction.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 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 58%; Gel chromatography (GPC) records the weight-average molecular weight M of this film-forming resin
wBe 4000～12000, 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) and methylene chloride, weight ratio according to 80:70:30:3600 adds in the reaction bulb, the 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 54%; GPC records the weight-average molecular weight M of this film-forming resin
wBe 10000～23000, molecular weight distribution is 1.9～2.2.
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) and tetrahydrofuran (THF), weight ratio according to 80:60:30:4600 adds in the reaction bulb, the 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 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 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 48%; GPC records the weight-average molecular weight M of this film-forming resin
wBe 15000～30000, molecular weight distribution is 2.1～2.5.
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 97nm, 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 (2)
1, the preparation method of 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, it is characterized in that: described film-forming resin contains the polymkeric substance of macromolecular structure shown in the formula I, as monomer 1, monomer 2 and monomer 3, is to be prepared from according to following steps with these three kinds of materials of formula II, formula III and formula IV---
Formula IV
1. under inert atmosphere, with methylene chloride, tetrahydrofuran or dioxane is solvent, above-mentioned three kinds of monomers are put into reaction vessel with polymerization initiator, stir, monomer 1, monomer 2, monomer 3 are (30～80) with the weight batching ratio of solvent: (30～80): (20～40): (3000～7000);
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.
2, the preparation method of 193nm far-ultraviolet photoetching according to claim 1 is characterized in that: the 4. used organic solvent of step is N-Methyl pyrrolidone, propylene glycol methyl ether acetate or tetrahydrofuran.
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| CNB2005100402250A CN100468194C (en) | 2005-05-25 | 2005-05-25 | 193nm far-ultraviolet photoetching rubber and its preparation method |
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| CN100468194C true CN100468194C (en) | 2009-03-11 |
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