Synthesis Of Matrix Resin For Photoresist And Their Performance Study

In recent years,the rapid development of electronic information industry has continuously promoted the performance of the integrated circuits.Photoresist,as one the most key material of integrated circuit industry development,directly affects the development of national economy,and develops with the integrated circuit industry synchronously to meet requirements of the innovation in terms of technology.As the feature size of integrated circuits evolves from micron,submicron to nanoscale direction of rapid development,the existing photoresist has been unable to meet the new lithography process requirements.Therefore,the research and development of new type of photoresist materials increasingly seem to be urgent.Film forning resin,as the main component of photoresist,has become the bottleneck,which restricts the development of the photoresist.This dissertation has synthesized a series of copolymers with different molecular structure,studied the synthetic process conditions of film forming resin and structure characterization,finally,discussed the relationship between matrix resin and performance of photoresist properties.The work in this dissertation includes the following parts:?1?Synthesis of linear photosensitive acrylic copolymer and its applicationSeries of copolymers P?AA-co-tBA-co-BZMA?were prepared by free radical polymerization with acrylic acid?AA?,tert butyl acrylate?tBA?and methyl benzyl methacrylate?BZMA?as monomers,then glycidyl methacrylate?GMA?was reacted with PTAB to introduce double bond to prepare photosensitive copolymer G-PTAB with different contents of double bond.The effect of solid content,initiator and chain transfer agent content,monomer ratio on properties of copolymer PTAB and G-PTAB were investigated.The structure and properties of the copolymer were characterized by FT IR,¹H NMR,GPC,TGA and DSC.Negative photoresist was prepared with G-PTAB as matrix resin,after UV exposure and development process,40?m line and space resolution was obtained.?2?Synthesis of branched photosensitive poly?styrene-alt-maleic anhydride?and its applicationBranched monomer vinyl benzyl mercaptan?VBT?was prepared by thiourea,and then branched poly?styrene-alt-maleic anhydride?copolymer was synthesized with styrene?St?and maleic anhydride?MAn?as monomer via mercapto chain transfer method.2-hydroxyethyl methacrylate?HEMA?was grafted into main chainof poly?styrene-alt-maleic anhydride?copolymer to introduce UV curable double bond.The structure and properties of photosensitive compolymers were characterized by FT IR,¹H NMR,GPC,TGA and DSC.Result showed that with increase of VBT content,the molecular weight of the copolymers decreased,Tg decreased,the initial decomposition temperature was around 200?.Negative photoresist were prepared using photosensitive copolymers with different VBT contents,and 30?m line and space patterns were obtained after UV cure and development.?3?Synthesis of deep ultraviolet matrix resin via RAFT polymerization and its applicationDeep ultraviolet photoresist copolymers P?ASM-co-St-co-tBA-co-MA?were prepared by RAFT polymerization using acetoxystyrene?ASM?,styrene?St?,tert butyl acrylate?tBA?and 2-methyl-2-adamantyl methyl acrylate?MAMA?as monomers,and the structure were characterized by FT IR and ¹H NMR.The optimum reaction condition was determined by single factor method and orthogonal experiment,the kinetics of polymerization of RAFT was also studied,showing living characteristics with linear relationship.Copolymerizaitons were prepared by two of ASM,St and tBA monomer,copolymer composition was analyzed and consistent with the theoretical simulation.Each monomer distribution in polymer main chain was also analyzed by segment sequence of the copolymer distribution.Positive photoresist was prepared by photo acid generator,additive and solvent,after exposure with 248 nm wavelength,0.18?m resolution was obtained.?4?Synthesis of molecular glass photoresist resin based on cyclotriphosphazene and its applicationHexachlorocyclotriphosphazene?HCCP?and p-hydroxy benzaldehyde were reacted to give aldehyde terminal group,cyclotriphosphazene as core,sodium borohydride was used to reduce the aldehyde to hydroxyl,and the structure was characterized by FT IR and ¹H NMR,¹³C NMR,³¹P NMR and TGA.Then di-tert-butyl dicarbonate ester was reacted with hexakis?4-?hydroxymethyl?phenoxyl?cyclotriphosphazene to introduce different contents of tBOC protecting group.X-ray diffraction showed better film forming performance.Positive photoresist were prepared by this molecular glass with different contents of tBOC protecting group and PAG,after exposure with365 nm wavenumber,development with 2.38w%tetramethyl ammonium hydroxide,the molecular glass resist with different tBOC protecting group contents can obtain clear images straight lines with resolution of 1?m?In conclusion,series of different structure of photoresist film forming resins were synthesized,the effect of different reaction conditions on the performance of film forming resin and their application in photoresist were demonstrated.The effect of different molecular structure and property on lithographic performance were aslo analyzed.