Chemically amplified resists (CARs) which involved the photoacid generator (PAG) have been widely used because of the high sensitivity. The inherent incompatibility between the polymer matrix and small molecular PAGs leads to problems including PAG phase separation, non-uniform initial PAG and photoacid distribution, as well as acid migration during the post-exposure baking (PEB) processes. The polymeric PAGs based resist systems which incorporated the PAG units into the main chain showed improved lithographic performance, such as faster photospeed and higher stability, lower outgassing, and lower LER than corresponding blend resists. In this paper, a novel type of polymeric PAGs based on poly (4-hydroxylstyrene) (PHS) was discussed. Chemically amplified photorssists were formed by the polymeric PAG and other film forming material containing acid labile groups. The polymeric PAGs showed advantage over the common small molecular PAG and patterns with 180 nm resolution was obtained in the 248-nm lithography.
With the growing demand of the electronics industry for smaller, higher resolution features, next generation
lithographic techniques, such as Extreme Ultraviolet(EUV) lithography have caused widely attention of the scientists.
As the EUV absorption is determined by the nature of atoms but not by the structure of molecules, poly(4-
hydroxylstyrene) (PHS) based resists can be employed in EUV lithography. Single-component resist system is
constructed by the polymers consisting of two major functional components, photoacid-generating unit and the acidlabile
group, which can help to alleviate the problem derived from the poor compatibility in multi-component resist
system. In this paper, PHS was used as raw material to prepare a novel polymer with sulfonuium salt group attached on
part of the benzene rings and the hydroxyl groups partly protected by t-BOC, which can be used as a novel kind of
single-component CA resist. The polymer can be dissolved in common resist solvents. The thermal stability, photolysis
and photolithographic property of the resist material were investigated.
In this work a few α-disulfone compounds with different substituents were prepared by a simple nitric acid oxidation of
corresponding disulfonylhydrazines which were prepared by reaction of sulfonyl chloride and aqueous hydrazine. Most
of the compounds are soluble in common organic solvents for photoresists. The thermal decomposition temperatures of
the compounds were detected to be above 190 °C. The UV absorption spectra of the α-disulfone compounds were
measured with the absorption peaks (λmax) around 250 nm. Quantum yields of the disulfone compounds in solution were
determined to be in the range of 0.4-0.6 with low pressure Hg lamp as exposure light source.
Recent years increasing attention has been given to molecular glass resist materials. In this paper, maleopimaric acid,
cycloaddition reaction product of rosin with maleic anhydride, was reacted with hydroxylamine and then further
esterified with 2-diazo-1-naphthoquinone-4-sulfonyl chloride to give N-hydroxy maleopimarimide sulfonate. The
carboxylic acid group of the compound was then protected by the reaction of this compound with vinyl ethyl ether or
dihydropyran. Thus obtained compounds were amorphous. When irradiated with i-line light, the 2,1,4-DNQ group
undergo photolysis not only to give off nitrogen gas but also generate sulfonic acid which can result in the decomposition of the acid labile group. So, a novel chemically amplified positive i-line molecular glass photoresists can be formed by the compound and other acidolytic molecular glass compounds. The lithographic performance of the resist materials is evaluated.
Novel ester acetal polymers can be synthesized by the reaction of common aromatic dicarboxylic acids with divinyl ether compound in the presence of organic solvent. These polymers have good solubility in commonly used solvents. The molecular weights of the acetal polymers are measured 6000 - 7000(Mn) with Mw/Mn of 1.5-2.5. The polymers show high thermal stability. The acidolytic reaction of the polymers undergoes rapidly at room temperature or at a little higher temperature. Making use of the acidolysis activity at room temperature of the acetal polymer, we can form new type of chemically amplified positive i-line photoresist with the main contents including phenolic resin, the acetal polymer and PAG(s-triazine). Clear pattern with resolution of 2-3&mgr;m was obtained in the lithographic experiment of the photoresist. The photosensitivity of the photoresist is below 50mj/cm2.
Molecular glass resists are low molecular-weight organic photoresist materials that readily form stable amorphous
glasses above room temperature. They can lead to high resolution patterns. New families of ester acetal molecular glass
materials have been created by the reaction between monocarboxylic acid and divinyl ethers. These organic materials
are monodisperse and amorphous. They can be dissolved in common solvents and possess high thermal stability. The
ester acetal compounds can be quickly decomposed at the presence of strong acid generated by photoacid generator
(PAG) at room temperature or higher temperature and become easily soluble in dilute aqueous base. They can form
positive photoresists together with PAG. The lithographic performance of the resist materials is being evaluated.
1,3-adamantanedicarboxylic acid and acrylpimaric acid were reacted with an aliphatic divinyl ether,
1,4-cyclohexanedimethanol divinyl ether, to give novel ester acetal polymers without phenyl group. These polymers can
be dissolved in common solvents and possess high thermal stability. The ester acetal polymer can be quickly
decomposed at the presence of strong acid generated by PAG above 100°C and become easily soluble in dilute aqueous
base. Two-component photopolymer consisting of the ester acetal polymer and PAG can be used as positive photoresists.
The polymer derived from 1,3-adamantanedicarboxylic acid displayed higher transparency at 193 nm and can be used
for 193 nm photoresist.
The reaction of acrylpimaric acid and several divinyl ether compounds, including 1,3-Bis(2-(vinyloxy)ethoxy)benzene,
2,2-bis(4-[2-(vinyloxy)ethoxy]phenyl)propane, and 1,4-Bis(2-(vinyloxy)ethoxy)benzene, can take place in the presence
of organic solvents to form novel ester acetal polymer with the average molecular weight of 4000-6000(Mn) measured
by GPC. These polymers can be easily dissolved in common solvents and show high thermal stability. The ester acetal
polymers can be quickly acidolyzed at the presence of strong acid generated by PAG above 100oC and become easily
soluble in dilute aqueous base. Two-component positive photoresists can be formed by the ester acetal polymer and PAG.
The lithographic performance of the resist material composed of the ester acetal polymer and a sulfonium triflate PAG
was studied on i-line exposure instrument. Clear pattern with 2 &mgr;m resolution was obtained and the photosensitivity was
below 20mj/cm2.
A kind of diacid, acrylpimaric acid, with condensed alicyclic structure and good film-forming property, was prepared by the Diels-Alder reaction of abietic acid and acrylic acid. In their solid film, the diacid can react with divinyl ether, such as 1,3-divinyloxyethoxybenzene when baked above 80oC and become insoluble in dilute aqueous base. Thus formed compound can be quickly decomposed at the presence of strong acid generated by PAG above 100oC and become easily soluble in dilute aqueous base. A positive photoresist can be formed by the diacid, divinyl ether and PAG. The measured photosensitivity is less than 50 mj/cm2 when exposed to low pressure Hg lamp (254nm). The diacid mixture displayed lower transparency than estimated at 193 nm and should be further purified to be used in 193 nm photoresist.
A convenient method was set up to measure the amounts of acid generated by PAGs and acid amplifiers based on the UV absorbance change of bromophenol blue aqueous solution with the addition of acid. The acid generating property of three different kinds of PAGs and acidolysis property of two 1-substituted cis-1,2-cyclohexanediol monosulfonates were investigated and discussed with this method. The measurements were performed in aqueous solution.
A few kinds of N-hydroxy maleopimarimide sulfonate derivatives were synthesized. These compounds have high solubility in commonly used solvents and high thermal stability. The UV absorption properties of these compounds in polyethylene glycol film indicate that they have suitable absorption and transparency at 193 nm wavelength. The photolysis and lithography of these compounds under radiation of low pressure Hg lamp were studied.
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