Osamu Yokokoji

Synthesis of new chiral compounds for cholesteric liquid crystal display

The synthesis and properties of (S)‐(2‐methylbutyl)benzene derivative and (S)‐2‐phenylpropionic acid derivatives were studied with a view to their application on cholesteric liquid crystal devices. Compared with available chiral compounds the new compounds exhibited larger helical twisting power and higher dielectric anisotropy. The relationship between structure and properties of these compounds is discussed.

Synthesis and properties of (E)-1,2-difluoroethylene derivatives: improvement of the ultraviolet light stability

The synthesis and properties of (E)-α,β-difluorostilbene derivatives were studied. In particular, we investigated three suppression methods of (E)–(Z) isomerisation by shortening the molecular conjugation length, which included the introduction of a fluorine atom into the ortho or para position of the benzene ring or the replacement of the benzene ring with a cyclohexane ring. The relationship between the molecular structure of liquid crystals and the level of isomerisation by ultraviolet (UV) light was discussed.

Development of partially fluorinated EUV-resist polymers for LER and sensitivity improvement

In order to improve EUVL resist characteristics, especially sensitivity, we have investigated two types of partially fluorinated resist polymers. The one was side chain fluorinated PHS type resist polymers. The other was main chain fluorinated resist polymers. Poly (p-hydroxystyrene) (PHS) type polymers with trifluorostyrene (TFSt) were synthesized and characterized their sensitivity behavior. From this evaluation, we found that PHS contained TFSt unit had a high sensitivity, keeping their etching durability. We expect that TFSt unit can work to enhance the resist sensitivity in PHS based EUVL resist polymers. Main chain fluorinated polymers based FIT unit (FITMAd and FITAdOM) were synthesized. FITMAd and FITAdOM showed high sensitivity compared to non fluorinated reference sample. From molecular weight measurement, we infer that the polymer main chain of FITMAd can be decomposed by irradiating with EUV light. The outgassing of FITMAd and FITAdoM were measured. There is no big difference between the total outgassing of FIT polymers and that of non fluorinated acrylic sample. And small amount of Hydrogen fluoride (HF) were detected. We infer that FITMAd and FITAdOM are decomposed then HF is generated under EUV exposure. From these results, we expect that FIT unit can work to enhance the resist sensitivity and can act main chain decomposed resist unit in EUVL resist polymers.

Development of fluoropolymer for 193nm immersion lithography

We had already developed several series of fluoropolymers, FPRs and FUGUs, having a partially fluorinated monocyclic structure and having acidic hydroxyl group, which acts as dissolution unit into alkaline solution. Then we have optimized these polymers for top-coat as the developer-soluble type in the 193nm immersion lithography. However the hydrophobicity of these polymers were a little poor due to its hydroxyl group. So we thought that the introduction of water repellent moiety into the these polymers structure is effective to improve the their hydrophobicity though the increase of water repellent unit in the polymer leads to lower dissolution rate in developer. To introduce as much as possible of hydrophobicity unit, we selected FUGU as platform, which has larger dissolution rate in developer than that of FPRs, We copolymerized FUGU with higher water-repellent component and obtained three copolymers, FUGU-CoA, FUGU-CoB, and FUGU-CoC. In this paper, we described characteristics and evaluation of these polymers. Most of these polymer showed an improvement of hydrophobicity, in particular FUGU-CoB had excellent hydrophobicity due to introduction bulky containing-fluorine group. In this study, we also investigated the interaction between the water and various polymers by using QCM method. The difference between FUGU and water repellent polymers for swelling behavior to water became clear by analysis of diffusion coefficient. We found that our new co-polymers have excellent diffusion coefficient than FUGU which was confirmed by QCM method used to evaluate water permeability and water diffusion in the materials.

Dry-etching resistance of fluoropolymers for 157-nm single-layer resists

Novel fluoropolymers having partially fluorinated monocyclic (5-membered and 6-membered ring) structure have been synthesized with radical cyclo-polymerization, which have C-F bond in the polymer main chain and also possess fluorocontaining acidic alcohol group. These polymers have excellent transparency lower than 1.0 μm-1 at 157nm wavelength, a small amount of outgassing, high sensitivity and good adhesion to the wafer. However, this fluoropolymer have lower etching resistance (half of conventional KrF resists) and it must be improved for applying to the single-layer resist. In this paper, we show the new model of the estimation of the dry-etching resistance for designing polymer compositions. It is well known that the model using carbon-atom-density as a parameter is useful for estimating dry-etching resistance. However, these models did not agree with the results of our fluoropolymers. Our new model was focused on the surface area and the volume of the polymer. We succeeded to explain the relationship between the dry-etching resistance and the composition of the fluoropolymer. According to this model, the compositions of fluoropolymer such as protective groups, protective ration and co-polymer units were optimized to improve their etching resistance.

Performances of resists for 157-nm lithography based on monocyclic fluoropolymers

Fluoropolymers are key materials for the single-layer resists used in 157-nm lithography. We have been studying fluoropolymers to determine their potential for use as the base resin and have developed a monocyclic fluorinated polymer with a blocking group of Cyclohexylcyclohexyloxymethyl (CCOM) that has high transmittance (an absorption coefficient of 0.64 μm-1) at a 157-nm exposure wavelength and high dry-etching resistance (a dry-etching rate of 1.75 times that of KrF resist) under organic bottom anti-reflective coating/hard mark dry-etching conditions. A resist based on our monocyclic fluoropolymer had high sensitivity. Using it, we were able to resolve a 60-nm line-and-space pattern using a 157-nm laser microstepper (numerical aperture = 0.85) with a resolution enhanced technology of an alternating phase-shifting mask. This polymer was demonstrated to simultaneously enable high transparency, high dry-etching resistance, and good imaging performance.

5,6-Difluoro-1H-indene derivatives: novel core structure of liquid crystals with high Δn and Δϵ

We have designed and synthesised the novel liquid crystal core structure, 2-phenyl-5,6-difluoro-1H-indene, based on preliminary calculation of the theoretical values of birefringence (Δn) and dielectric anisotropy (Δϵ). These compounds have been proved to have high nematic–isotropic transition temperature, and high optical anisotropy values with long molecular conjugation length. The introduction of lateral fluorine atoms into the 2-phenyl group of 5,6-difluoro-1H-indene derivatives leads to low viscosity and high dielectric anisotropy.

A new monocyclic fluropolymer structure for 157-nm photoresists

We earlier developed a series of fluoropolymers (FPRs) for use as first-generation 157-nm photoresist polymers. These FPRs have a partially fluorinated monocyclic structure and provide excellent transparency. However, their etching resistance is low (half that of conventional KrF resists) and an insufficient dissolution rate in tetramethylammonium hydroxide (TMAH) solution. To improve the characteristics of these polymers, while retaining high transparency, we had to redesign the main chain fluoropolymer structure. In this paper, we describe a new monocyclic fluoropolymer structure for a second-generation 157-nm photoresist polymer. This structure also has a fluorine atom in the polymer main chain, as well as a fluoro-containing acidic alcohol group. We synthesized two types of fluoropolymers, ASF-1 and ASF-2. We found that ASF-1 had transparency of 0.18 μm-1, better than that of the FPRs, and the etching resistance was improved. Unfortunately, the dissolution rate was poor. On the other hand, ASF-2 showed even better transparency of 0.1 μm-1, improved etching resistance, and a dissolution rate of more than 600 nm/s, which is sufficient for use as a resist. The introduction of a protecting group (e.g., the methoxymethyl or adamantylmethoxymethyl group) to the hydroxyl group of ASF-2 can be done after the polymerization reaction. Using partially protected ASF-2 with an appropriate protecting group, we were able to fabricate a sub-60-nm line-and-space pattern.

The modeling of immersion liquid by using quantum chemical calculation

For realizing next generation 193nm immersion lithography, developing suitable high refractive index liquid is an very important issue. To overcome the trade off relationship between high refractive index (optimally more than 1.6 ) and low absorbance (similar degree with H2O 0.0036cm-1), the molecular modeling based on quantum chemical ab-initio calculation was performed. We have successfully developed the predictive method of frequency-dependent refractive index for liquid and its absorbance. Then, we tried to estimate these properties to search for optimal candidates. In this paper, we report on the estimated results of the refractive index n and the absorbance at 193nm for some candidate compounds. We believe we could demonstrate the usefulness of the predictive method by using the quantum chemical calculation for developing new liquids, even if there were some degree of errors in the absolute values. We have found the -SO2- (like sulfone, sulfonate, sulfate) containing five- and six-membered ring compounds such as sulfolane and sultone etc. would achieve both high refractive index around 1.6 and relatively low absorbance. XeF4O and Bi(CF3)3 ,unfortunately, had absorption at 193nm due to the weak binding outer valence electrons. In the case of alkyl Si and Ge, Si(CH2CH3)4 might have a good balance of refractive index 1.59 and relatively low absorbance. Si(CH3)3CH2CH2OH and Ge(CH2CH3)4 were estimated to have refractive index of over 1.6, but have been estimated these might have sightly stronger absorption.

Highly hydrophobic materials for ArF immersion lithography

In immersion lithography, the impact of water on resist performance and the possibility of damage to the lens by the components eluted from the resist material are seriously concern. And much work has shown that controlling the water-resist interface is critical to enabling high scan rates. Many topcoat materials have been developed to control the aforementioned interfacial properties. Developable topcoats have been particularly investigated as suitable candidates for its applicability to the resist developing process. Achieving the balance between the low surface energy required for higher receding contact angle and the base solubility for topcoat removal is challenging. We have already reported FUGU polymer which have partially fluorinated monocyclic structure and hexafluoroalcohol(HFA) group and showed that its developer solubility was excellent but hydrophobicity was insufficient for high scan rate. We have also reported that co-polymers of FUGU and highly fluorinated monomers which have perfluorinated cyclic structure had sufficient hydrophobicity but lower developer solubility. We have found that it was difficult to use these copolymers in themselves as topcoat. But by blending of moderate amount of these copolymers into FUGU polymer, we have finally obtained highly hydrophobic developer-soluble topcoat. Hydrophobicity can be controlled by blending ratio. Furthermore we have newly successfully synthesized a series of fluoropolymers, FIT polymer partially fluorinated monocyclic structure and having carboxylic acid group as developer-soluble unit. When FIT polymer as well as FUGU polymer, was blended to highly hydrophobic copolymer, the blended polymer also showed higher hydrophobicity keeping sufficient developer solubility.