Polymeric materials have been utilized in semiconductor industries such as pattern formation materials. One of the drawbacks of such polymers is the lack of etch resistance. Metal infiltration into polymer matrices is an emerging technology that could overcome the issue. The gaseous organo-metal precursors penetrate into polymer matrices where they are oxidized to form stable metal oxides. Thus formed organic-inorganic hybrid material shows superior etch-resistance which enables to form patterns with high aspect ratio [1]. One of the most commonly studied processes is the infiltration of trimethylaluminium (TMA) into polymethylmethacrylate (PMMA). One of the issues of this technology is that increase in volume of the polymer after the infiltration is inevitable, since metal oxides are added to the polymer. For example, we observed over 10 % of volume expansion for the combination of PMMA and TMA [2]. If this technology was dedicated to small feature sizes, it would be preferable to maintain its original shape. Poly(tert-butylmethacrylate) (PtBuMA) has a similar structure to PMMA except that it has a tert-butyl group on its side-chain instead of a methyl group. This polymer is known to decompose above 180 degree Celsius, releasing the butyl group in form of 2-butene. If the out-going of tert-butyl group and the in-coming of TMA occurs simultaneously under ambient temperature, we can expect to see a balance of volumetric shrinkage and expansion. In this paper, a concept using PtBuMA to compensate the volume increase after metal infiltration is described.
One of technical issues of directed self-assembly lithography is extremely narrow patterning range. It is really difficult to make not only smaller patterns (pitch of less than 30nm) because of self-assembling limit but also middle patterns (pitch of more than 60nm) because of material synthesis issues. This paper describes wide–range directed self-assembly lithography which enables not only narrow patterns but also wide patterns using newly developed block copolymer. One block of the new block copolymer is easily metalized selectively by metalize technology and it is confirmed that dry etching resistance is markedly improved.
Molecular resists are expected to offer the advantages of high resolution and low line width roughness (LWR) for the
next-generation lithography. We developed a new molecular resist that showed high resolution by introducing an
efficient acid-leaving group to an amorphous molecule, 1,3,5-Tris(p-(p-hydroxy- phenyl) phenyl) benzene (THTPPB).
The lithographic properties such as sensitivity, developing rate, and adhesion are considered to be controlled using a
suitable acid-leaving group. A molecular resist of THTPPB to which is attached with an alicyclic acid-leaving group,
hyperlactyl vinyl ether group (HPVE) showed a high resolution for electron beam (EB) lithography and good etch resistance. Half-pitch 36 nm line-and-space (1:1) positive pattern was fabricated using 100 keV EB with chemically amplified molecular resist based on HPVETPPB.
A novel molecular resist based on a new amorphous molecule, a truxene derivative, was designed and synthesized.
Truxene is characterized as an amorphous solid with a high glass transition temperature (Tg). 70 nm line-and-space (1 : 1) positive pattern was fabricated by the exposure of a low-energy electron beam (5 keV) using the new molecular resist.
The new molecular design of resists based on the truxene derivative is promising with regard to development of more
efficient molecular resists.
We have produced aluminum wire grids with 33 nm periodicity using a thin film of a self-assembling cylinder
forming diblock copolymer as a template. These grids, supported on fused quartz wafers, function as transmission
polarizers for visible and near-ultraviolet lights and are a thin design, compared to commercially available polarization
prisms. Their polarization efficiency is measured to be near 50% in the visible. Quantitative comparison with a new
theoretical analysis of such wire grids indicates that they should perform well into the far UV. This analysis also
explains a reversal in polarization direction at short wavelengths which we observe in our specimens. This is an
expanded version of a previous paper.1
Recent advances in the 193-nm single-layer resist for forming finer patterns have led us to search for new resist materials for the ArF excimer laser. We describe novel, mass productive single layer resist based on hybrid hyper lactonic polymer which has high resolution, good hydrophilicity, and dry etch resistance. Further, we investigate the lactonic polymer, which has Mass-productive Ultimate Norbornyl group with Outstanding Solubility (MUNGOS).
Acrylate monomers containing alicyclic side chains featuring a series of polar substituent groups were assumed to be model compounds. Solubility parameters were calculated for the corresponding acrylate polymers. These acrylate monomers were synthesized using a novel aerobic oxidation reaction employing N-hydroxyphtalimide (NHPI) as a catalyst, and then polymerized. These reactions were confirmed to be applicable for the mass-production of those compounds. The calculation results agreed with the hydrophilic parameters measured experimentally. Moreover, the relationship between the resist performance and the above-mentioned solubility parameter has been studied. As a result, a correlation between the resist performance and the calculated solubility parameter was observed. Finally, resolution of 0.13-micron patterns, based on the 1G DRAM design rule, could be successfully fabricated by optimizing the solubility parameter and the resist composition.
The resist comprising naphthalene rings instead of benzene rings was developed for ArF excimer laser lithography. Naphthalene shows outstanding dry etch resistance, stronger adhesion to silicon surface and low hydrophobicity compared with most alicyclic compounds. Di-tert-butyl 2-[(1- adamanthyl) carbonylmethyl] (ADTB) was developed as an additive to improve the characteristics of development of base polymer. Although ADTB has tert-butyl protective groups, the decomposition temperature is low compared with that of polymer which has a tert-butyl protective group. Moreover, the dry etch resistance of the resist becomes greater as ADTB content increases. 0.133 micrometers L/S patterns were fabricated using Nikon's ArF prototype exposure system. Next, in order to improve the adhesion of the resist having the alicyclic frame, introduction of naphthalene in to the resist was attempted. The new resists which has naphthalene frame showed stronger adhesion and 0.15 micrometers L/S patterns were fabricated using the ArF exposure system with the standard developer.
Recent advances in the single-layer resist for forming finer patterns have led us to a search for new resist materials for the ArF excimer laser. We describe a novel, environmentally friendly, single-layer resist based on a menthyl acrylate copolymer protected with a cleavable alicyclic group and the absorption band shift method.
This paper focuses on the inhibition efficiency of t-Boc derivatives of bis-phenols. Several t- Boc derivatives of bis-phenols were synthesized and their inhibition effects were evaluated in novolac resin and poly (4-hydroxystyrene) (PHS). When the novolac resin was used as the matrix polymer, the inhibition effects were thought to be governed by both the hydrophobicity and molecular size of the inhibitors. On the other hand, in the case of PHS, the hydrophobicity of the inhibitor molecule was thought to be the dominant factor responsible for decreasing dissolution rates. In addition, the effects of the basic components of the developers were also investigated. Solutions of sodium hydroxide, tetramethylammonium hydroxide and tetraethylammonium hydroxide were employed as developers. The effects of the basic components on the dissolution rates of the resists varied with the matrix polymer of the resist. The dissolution rate of novolac resin was higher in NaOH solution than in the developers consisting of organic bases. However, the dissolution rates of novolac resin samples containing dissolution inhibitors were lower in NaOH solution than in developers consisting of organic bases. This phenomenon may be attributable to the hydrophilic properties of the cation of a developer.
A novel simulator using the Monte-Carlo method, which simulates molecular-like movements and reactions in chemically amplified resist systems, has been developed in order to clarify the mechanism of amine additive. The simulation program simulates diffusion phenomena with random-walked acids and amine molecules, and reactions of deactivation (neutralization) and inhibitor cleavage in every movement of the molecules. It was found that the amine in the exposed area was rapidly deactivated, and the concentration profile of the remaining amine was rapidly changed to an inversely shaped profile of that of the acid. This means that the remaining amine prevents diffusion of acids outside the exposed area by functioning as a barrier during almost the whole period of post-exposure bake (PEB). These concentration profiles lead to an enhancement of stability of pattern sizes and reduction of edge roughness of the pattern. Environmental stability was also calculated, and amine additive was also found to prevent contamination from the environment in the initial period of the PEB.
The VUV-absorption spectrum of aromatic compounds can be red-shifted toward longer wavelengths to make the window of absorption align with 193 nm by extending the conjugation length of the double bonds. Based on this observation, the new concept of absorption band shifting is proposed as a way to increase the transparency of resist components for 193 nm ArF excimer laser exposure. A chemically amplified single-layer ArF excimer laser resist consisting of naphthalene-containing photoacid generator, a dissolution inhibitor, and base polymer has been newly developed. Using this resist, a 0.17 micrometers line/space pattern with a vertical resist profile was resolved by a prototype 0.55 NA projection lens for ArF excimer laser exposure, and a resolution limit of 0.16 micrometers was achieved.
The effect of amine additives in chemical amplification resists is discussed. Phenolic amines such as 4-aminophenol and 2-(4-aminophenyl)-2-(4-hydroxyphenyl) propane were investigated as model compounds from the viewpoint of sensitivity, diffusion and resolution. Equal molar amounts of acid and amine deactivated at the very beginning of post-exposure bake, and could not participate in decomposing the inhibitor as a catalyst. Only the acid which survived from the deactivation diffuses in the resist, decomposing the inhibitors from the middle to late stage of PEB. The basic additives reduce the diffusion range of the acid, especially for long-range diffusion, resulting in higher contrast at the interfaces between the exposed and unexposed areas. In addition, the amine concentration required is found to be less than the concentration which causes the resist sensitivity to start decreasing.
Quantum chemical calculation is applied to investigate the reaction mechanism of sulfonyl acid generator and the transparency of the resist material. We have found that electron absorbed dimethylsulfone can be easily decomposed by relatively low energy (2.95 Kcal/mol), reaching to the decomposed status of methyl radical and methyl sulfonyl anion. This was thought to be an initial step in the electron acid generation reaction of the sulfonyl compounds. The total molecular energy of dimethyl sulfone anion was found to be higher than that of the neutral dimethylsulfone. On the other hand, sulfone derivatives with electron-withdrawing groups, such as methyl sulfonyl acetonitrile, usually have higher energy (about 41 kcal/mol) than those for their anion. This suggests that the electron withdrawing groups enhance the electron affinity of the sulfone compounds, which are also considered to increase the efficiency of acid generation. Additionally, another quantum chemical study was carried out in order to improve transparency of the aromatic species in resist for ArF excimer laser. Using configuration interaction (CI) methods of molecular orbital theory, the substituent effects of UV absorption in the aromatic compounds were investigated. As a result, significant red sifts in Amax were observed in the conjugated aromatic rings, which increases the transparency at 193 nm wavelength region.
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