A high resolution negative working resist,LMR-UV,for g- and i-line lithography

LMR-UV (“low molecular weight resist for uv lithography”), a naphthoquinone-diazide sulfonic acid ester of a novolak resin, is a negative working resist. The mechanism of insolubilization of LMR-UV is based on the facts that the naphthoquinone-diazide moiety is decomposed to indenecarboxylic acid (polar compound) by photolysis upon UV irradiation and that the irradiated resist film insolubilizes in a non-polar developer. LMR-UV reliably forms 0.6 μm lines and spaces over a reflective substrate with steps by using a g-line stepper having a 0.35 NA lens. 0.6 μm-wide aluminum patterns over topography are obtained by use of g-line exposure and reactive ion etching. By use of an i-line aligner (NA = 0.42), LMR-UV resolves 0.25 μm space patterns with overhang profiles. The profiles are due to the large absorption coefficient of 3.8 μm^?1. 0.3 μm wide aluminum patterns are formed by i-line exposure and lift-off metallization.     

Epoxy resins for deep UV lithography

A negative resist based upon photo-acid initiated cationic polymerization of an epoxy resin (1, 2) was reported in the early eighties with the advent of onium salts (3–5). An efficient acid generating onium salt, triphenylsulfonium hexafluoroantimonate (6), absorbs light in the deep UV producing acid upon direct photolysis in this region of the spectrum. The resin component of such a negative resist system must be optically transparent over the exposure wavelengths to obtain vertical image profiles. Another difficulty often encountered with crosslinking negative resists is swelling of the crosslinked matrix during development with organic solvents. This swelling manifests itself in distorted images and/or complete adhesion loss, especially when submicron features are involved. Our goal has been to address these problems and develop an organic developable deep UV resist capable of providing submicron images. Optically transparent commercial resins, styrene-allyl alcohol copolymers, have been converted to glycidyl ethers, thereby providing cationically polymerizable functionalities. Careful choice of the resin was made to obtain reactive ion etch resistance, thermal stability, good adhesion, and coating properties. The synthetic procedure and characterization of the epoxy resin will be presented. The effect of the molecular weight distribution upon swelling during development and general solubility properties also will be discussed. Resist formulations exhibited sensitivities of 19 to 30 mJ/cm² on a Perkin Elmer 500 in the deep UV (UV2) mode. The electron beam sensitivity is 3 to 5 μC/cm² at 20 KeV. Submicron images have been generated in both optical and electron beam lithography.     

Recent resist developments in Japan—a review

Several kinds of resist materials for microlithography have been developed in Japan. Poly(4-vinyl phenol) sensitized with 3,3′-diazidodiphenyl sulfone has been proved to be a high resolution negative deep UV resist with high sensitivity and good resistance to dry etching. The use of this resist enables a 1:1 projection printer to replicate fine patterns with 1 micrometer (μm) minimum feature size at the rate of 90 wafers per hour. Poly(methyl isopropenyl ketone) (PMIPK) has been investigated as a positive deep UV resist. Several resists composed of PMIPK with or without sensitizers are commercially available. Dry-developable photo- and deep UV resists comprising PMIPK and aromatic bisazides have been developed. Poly(glycidyl methacrylate) having the sensitivity of 0.4 micro Coulomb (μC)/per square centimeter (cm²) is now being routinely used as a negative electron beam resist in the fabrication of chromium masks. Recently, aromatic polymers such as chloromethylated polystyrene, iodinated polystyrene, chloromethylated poly(α-methylstyrene), poly(vinylnaphthalene) and its copolymers have been investigated as dry-etching resistant electron beam resists.     

A negative resist for KrF excimer laser lithography

The design and preparation of a series of negative resists for KrF excimer laser lithography are described. Each resist is composed of poly(hydroxystyrene) and an aromatic azide. The base resin shows high transmittance of 62%/μm at 248 nm, when p-ethylphenyl p-azidophenylsulfonate. 4-azido-4α-methoxy-chalcone, 1-(4 azidobenzylidene)-3-(α-hydroxy-4-azidobenzyl)-indene, 4,4α-diazido-3,3α-dimethoxybiphenyl, or 1-(4-azidostyryl)-5, 5-dimethyl-2-cyclohexen-1-one is employed as a sensitizer. These azides are obtained by red-shifting the absorption maxima to lower energy regions than the exposing wavelength of 248 nm. Transmittance of resists can be controlled from 10 to 30%. The resist is exposed with a KrF excimer laser stepper and developed in an alkaline solution. Sensitivities of about 15 mJ/cm² are observed. A good, subhalf-micron resist profile is achieved. The photochemical reaction mechanisms of poly(hydroxystyrene) and 4,4α-diazido-3,3α-dimethoxybiphenyl were studied at 248 nm and 313 nm exposure. Quantum yield for photodecomposition at 248 nm is seven times larger than that at 313 nm, but dissolution-inhibition effects are larger at 313 nm exposure. Consequently, the resist shows higher sensitivity at 313 nm than at 248 nm.     

Polydiallylorthophthalate resist for electron-beam lithography

Polydiallylorthophthalate, PDOP, of low molecular weight and low molecular weight dispersivity has been prepared and investigated as a negative resist for electron-beam, X-ray and ultraviolet lithographies. The resist polymers were prepared by a conventional fractional precipitation method. It has been found that a high resolution pattern is obtained by using a molecular weight of 1 × 10⁴ and an M_w/M_n < 2. This gives a good solubility difference between the exposed and unexposed portions in the developer. Resolution is less than 1 μm without any scum. Sensitivity for 15 kV electron bourns is 4 × 10⁶C/cm²; and for X-rays (Al Kα) it is 100 mJ/cm². Sensitivity for UV is 10 times that of poly(methyl methacrylate), and resistance for C₃F₈ dry etching is comparable to AZ-1350J.     

A novel positive resist for deep UV lithography

A novel positive resist was prepared by sensitizing poly(p-trimethylsilyloxystyrene) with p-nitro-benzyl-9, 10-diethoxyanthracene-2-sulfonate (NBAS) which was found to be a deep UV bleachable acid precursor. The silylated polymer is converted to alkaline soluble poly(p-hydroxy-styrene) in the presence of acid and a small amount of water. The photoresist gives high resolution positive patterns on imagewise exposure with deep UV light with a sensitivity of 15 mJ/cm².     

Profile modification of resist patterns in optical lithography

A method is described to modify profiles of resist patterns in novolac and diazo-oxide containing systems. After patterning of the resist, two successive uniform flood exposures are given, one with deep UV (254 nm) at water-free conditions and the next with near UV (λ > 300 nm) at normal atmospheric conditions. The profile which results after development is vertical, concave or overhanging depending on flood exposure conditions and development processing. As the method includes a flood near UV exposure at atmospheric conditions the imagewise exposure energy can be reduced to approximately 35 percent of the normal value. Furthermore it gives also the possibility of using the resist as a deep UV resist. Another important implication is that standing wave effects are completely eliminated.     

A water‐developable negative photoresist based on the photocrosslinking of N‐phenylamide groups with reduced environmental impact

A water‐developable negative photoresist based on the photocrosslinking of N‐phenylamide groups was prepared by the copolymerization of 4‐styrenesulfonic acid sodium salts (SSS) with N‐phenylmethacrylamide (copolymer A) or p‐hydroxy‐N‐phenylmethacrylamide (copolymer B), and its properties such as solubility changes, photochemical reaction, and photoresist characteristics were studied. The copolymer containing a relatively higher amount of SSS units was soluble in water. Solubility changes of the copolymers in the various buffer solutions of pH 4 ～ 11 and in water upon irradiation were observed by the measurement of insoluble fraction. The copolymers were soluble in water before irradiation, whereas they became insoluble upon irradiation with the UV light of 254 nm. The photochemical reaction of the copolymer studied by the UV and IR absorption spectroscopies indicated that a photo‐Fries rearrangement was favored for copolymer A, whereas a photocrosslinking reaction was predominate for copolymer B. Resist properties of the copolymers were studied by measurement of the normalized thickness and by development of the micropattern. Negative tone images with a resolution of 1 μm were obtained with these materials that have a sensitivity (D) of ～ 1100 mJ/cm² with an aqueous developing process.© 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1172–1180, 2002     

Photografting of unable‐to‐be‐irradiated surfaces. I. Batch vapor‐phase process by one‐step method

Surfaces unable‐to‐be‐irradiated are those that could not be directly exposed to UV irradiation because of their irregular structure or instability under UV irradiation. It is difficult to conduct surface photografting on these kinds of surfaces with conventional photografting methods. Here, a novel one‐step surface photografting method is introduced, by which some monomers were smoothly grafted on the surface of polymer substrates located in a region out of the reach of UV radiation. The mechanism is that the photochemical reaction is separated into three events, absorbing UV light in one place, then transporting light energy to another place, and reacting there; in other words, the conventional photochemical reaction is separated by space and time, and the key point is that the substrate does not need to be exposed to UV irradiation. The occurrence of grafting polymerization was proved by UV–vis, ATR‐IR, SEM, XPS, and water contact angle measurements. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2269–2276, 2006     

Poly(4-chlorostyrene), a new high contrast negative E-beam resist

PCS(poly-4-chlorostyrene) has previously been evaluated as a negative e-beam resist, but although the sensitivity was good [2 to 5μC/square centimeter (cm²)], the contrast (γ) was poor (1.1 to 1.5). Recent experiments have shown that contrast is not only a function of molecular weight distribution (MWD), but can also be affected by polymerization conditios. Among these are: branching, head to head linkages, and oxygen in backbone. PCS was prepared via thermal free radical solution polymerization, and then fractionated by differential solvation techniques. Reactions occurring during polymerization and crosslink formation on irradiation will be discussed. For molecular weights of 700 and 300K respectively (same MWD), the sensitivity was 2 and 5μC/cm², while the contrast (γ) was 3.5 for both. This is the highest reported contrast for a polymeric negative resist. The resist can then be UV hardened after development, and will not flow at 200°C. The RIE etch rate is ～1/2 that of PMMA in various plasmas.     

Azide-phenolic resin UV resist (MRL) for microlithography

Poly(4-vinylphenol) sensitized by an aromatic monoazide compound (4-azidochalcone), called MRL (Micro Resist for Longer wavelengths), has been prepared and evaluated as a negative UV resist. The resist is sensitive to radiation in the 300 to 400 nm region. The sensitivity of MRL is comparable to that of a positive quinonediazide photoresist under exposure to unfiltered light from a high pressure Hg lamp. An aqueous base developer removes the unexposed areas of MRL with no evidence of swelling of the exposed areas, indicating its high resolution capability. The main products in the exposure of MRL films are found to be primary and secondary amines. It is concluded that the formation of secondary amines attached to the polymer chain is responsible for the insolubilization of the exposed MRL in the base developer.     

Novel positive deep UV resist for KrF excimer laser lithography

A novel positive deep UV resist for KrF excimer laser lithography has been developed. The resist is composed of 1,7-bis(4-chlorosulfonyl phenyl)-4-diazo-3,5-heptanedione as the alkaline dissolution inhibitor and an alkali-soluble sytrene polymer as the main-polymer. 1,7-bis(4-chlorosulfonyl phenyl)-4-diazo-3,5-heptanedione has great capability of alkaline dissolution inhibition. High thermal stability and excellent photobleachability at 248 nm of the compound are also characterized. The alkali-soluble styrene polymer has a high transmittance of 70% in 1.0 μm thickness at 248 nm. The novel positive resist had an excellent property for dissolution kinetics and photobleaching. We achieved high aspect ratio half-micron pattern fabrication in 1.0 μm thickness using the new resist.     

Photoinduced ionic conductivity in poly(ethylene glycol) containing malachite green leuco hydroxide

Summary Photoinduced ionic conductivity in poly(ethylene glycol) 400 (PEG400)/malachite green leuco hydroxide (MGLOH) was analyzed with photochemical reaction of MGLOH in its matrix. The resonance structure in photogenerated cation lay in the favor of 4,4-(dimethylamino) triphenylmethylcation (MG⁺) under UV irradiation. The change in the ionic conductivity was discussed with that in glass transition temperature (Tg) of the matrix on UV irradiation.     

一种新型含肉桂酸酯结构的螺吡喃光致变色染料的合成与性能研究

A novel bifunctional dye containing spirobenzopyran and cinnaznoyl moiety has been prepared and its photochromic behavior following irradiation at different wavelengths of monochrome UV light was investigated.The colourless bifunctional dye in film or solution exhibits unusual photochromism through structural and geometrical transformation from spirobenzopyran to merocyanine accompanying with photocrosslinking reaction in cinnamoyl moieties. Two kinds of photochemical reaction were achieved by irradiation at the different wavelengths of monochrome UV light (275 nm, 365 nm) selectively. The photochromic process of the bifunctional dye was discussed and the dynamic behaviors of the decolorization process were investigated.     

Polyimide surface modification by pulsed ultraviolet laser irradiation with low fluence

Surface modification on a polyimide film by pulsed ultraviolet (UV) laser irradiation with a fluence below its ablation threshold was studied by X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and UV-vis spectroscopy. It was observed that a photochemical reaction occurred and hydrophilic groups, such as —OH and —COOH, formed on the polyimide surface after irradiation. In addition, a ripple microstructure formed on the surface when the angle of incidence of the laser beam was 20–50^o. The contact angle of the polyimide surface with water decreased and the adsorption ability of the surface to a water-soluble dye clearly increased after laser irradiation. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2739–2743, 2001     

Photoinitiated surface grafting of synthetic fibers,I. Photoinitiated surface grafting of ultra high strength polyethylene fibers

Photoinitiated surface grafting of acrylic monomers has been carried out onto high strength polyethylene (HSPE) yarn by means of a continuous process. The grafting reaction is initiated by UV irradiation of the yarn after presoaking in an acetone solution of initiator and monomer. Four initiators, benzophenone (BP), 4-chlorobenzophenone (4-CBP), 2-hydroxy-2-cyclohexylacetophenone (HHA), and 2,2-dimethoxy-2-phenylacetophenone (DMPA), and two monomers, acrylic acid (AA) and acrylamide (AM), have been used. After short irradiation time (10 to 20 s) successful grafting is obtained, as shown by ESCA and IR-ATR spectra, dye adsorpotion from aqueous solution, and measurements of adhesion of single filaments to epoxy resin. Grafting efficiency of 74% has been reached for AA as monomer (26% is homopolymer). The tensile strength and modulus of the HSPE yarn are retained in the grafting process. The degree of surface grafting is mainly a function of structure and concentration of monomer and photoinitiator in the presoaking solution and of the irradiation conditions used. Increasing irradiation time gives increasing amounts of grafted polymer up to a certain limiting value. The reactivities of the four initiators have been compared showing the highest grafting yields of AA with BP and of AM with 4-CBP as photoinitiator. AA grafted HSPE yarn can be dyed to rather deep color by dipping in an aqueous solution of Crystal Violet. Increased dye absorption by a factor of up to seven has been measured for yarn grafted with AA to the maximum level obtained. The filaments of the grafted yarn show increased adhesion to epoxy resin by a factor of up to five compared with the ungrafted filaments.     

Aqueous base developable deep-UV resist based on chemically amplified crosslinking of phenolic resin

The principle of chemical amplification has proven to be successful for the design of highly sensitive, high resolution resist material. In many cases a strong Broensted acid, generated by photolysis of onium salt precursors, has been used to catalytically cleave an acid labile blocking moiety. A new approach to negative tone resist is based on acid catalyzed cleavage of acetal blocked aromatic aldehydes, which act as “latent electrophiles” and, under the influence of strong acid, react with the surrounding phenolic resin. If the acetal is polyfunctional or incorporated in a phenolic polymer chain, an increase in molecular weight, due to crosslinking, is observed. The resist is highly sensitive and allows the resolution of 0.5 μm features without swelling.     

Photosensitive polymers containing pendent chalcone moieties via oxyethylene group

Vinylchalcone derivatives were prepared by the reaction of the sodium salt of 4-hydroxychalcone with 2-chloroethanol, followed by esterfication of the hydroxy groups with methacryloyl chloride in the presence of triethylamine as a base. The photosensitive monomers, 4-(methacryloyloxyethoxy)chalcone and its 4′-methyl and 4′-chloro-derivatives, have been homo- and copolymerized with p-nitrophenylmethacrylate under free radical conditions to give the copolymers containing different ratios of photosensitizer group. The photosensitivities of the polymeric chalcone derivatives were investigated through their photochemical reactions on exposure to UV light and measuring the changes in UV spectra before and after irradiation. The results of these measurements indicate that the insolubilization percentage, i.e. the rate of the double bond disappearance depends on the effects of (i) the time of exposure to UV light, (ii) the position of the substituent in the phenyl ring of the chalcone, (iii) the spacer between the active moiety and the polymer backbone, and (iv) the ratio of the photosensitizer group.     

Studies on the photodegradation of polarized UV‐exposed PMDA–ODA polyimide films

Polarized Fourier transform infrared (FTIR) and ultraviolet‐visible (UV‐VIS) spectroscopy were used to investigate the photodegradation direction of polarized UV (PUV)‐irradiated polyimide (PI) films based on pyromellitic dianhydride (PMDA) and 4,4′‐oxydianiline (ODA). PI films strongly absorb below 350 nm, resulting in a photochemical reaction of the PI. PUV irradiation of the PI film caused a decrease of all existing peaks and formation of new peaks at 3258, 1748, and 1710 cm^?1 in the IR, due to degradation of the PI molecules. The preferential degradation of PI molecules parallel to the PUV irradiation direction results in the predominant orientation of the remaining PI molecules perpendicular to the PUV irradiation direction. But rubbing of the PI films induced orientation of the PI molecules parallel to the rubbing direction. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3072–3077, 2002     

Photoinitiated cationic polymerization of epoxides

Difunctional epoxy monomers have been polymerized cationically by UV irradiation in the presence of a triarylsulfonium photoinitiator. The curing process was followed quantitatively by monitoring the disappearance of the epoxy group by infrared spectroscopy and the insolubilization and hardening of the resin upon UV exposure. The addition of epoxidized soyabean oil (ESO) to an aromatic diepoxide was shown to accelerate the crosslinking reaction with formation of a tight polymer network. The photoinitiated copolymerization of ESO with a cycloaliphatic diepoxide proceeds extensively and leads within seconds to a fully cured insoluble material showing increased hardness, flexibility and scratch resistance. Interpenetrating polymer networks have been generated by a short UV‐irradiation of blends of acrylate and epoxy monomers. © 2001 Society of Chemical Industry