Ultrafast deep UV lithography using excimer lasers

Various excimer laser wavelengths have been used, both in mid- and deep-UV regions—308 nanometers (nm) from XeCl, 249 nm from KrF and 222 nm from KrCl–to delineate images in a number of resists. The quality of the images obtained with the laser exposures, the absence of speckle, and the insignificant loss of resist reciprocity make excimer laser lithography an attractive technique. The ultrafast exposures possible with this method significantly lessen the sensitivity requirements on deep UV resists, making the choice of the resist more flexible.     

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.     

Tetrahydropyranyl- and furanyl-protected polyhydroxystyrene in chemical amplification systems

Tetrahydropyranyl- (THP) and furanyl- (THF) protected polyhydroxystyrene (PHS) polymers have been investigated for their potential use in conjunction with onium salt acid precursors to yield high-sensitivity resist systems. The synthesized polymers have high transmittance at 248 nm (the wavelength used in next-generation excimer laser, KrF exposure tools). At 248 nm the transmittance for a 1-μm thick film is ～ 80% (Abs = 0.097 μm^?1). The acid sensitivity of the acetal functionality at room temperature is high, requiring careful handling of all materials to prevent any premature deprotection of the hydroxy group. The highest lithographic sensitivities obtained so far with a system consisting of poly(p-tetrahydropyranyl-oxy-styrene) base resin and 1 mol % of bis (p-tert-butyl phenyl) iodinium triflate (TBIT) was ～ 2 mJ / cm². High-resolution line and space patterns (0.35 μm) were obtained with a system comprising PHS-p-THP and an acid precursor, using an excimer laser step and repeat exposure at 248 nm.     

Study on organosilicon positive resist. III. Organosilicon positive excimer laser resist (OSPR-2016)

A new alkali-developable organosilicon positive excimer laser (KrF) resist (OSPR-2016) has been developed for a bilayer resist system. OSPR-2016 is composed of poly(p-hydroxybenzylsilsesquioxane) and methyl cholate-tris (α-diazoacetoacetate). The ratio is 72.5 : 27.5 w/w. A sample of 0.5-μ thick OSPR-2016 resolved 0.35 μ L&S patterns when exposed to a dose of 320 mJ/cm² from an excimer laser projection printer (NA = 0.37).     

Positive excimer laser resists prepared with aliphatic diazoketones

A new class of alkali-developable positive excimer laser (KrF) resists is described. Novel α-diazoacetoacetates derived from aliphatic polyfunctional alcohols were synthesized. These compounds undergo photolysis upon deep UV exposure to yield carboxylic acids, and exhibit excellent bleaching effects. Some of them, especially those having steroid skeletons, act as effective dissolution inhibitors. The composites prepared from these compounds and poly(p-hydroxybenzylsilsesquioxane) were used as alkali-developable positive deep UV resists, whose sensitivities depend on the number of photoactive groups in one photoactive molecule. Imaging results of KrF excimer laser projection printing are presented.     

Well‐defined diblock and triblock copolymers for KrF lithography

One of the major components of a photoresist formulation is polymer resin. Well‐defined diblock and random copolymer of tert‐butyl acrylate (tBA) and 4‐acetoxystyrene (StyOAc), as well as triblock and random tertpolymer of tBA, StyOAc, and Sty were prepared by reversible addition fragmentation chain transfer polymerization (RAFT) process. The polymers all possess M_w about ten thousand and PDI less than 1.23. After hydrolysis under basic condition, the hydroxystyrene (StyOH) analogs are obtained and then are formulated as photoresist. Lithographic evaluation under KrF excimer laser shows that random copolymer based photoresist exhibits better S/L patterns according to SEM images. However, the lithographic performance of the terpolymer based resists is similar. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Poly(t-butyl-3α-(5-norbornene-2-carbonyloxy)-7α,12α-dihydroxy-5β-cholan-24-oate-co-maleic anhydride) for a 193-nm photoresist

A copolymer of t-butyl-3α-(5-norbornene-2-carbonyloxy)-7α,12α-dihydroxy-5β-cholan-24-oate and maleic anhydride was synthesized as a matrix polymer for ArF excimer laser lithography. The polymer has an excellent transmittance at 193 nm and possesses good thermal stability up to 255°C. The resist formulated with the polymer showed better dry-etching resistance than the conventional KrF excimer laser resist for chlorine and oxygen mixed gas. A 0.15 μm line and space patterns were obtained at a dose of 18 mJ cm⁻² using an ArF excimer laser stepper.     

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 study of CO2 and excimer laser treatments of poly(etheretherketone)

CO₂ and excimer laser (193, 248, 350 nm) treatments were performed on poly(etheretherketone) (PEEK). High fluence excimer laser irradiation induced efficient etching, mainly due to thermal effects. The irradiation with CO₂ lasers and high fluence excimer lasers introduced limited changes in surface chemistry and morphology. Low fluence excimer laser irradiation, particularly at 193 nm and 248 nm, favored the occurence of photochemical phenomena. Surface chemical modifications leading to oxygen depletion and preferential elimination of the ketonic bridge were assessed. At the same time surface morphological alterations were found, diffraction effects led to cone-like structures while the redeposition of heavy oligomers caused the formation of debris on the surface.     

Incubation phenomena during UV‐pulse excimer laser processing of silicone elastomers

Observations of the interaction of poly(dimethylsiloxane) (PDMS) sheet (210 μm thick) with KrF excimer laser irradiation (λ = 248 nm), with low energy of 50 mJ/pulse are presented. The negative ablation or swelling of the material caused by low frequency pulse irradiation is characterized by optical microscopy, μ‐Raman spectrometry and X‐ray micro‐tomography. The appearance of defected areas in the form of cones inside the sheet and changes of material chemistry are discussed. These phenomena are considered as a precursor of the ablation occurring after passing a threshold of absorbed laser irradiation energy. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44541.     

Preparation of Ultrafine Fe–Pt Alloy and Au Nanoparticle Colloids by KrF Excimer Laser Solution Photolysis

We prepared ultrafine Fe–Pt alloy nanoparticle colloids by UV laser solution photolysis (KrF excimer laser of 248 nm wavelength) using precursors of methanol solutions into which iron and platinum complexes were dissolved together with PVP dispersant to prevent aggregations. From TEM observations, the Fe–Pt nanoparticles were found to be composed of disordered FCC A1 phase with average diameters of 0.5–3 nm regardless of the preparation conditions. Higher iron compositions of nanoparticles require irradiations of higher laser pulse energies typically more than 350 mJ, which is considered to be due to the difficulty in dissociation of Fe(III) acetylacetonate compared with Pt(II) acetylacetonate. Au colloid preparation by the same method was also attempted, resulting in Au nanoparticle colloids with over 10 times larger diameters than the Fe–Pt nanoparticles and UV–visible absorption peaks around 530 nm that originate from the surface plasmon resonance. Differences between the Fe–Pt and Au nanoparticles prepared by the KrF excimer laser solution photolysis are also discussed.     

Effect of a deprotection group on acrylic photoresist

This study is synthesized and investigated polyacrylate single layer resist (SLR) using t-amyl alcohol as a deprotection group. The t-amyl group of the copolymer resist and dissolution inhibitor (DI) in this chemically amplified photoresist (CAMP) was deprotected by a light stimulated photoacid generator (PAG) upon post exposure bake (PEB). The polarity change of the system from a hydrophobic to a hydrophilic property made the exposed region soluble in the base developer. KrF and ArF excimer lasers were used to test resists using two components (PR and PAG) and three components (PR, DI and PAG) in the resists. This study also investigated the different effects of exposure dose, developer concentration, and content between t-amyl and t-butyl methacrylate on lithographic performance of resists.     

Surface pretreatment of glass fiber-reinforced liquid crystalline polymer composites by excimer laser for adhesive bonding

This paper reports the results of using a new laser surface pretreatment technique to improve the strength of adhesive joints. A high power KrF excimer laser at 248 nm output was used to surface-treat a glass fiber-reinforced liquid crystalline polymer (LCP) composite. With optimum process parameters, the polymer matrix at the surface was etched away efficiently and the bare fibers anchored on the matrix were left dangling and undamaged. The surface morphology produced by this new technique resulted in high quality adhesive joints. Both lap-joint and butt-joint configurations were investigated. A 350% improvement in the butt-joint strength was achieved by this new pretreatment technique as compared with that of the untreated one.     

Polysilanes: Photochemistry and deep UV lithography

The photochemistry of poly(cyclohexylmethylsilane) (PCHMS) has been studied, and PCHMS homopolymer has been shown to be useful for high resolution, deep UV pattern generation either by using a commercial 1:1 projection printer operating in the deep UV or by an excimer laser stepper at 248 nm. In the case of the excimer laser stepper, images 0.5 μm and smaller have been printed, which represents an improvement over the 0.8 μm limit previously reported for polysilane copolymers.     

Excimer laser projection patterning with and without resists

Projection imaging with the deep-UV (193 nm) and VUV (157 nm) output of an excimer laser has been applied to submicrometer patterning of thin films by injected-defect, surface-chemical, and solid-transformation processing. The methods have been designed to take advantage of the short-wavelength, high-peak-intensity pulsed radiation from these sources. Examples are described of pattern definition by exposure of multilayer organic resists, by maskless etching and doping of solids in reactive vapors, and by solid-state chemical transformations in inorganic Al/0 films. Well-resolved 0.4-μm lines and spaces have been achieved. Required doses, between 0.04 and 1 J/cm², are compatible with single- or multi-pulse step-and-repeat projection patterning with a small excimer laser.     

Laser-induced phase transitions in ion-implanted diamond

Results are reported on the study of phase transformations in D⁺ (deuterium) ion-implanted diamond single crystals induced by nanosecond pulses of a KrF excimer laser (λ=248 nm). Multipulse laser irradiation at fluences lower than the graphitization thresholds resulted in progressive annealing, pronounced in an increase of the optical transmission and surface contraction. A non-linear defect distribution in a near-surface layer was found to strongly affect the annealing and graphitization processes; higher annealing efficiency and higher graphitization thresholds were observed under irradiation conditions when a laser beam was incident onto a buried defective layer through diamond, i.e., onto a ‘back’ side of the diamond sample opposite to the ion-implanted side. The influence of non-uniform laser-induced heating of defective diamond material on characteristic features of the phase transitions is discussed.     

Chemical structure change of a KRF‐laser irradiated PET fiber surface

Laser ablation of a poly(ethylene terephthalate) fabric with an excimer laser beam (248 nm) was analyzed by color tests, and the chemical structure change of the surface was studied. This analysis suggests the possibility of the formation of both OH and CHO groups on the poly(ethylene terephthalate) surface. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2027–2031, 1999     

Evaluation of pressure-sensitive tape adhesion and backing directionality by excimer laser methods

The effects of 248 nm KrF excimer laser irradiation on a pressure-sensitive adhesive tape bonded to a glass substrate were investigated as a possible method to evaluate the quality of adhesion, as well as the directionality induced during manufacture. The model pressure-sensitive tape consisted of biaxially-oriented polypropylene (PP) tape coated with a hot-melt rubber resin. Analysis of the front-shot experiments, which were performed by irradiation through the PP backing, allowed correlation between the excimer laser irradiation-induced detachment and the peel adhesion strength. For this purpose, peel tests were performed before and after laser shots. The directionality induced during manufacture resulted in a more ablated area in the strength direction than in the transverse direction when the bonded tapes were irradiated with an elliptically-shaped laser beam above the ablation threshold. A correlation was found between the detachment bubbles created by irradiation below the ablation threshold and their respective peel adhesion values, which allows us to evaluate the quality of adhesion for pressure-sensitive tapes. Thus, a method to evaluate the quality of adhesion using an excimer laser is proposed based on the findings of this work.     

Synthesis and characterization of thermotropic liquid crystalline poly(azomethine ether)s

Two series of monomers, namely 4,4′-diformyl-α,ω-diphenoxydecane and 4,4′-diformyl-3,3-methoxy-α,ω-diphenoxydecane, were prepared from 1,10-dibromodecane with p-hydroxybenzaldehyde and 4-hydroxy-3-methoxybenzaldehyde (vanillin), respectively. The poly(azomethine ether)s were prepared by solution polycondensation using 4,4′-diformyl-α,ω-diphenoxydecane, 4,4′-diformyl-3,3-methoxy-α,ω-diphenoxydecane with various diamines. The monomers and polymers were characterized by intrinsic viscosity, FT-IR, ¹H, and ¹³C NMR spectroscopy. The thermogravimetric analysis reveals that the polymers are stable up to 320-500 °C and decomposed with good char yield. The thermotropic liquid crystalline properties of the polymers were examined by differential scanning calorimetry (DSC) and their textures observed under hot stage optical polarized microscopy (HOPM). All the polymers were exhibited thermotropic liquid crystalline properties except tetramethylene diamines-based polymers.     

Dry developable resist in e-beam and sr lithography

Dry developable resists comprised of poly(methyl isopropenyl ketone) (PMIPK) and 4-methyl-2,6-dI-(4′-azldoben-zylidene)-cyclohexanone-1 gave excellent results in SK lithography, i. e., high aspect ratio resist patterns with vertical walls were easily obtained by maskless dry etching in the single layer resist process. Because of the simplicity of single layer resist processing and the high etch rate in maskless dry etching for the formation of thick resist patterns, the dry developable resist in SR lithography may be advantageous to the multilayer resist for the purpose of generating high resolution, thick resist patterns with vertical walls. The resolution limit of the dry developable resist which reproduces the designed dimensions was 100 nm line and 200 nm space when a conventional e-beam apparatus was used at 20 KV in the dry developable multilayer resist process.