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.     

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.     

Synthesis and lithographic evaluation of poly[(methacrylic acid tert-butyl cholate ester)-co-(γ-butyrolactone-2-yl methacrylate)]

Poly[(methacrylic acid tert-butyl cholate ester)-co-(γ-butyrolactone-2-yl methacrylate)] was synthesized and evaluated as a new 193-nm chemically amplified photoresist. This polymer showed good thermal stability up to 240 °C and had a good transmittance at 193 nm. This material showed good resistance to CF₄-reactive ion etching. The resist patterns of 0.15 μm feature size were obtained at a dose of 11 mJ cm⁻² using an argon fluoride excimer laser stepper.     

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.     

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.     

Design and synthesis of new photoresist materials for ArF lithography

A new class of photoresist matrix polymers based on vinyl ether–maleic anhydride (VEMA) alternating copolymers was developed for ArF single‐layer lithography. These polymers were synthesized by copolymerization of alkyl vinyl ether and maleic anhydride alternating copolymers with acrylate derivatives containing bulky alicyclic acid‐labile protecting groups. The resulting polymers showed good control of polymerization and high transmittance. Also, these resists exhibited good adhesion to the substrate, high dry‐etching resistance against CF₄ mixture gas (1.02 times the etching rate of deep UV resist), and high selectivity to silicon oxide etching. Using an ArF excimer laser exposure system with 0.6 NA, 120‐nm L/S patterns were resolved under conventional illumination. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 165–170, 2004     

<Emphasis Type="Bold">Photo-sensitive bio-based copolymer containing cholic acids: novel functional materials for 248nm photoresist</Emphasis>

Cholic acid is a class of biological compounds that exhibit valuable properties, and have been applied in many fields due to its special chemical structures for many areas. In this study, poly[(methacrylic acid tert-butyl cholate ester)-co-(acetoxy styrene)] [P(MATC-co-AS)] was synthesized from cholic acid, then the final copolymer poly[(methacrylic acid tert-butyl cholate ester)-co-(p-hydrostyrene)] [P(MATC-co-HS)] was obtained after P(MATC-co-AS) was hydrolysized. The structure and properties of the copolymers were determined through nuclear magnetic resonance, gel permeation chromatography, UV spectrometry, thermogravimetric analysis, and differential scanning calorimetry. The ultraviolet spectra of the copolymers indicate that they exhibit excellent optical transmittance at 248 nm. Moreover, the photolithography performance of a positive-tone photoresist based on the copolymers were evaluated using an KrF laser exposure system. The results indicate that a resolution of 0.25 μm could be achieved at a low exposure dose.     

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.     

Oberflächenstrukturierung polymerer Fasern durch UV-Laserbestrahlung, 15. Beschreibung des Temperaturfeldes in PETP-Polymeren während und nach der Laserbestrahlung mit einem gepulsten UV-Laser

For understanding the generation of UV laser induced surface structures of PETP polymers the temperature field within the irradiated surface is calculated in dependence on the laser irradiation wavelength (193 nm, 248 nm, 308 nm), pulse time, pulse form, the irradiation intensity and depth, using temperature-independent material data of PETP polymers known from literature. For this purpose the solution function of the one-dimensional heat differential equation is used. Depending on the order of magnitude of the absorption coefficient of the polymer for UV light of different wavelengths, surface temperatures of approx. 16 000°C (193 nm), 11 000°C (248 nm) and 500°C (308 nm) are calculated at the end of the laser pulse. The temperature input within the polymer layer is limited to only a very small penetration depth. For the irradiation with the two laser wavelengths of 193 nm and 248 nm this is less then 0.4 μm. The cooling process is considerably slower, reaching the initial temperature after approx. 4 μs.     

Effect of melt annealing on the phase structure and rheological behavior of propylene–ethylene copolymers

The morphological and rheological properties of a commercial propylene‐ethylene copolymer (PEC) and a series of blends with different concentrations of poly (ethylene‐co‐propylene) are investigated. The blends are prepared mixing PEC with fractions obtained from it by solvent extraction. The phase structure of samples exposed to different thermal and mechanical histories was analyzed using scanning electron microscopy. The linear viscoelastic properties of the molten polymers were measured using different test sequences that include dynamic frequency and time sweeps. The phase structure of most blends changes dramatically with time when the polymers are kept in the molten state due to the coalescence of the domains. For example, the initial morphology of PEC which presents domains of ～1 μm diameter changes to regions of more than 10 μm of average diameter after 90 min at 178°C at rest. Coincidentally, the dynamic moduli of the blends change during annealing reaching values that depend on the mechanical history. For example, the elastic modulus of PEC increases ～32% during a dynamic time sweep of 45 min using a frequency of 0.1 s^?1, while it decreases ～18% when a frequency of 1 s^?1 is applied. Moreover, the modulus measured at 0.1 s^?1 of samples annealed at rest during 45 min is ～58% larger than that of the fresh material. POLYM. ENG. SCI., 47:912–921, 2007. © 2007 Society of Plastics Engineers     

Optical properties of transparent polycrystalline ruby (Cr:Al2O3) fabricated by high-pressure spark plasma sintering

Doped transparent ceramics with high optical quality can serve as materials for photonic applications such as laser gain media. In that regard, transparent polycrystalline alumina has potential for high-power applications due to its excellent physical and chemical properties, combined with unique doping possibilities. However, optical birefringence of Al₂O₃ crystals make achieving sufficiently high optical transmittance a processing challenge. In the present study, we demonstrated fabrication of highly transparent 0.5 at.% Cr:Al₂O₃ ceramics by high-pressure spark plasma sintering (HPSPS). The optical properties of these polycrystalline ruby ceramics were analyzed in order to assess possible laser operation (at 694.3 nm). The obtained ceramics exhibit high in-line transmittance (～72.5 % at 700 nm), equivalent to a scattering coefficient of 2.15 cm^?1, and characteristic ruby photoluminescence. The theoretically estimated lasing threshold and percentage of absorbed pump power indicate that such ruby ceramic lasers could operate at reasonable thresholds of 80?225 mW with short lengths of 0.5?5 mm. Thus, HPSPS is a promising method for producing laser-quality doped transparent ceramics for compact laser systems.     

A sub-0.5 μm bilevel lithographic process using the deep-UV electron-beam resist p(si-cms)

Optimization of the deep-UV and electron-beam lithographic properties of a copolymer of trimethylsilylmethyl methacrylate (SI) and chloromethylstyrene (CMS), P(SI-CMS), within a weight average molecular weight range of 1.4 to 4.1 × 10⁵ and 90 to 93 mole percent SI composition has been achieved. The solubility behavior of P(SI-CMS) resist was examined using the Hansen 3-dimensional solubility parameter model and dissolution rate measurements. Swelling of the resist has been minimized through the identification of a single component developer (2-propanol) and rinse (water) system. For the material containing 90 mole percent SI (14.9 weight percent Si) and M?_ω = 1.4 × 10⁵, the sensitivity to 248 nm radiation is 65 mJ/cm² and to electron-beam exposure is 3.4 μC/cm² at 20 kV. This material Is applicable to bilevel lithographic processes, and the O₂ reactive ion etching (RIE) rate is 16 times slower than standard hard-baked photoresist. Using a He/O₂(60/40) RIE pattern transfer process, 0.4 μm line/space patterns have been resolved in a 1.3 μm bilayer structure for deep-UV exposures, and 0.25 μm imaging has been demonstrated in a 0.7 μm thick planarizing layer using electron beam irradiation. The loss in linewidth associated with the 0.25 μm process is ～0.04 μm.     

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.     

Preparation of polymers with pendant quinonoid groups and their photocrosslinking with visible light irradiation

Photosensitive polymers with pendant quinonoid groups were prepared by the reaction of p-(benzoquinon-2-ylthio) acetic acid (QTAA) or p-(p-benzoquinon-2-ylthio)benzoic acid (QTBA) with hydroxyethyl methacrylate-methyl methacrylate copolymer. The polymers showed a strong π-π^* absorption band at around 410 nm and were efficiently crosslinked by visible light irradiation. Somewhat higher photosensitivity of QTAA-bound polymer compared with that of QTBA-bound polymer suggested some contribution of intramolecular hydrogen abstraction of QTAA to the photocrosslinking.     

Deposition of functionalized single wall carbon nanotubes through matrix assisted pulsed laser evaporation

Single-wall carbon nanotubes (SWCNTs) functionalized with oxygen-containing groups were deposited onto glass substrates by matrix assisted pulsed laser evaporation (MAPLE). The experiments were performed by subjecting ultraviolet laser pulses (KrF¹ excimer laser, 248 nm wavelength) to frozen SWCNT-toluene targets placed in a parallel plane a few cm in front of the substrate. The morphology, structure, and chemical composition of the deposited materials were studied through atomic force microscopy, high resolution transmission electron microscopy, Raman spectroscopy and X-ray photoelectron spectroscopy. The influence of the laser fluence on the material structure was investigated. The results indicate that the functionalized SWCNTs can be transferred by MAPLE at low laser fluences without the alteration of the structure of the initial material used as targets in MAPLE experiments. An increase of the fluence leads to the decomposition of the functional groups, mainly carboxylic acid groups, without degradation of the SWCNT structure whereas, at the highest fluences, the amorphization and even coalescence of the carbon nanotubes takes place.     

Solid-state-reaction fabrication and properties of a high-doping Nd:YAG transparent laser ceramic

High-quality neodymium-doped yttrium aluminum garnet (Nd:YAG) transparent ceramic (4.0 mole percent) was fabricated by a solid-state reaction method and vacuum sintering. The microstructure, optical transmittance, spectral properties and laser performance were investigated. The average grain size of the sample is about 10 mm. The transmittance of a 2.8-mm thick sample reaches 79.5% at the laser wavelength of 1064 nm. The highest absorption peak is centered at 807 nm and the absorption coefficient is 13.9 cm⁻¹. The absorption coefficient at the laser wavelength is 0.2 cm⁻¹. The main emission peak is at 1064 nm and the fluorescence lifetime is 102 μs. A laser diode (808 nm) whose maximum output is about 1000 mW was used as a pump source and an endpumped laser experiment was performed. The 1064 nm-CW-laser output was obtained and the threshold is 733 mW. With 998 mW of maximum absorbed pump power, a laser output of 17 mW is obtained with a slope efficiency of 6.1%. __________ Translated from Journal of The Chinese Ceramic Society, 2007, 35(12): 1600–1604 [译自: 硅酸盐学报]     

Poly(arylazophosphonates): New Arylazophosphonate‐Containing Polyurethanes and Polyesters for Laser Ablation Structuring

In this article we report the preparation of new arylazophosphonate‐containing polymers, poly(arylazophosphonates), via polycondensation reactions of bifunctional hydroxy functionalized arylazophosphonate‐containing monomers with isocyanate or acid chloride comonomers. The polyurethanes and polyesters were characterized by common methods such as ¹H, ¹³C, ³¹P NMR, FTIR, UV/visible spectroscopy, DSC, and GPC measurements. In addition, a number of polymer structuring experiments (macro and micro experiments) by means of laser ablation with a XeCl excimer laser were performed. In macro experiments, pulse number and fluence were investigated systematically and their influence on the ablation depth was discovered. In micro experiments, structures of high quality were obtained which possess clear contours without any debris on the polymer surface. Structures in the sub micron range were created by applying a phase mask. These high quality results indicate that the poly(arylazophosphonates) are well suited materials for laser ablation structuring with XeCl excimer lasers (e.g. for microstructuring or microlithography).

SEM image of sub micro structures of polymer APU 5 generated in experiments using a phase mask (line width: 0.3–0.5 μm, trench width: 0.3–0.5 μm, fluence: 3 J/cm²).     

Fluorescence Particle Counter for Detecting Airborne Bacteria and Other Biological Particles

We have constructed a laser-based particle counter that detects the fluorescence, as well as the elastic scattering, from individual airborne particles as they traverse a laser beam. This fluorescence particle counter (FPC) can detect fluorescence from μm-sized Bacillus subtilis spore agglomerates when illuminated with intense light at 488 nm from an argon ion laser, either ～ 0.7 kW cm^?2 extracavity or ～ 50 kW cm^?2 intracavity. We suspect that flavins in the spores are the molecules primarily responsible for the fluorescence, because the peak fluorescence emission of the biological materials at this excitation wavelength is in the range 530–550 nm, which is characteristic of flavins. Fluorescence from kaolin, hematite, and polystyrene particles was not detectable; the lack of fluorescence indicates that the FPC may be able to differentiate between biological and nonbiological aerosols. The FPC samples aerosol-laden air at a rate of ～ 1 mL s^?1, and is capable of measuring aerosol concentrations up to several thousand per milliliter. The FPC may be helpful in detecting and characterizing airborne bacteria and other airborne particles of biological origin.     

Synthesis and characterization of negative‐type photosensitive polyimides based on cyclobutane‐1,2,3,4‐tetracarboxylic dianhydride

A series of negative‐type photosensitive polyamic acids (PAAs) with various molecular weights was synthesized from cyclobutane‐1,2,3,4‐tetracarboxylic dianhydride, 2‐(methacryloyloxy)ethyl‐3,5‐diaminobenzoate, and 2‐(methacryloyloxy)ethyl‐4‐aminobenzoate in N‐methyl‐2‐pyrrolidone. We investigated the degree of planarity, transmittance, and thermal stability for the PAAs after the photoirradiation reaction at an exposure dose of 200 mJ/cm². The films prepared from the PAA with the lowest molecular weight (PAA‐1) exhibited a higher degree of planarity and transmittance compared with those of the film prepared from the PAA with the highest molecular weight (PAA‐4). The initial decomposition temperatures of the cured PAAs with different molecular weights were similar and were stable up to around 300°C. Further, the photosensitivity and transmittance of PAA‐1 were investigated in the presence of photoinitiators at 365–400 nm with a high‐pressure mercury lamp. The resolution of the photocured film was about 50 μm. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2300–2308, 2005