Naphthoquinone Diazide Research Articles

Resolution capability of resist patterns and throughput using alkaline treatment under ultrasonic irradiation

Alkaline treatment of the photoresist under ultrasonic irradiation has been investigated to improve the resolution capability of resist patterns with higher throughput. The selectively dissolved phenol resin for the combination of the alkaline treatment with ultrasonic irradiation was increased by 2.3 times compared to the solely alkaline treatment. The sensitizing effect of naphthoquinone diazide (sensitizer) based on phenol was increased to 0.46 against dip treatment of 0.31. As a result, resist sensitivity was increased to 26% and the resolution capability was drastically improved. Consequently, the 0.5 μm line and space resist patterns were resolved completely with fine profile by using the photoresist with a 0.7 μm resolution limit together with g-line exposure machine with a 0.6 μm resolution limit. As a consequence, a high throughput of 25 wafers min−1 was achieved, which was more than 25 times higher than that of electron beam lithography.

Heat Resistance and Electrophysical Characteristics of Polyheteroarylenes and Ferroelectric–Polymer Film Composites Based on Them

Structurally related poly(amido-o-hydroxy amides) derived from 5,5-methylenebis(2-aminophenol) with tetramethylsiloxane and heteroaromatic (benzoxazole and benzotriazole) fragments incorporated in the second amine component or formed by polyheterocyclization of the corresponding prepolymers were prepared. The effect of modifying fragments introduced into the base poly(o-hydroxy amide) on the heat resistance of powders and films and of films of photosensitive compounds based on the synthesized polymers with the naphthoquinone diazide component was analyzed. The electrophysical parameters of the polymer films and film composites with a nanodispersed ferroelectric filler, (PZT: ceramic powder with the composition Pb0.81Sr0.04Na0.075Bi0.075(Zr0.58 Ti0.42)O3, Russian brand PZT-1), prepared on the basis of modified polymer binders, were determined. Introduction of 20 mol % sulfur-containing fragments into the polymer binder ensures a 50–65˚C increase in the heat resistance for all types of films without increasing the level of the dielectric loss for the composite coatings.

Reflection Spectra Modification of Diazoquinone-Novolak Photoresist Implanted with B and P Ions

We investigate FP9120 positive photoresist films 1.8 μm thick that are spin-coated on the surface of KDB-10 (111) silicon wafers and implanted with В+ and Р+ ions by measuring the reflection’s spectra. It is shown that implantation reduces the refractive index of the photoresist. In the opacity region of the photoresist film, the reflection coefficient grows with an increasing implantation dose, especially in the case of P+ ion implantation. The spectral dependences of the optical length for the implanted photoresist films have two regions with anomalous dispersion near the wavelengths of 350 and 430 nm, which correspond to the absorption bands of naphthoquinone diazide molecules.

Atmosphere Dependability of Physical Properties of Novolak Resist during Heat-Curing Process for GMR Head

A novolak resist with naphthoquinone diazide is available to produce a coil insulating layer for a GMR head by heat-curing process. The relationship between the molecular structures of several properties, i.e., internal stress, thermal expansion, and desorption of gases from the insulating layer is studied. The effects of the atmospheres of N2, O2, and air on the properties of the insulating film upon heat-curing are also examined. The prepared novolak resist is analyzed the measurements of TGA, DSC, IR, GPC, UV, internal stress, thermal expansion, and Thermal Desorption Spectroscopy (TDS). The mechanism for hardening of the novolak resist is also discussed.

Full Color Screen by EPD Combined with Photolithography for Flat Panel Displays

Electrophoretic deposition (EPD) was employed for applying a phosphor coating for use in the fabrication of a full color screen consisting of red (R), green (G), and blue (B) phosphors. Patterned phosphor layers with a high packing density and uniformity can be fabricated by EPD combined with photolithography. For this process, R, G, and B phosphors were deposited on a patterned indium tin oxide glass by means of a commercial positive photoresist based on novolac resin and naphthoquinone diazide. The phosphor can be deposited on the patterned conductive substrate, but not on the surface of the photoresist film, because the photoresist has insulating properties. Conventional photolithographic conditions could not be used for this deposition because the commercial photoresist was soluble in the alcoholic solvent, which was used during the phosphor deposition. Instead, an insoluble photoresist was obtained by optimizing the baking temperature. Patterned color screens were studied using scanning electron microscopy and photoluminescence spectroscopy. The adhesion strength of the patterned color screens was substantially improved by the use of a coating of aqueous solution including polyvinyl alcohol and ammonium dichromate, followed by curing under UV light. © 2004 The Electrochemical Society. All rights reserved.

Photochemical reactions of diazodihydronaphthalenonesThese compounds are often referred to as naphthoquinone diazides in the literature. in cyclic ethers

Photolysis of 4-diazonaphthalen-1(4H)-one (1a), 2-methyl-4-diazonaphthalen-1(4H)-one (1b) and 4-diazo-2-nitronaphthalen-1(4H)-one (1c) in neat THF and 1,4-dioxane produced a variety of products depending on the 2-substituent and the solvent. While 1a and 1c produced predominantly insoluble copolymers in both solvents, 1b produced, besides small amounts of copolymers, a novel polyether bridged naphthalene, 2,3:11,12-bis(2-methyl-1,4-naphthylene)-18-crown-6 (2b), 1,4-dioxa-3′-methyl-4′-oxo-1′,4′-dihydronaphthalene-1′-spiro-5-cycloheptane (3b), 2-methyl-4-(1,4-dioxan-2-yl)naphthol (4b) and 2-methylnaphthol (5b) in dioxane, and 3′-methyl-4′-oxo-1′,4′-dihydronaphthalene-1′-spiro-2-pyrane (3b′), 2-methyl-4-(tetrahydrofuran-2-yl)naphthol (4b′) and 5b in THF. Compound 2b is characterised by X-ray crystallography.

Photosensitivity and physicochemical properties of the two-layer photoresist based on naphthoquinone diazide and cyclorubber

The possibility was examined of preparing a model of a two-layer photoresist based on a photo-sensitive layer of naphthoquinone diazide (FP-383), a planarizing layer of cyclorubber (FN-11), enhancing the photosensitivity and physicochemical resistance of FN-11 films after irradiation through thenaphthoquinone diazide layer and its removal by development in KOH.

A New Simple Method for Fabrication of Fine Metal Patterns

AbstractWe developed a new method for easy fabrication of micrometer-scale fine metal patterns on substrates. The patterns can be fabricated at low cost, at low processing temperature, and on uneven substrates as well as on plane surfaces. The method involves, first, forming hydrophilic and hydrophobic patterns on the substrates, and, second, depositing metal by electroless plating on the hydrophilic area. Hydrophilic and hydrophobic patterns were formed on a sensitizer containing naphthoquinonediazide (NQD) units coated on the substrates by the exposure. In the exposed areas, metal particles that are catalysts for electroless copper plating were adsorbed in the ion-exchange reaction and then the reduction treatment was performed. Copper was selectively deposited by the self-catalyst mechanism, according to the exposed patterns. All experimental processes can be carried out at room temperature. Using this new method, copper line patterns of 25 μm and copper dot patterns of 15 μm diameter were fabricated on the substrate.

Synthesis of 2-Amino-1,2,3-triazole Derivatives from Vicinal Diazides

Triphenylphosphine reacts with naphthoquinone diazide to form almost quantitatively the phosphorane of a unique 2-amino-1,2,3-triazole derivative. This compound undergoes an aza-Wittig reaction with aldehydes and is readily hydrolyzed to the free 2-amino-1,2,3-triazole. The free amine reacts normally with acids and aldehydes. The 2-amino-1,2,3-triazole system is stable and high melting, and most derivatives give the parent ion as the largest peak in the mass spectrum. The compounds absorb at 300−350 nm with a strong emission in the range 500−700 nm, depending upon the substituents. Cyclic voltammetry shows one reversible, single-electron reduction wave.

Synthesis and evaluation of positive‐acting photosensitive polyimides with phenol moiety

AbstractNovel positive‐acting photosensitive polyimide resists (1) developable with an alkaline aqueous solution were prepared. The resists consisted of a naphthoquinone diazide (NQ) and a polyamic acid bearing hydroxyphenyl groups (PA). The hydroxyphenyl moieties are newly incorporated by adding 2‐N,N‐dimethylaminoethyl‐3‐hydroxybenzoate (m‐PEA) or 2‐N,N‐dimethylaminoethyl‐4‐hydroxybenzoate (p‐PEA) to the polyamic acid, through ionic interaction between the carboxylic acid and the amine. The NQ acts as a solution inhibitor for the PA by the interaction with the hydroxyphenyl moiety. This system is similar to that of phenol‐novolac resin/NQ resists currently conducted in the fabrication of the Large Scale Integrated circuit (LSI). The resist (1) is exposed to a G‐line and is developed with tetramethylammonium hydroxide aqueous solution to provide fine patterns, proving that the (1) is compatible with LSI‐production lines currently applied. A novel polyamic acid‐curing mechanism found in the course of this study is also reported. © 1995 John Wiley & Sons, Inc.

Synthesis and characterization of a naphthoquinonediazide positive photoresist derived from bis(hydroxymethyl)phenol

AbstractA new photosensitive naphthoquinonediazide (NQD) was synthesized from 2,6‐bis‐(hydroxymethyl)‐3,4‐dimethylphenol and toluene diisocyante. NQD was identified by using IR, NMR and elemental analyses. Photobleachable characteristics were evaluated by UV spectrophotometry. Applications of the NQD on the photolithography as a positive working photoresist were investigated. The aqueous solution of NQD, novolak, cellosolve acetate, and DMF was used as a photosensitive material. It was found that NQD synthesized in this investigation can be used as an effective component in a positive photoresist. Optimal conditions of the UV dose, coating thickness, and development of the resist system were estimated. Resolution of the positive resist was evaluated by SEM technique. Effects of UV dose, exposure time, development time, and exposure UV wave length on the sensitivity and resolution of the photoresist were investigated.

Crosslinking in halogen containing novolac electron beam negative resists

AbstractHalogenophenol novolac (HPN)‐based negative resists exhibit excellent sensitivity and pattern resolution properties. The HPNs act as synergists for crosslinking with other irradiation labile compounds such as naphthoquinone diazide and bisazide vs. hydrogen halide (HX) elimination reaction, resulting in additional crosslinking, probably by aryl radical recombination and/or addition. We describe a new resist formulation based on HPN binder and melamine crosslinker (Cymel 303). In this case the irradiation induced HX elimination additionally catalyzes the melamine crosslinking.

Laser photolysis of naphthoquinone diazide in cyclohexane – two‐laser chemistry

AbstractThe laser photochemistry of 1,2‐naphthoquinone‐diazide‐(2)‐5‐sulfonic acid phenylester in cyclohexane has been investigated. The photolysis experiments have been done using a KrF laser pulse (generation pulse) and a nitrogen laser pulse (transformation pulse) with various time delay from 40 ns up to 1 s. At a time delay between the two laser pulses in the μs‐region, the formation of indene and cyclohexyl‐indene derivatives has been observed, additional to the corresponding indenecarboxylic acid. The laserspecific formation of these compounds is the result of the electronic excitation of the intermediately formed ketene and its reaction by decarbonylation. The time delay for getting a high yield of the indene and the cyclohexyl‐indene derivatives correlates closely with the rise time and the life time of the ketene.

Positive photosensitive polyimides using polyamic acid esters with phenol moieties

AbstractPolyimide resists developable with basic aqueous solutions were realized by polyamic acid esters with phenol moieties (PPh's) and naphthoquinone diazides. The polyimide precursors (PPh's) were synthesized from diamines and dicarboxylic acids that have phenol moieties through ester linkage. A selective reaction of alcohol groups with acid dianhydride groups made the synthesis of the PPh's possible, even if the phenol groups were in the reaction mixtures. The PPh's were soluble in basic aqueous developer, but their dissolution rates were too low for use as resists. To increase the resist dissolution rate, polyamic acids were added to the PPh's. By adjusting the dissolution rates in basic aqueous developers, fine patterns could be realized. The polyimide resists had high thermal stability and reliable adhesive property to silicon substrate. © 1994 John Wiley & Sons, Inc.

Photosensitive polyimides consisting of simple mixtures of 4‐substituted diazonaphthoquinones and polyamic acids

AbstractPolyimide resists that can be developed with a basic aqueous solution were produced by simple mixtures of conventional polyamic acids and naphthoquinone diazides in which sulfonate groups are substituted at the 4‐position. The diazonaphthoquinones bearing electron‐withdrawing groups gave negative tone resists. On the other hand, those bearing electron‐donating groups gave positive tone resists. The difference in the resist behaviors depending on the photoactive structure was explained by crosslinking caused by photogenerated sulfonic acids. The thermal stability of polyimides prepared from the resists was almost the same as that of conventional polyimides.

Positive chemically amplified resists using naphthoquinone diazides as photo-acid-generators.

Positive chemically amplified resists using naphthoquinone diazides as photo-acid-generators.

Photosensitive polyimides developable with basic aqueous solutions (II)

AbstractPositive and negative photosensitive polyimides developable with basic aqueous solutions are reported. The results consist of poly amic acids and naphthoquinone diazides in which sulfonate groups have to be substituted at 4‐position. It depends on the naphthoquinone structures whether positive or negative patterns are obtained. In order to fabricate resist patterns, High‐Temperature‐Post‐Exposure‐Process (HIT‐PEB) must be utilized. The reaction mechanisms are also discussed. © 1992 John Wiley & Sons, Inc.

Study on organosilicon positive resist. II. Organosilicon positive photoresist (OSPR–1334) and its application to bilayer resist system

AbstractA new alkali‐developable organosilicon positive photoresist (OSPR–1334) and a bilayer resist process with OSPR–1334 has been developed. OSPR–1334 is composed of poly(p‐hydroxybenzylsilsesquioxane) and naphthoquinone diazide. The sensitivity and the resolution are almost the same as those of conventional novolac‐based resists when aqueous tetrakis (2‐hydroxyethyl) ammonium hydroxide is used as a developer. Also, OSPR–1334 has excellent resistance to O2RIE. The etching rate is 3.6 nm/min, while that of polyimide resins or hard‐baked novolac‐based resists is 100 nm/min. OSPR–1334 is suitable for use as the top layer of the bilayer resist system. OSPR–1334, after O2RIE, can be eliminated by dissolving an unchanged layer followed by spinning out or filtrating a changed surface layer. Submicron patterns with a high aspect ratio can easily be obtained with this bilayer resist process.

Laser photolytic and low temperature investigations of naphthoquinone diazides in Novolak films

The spectral and the kinetic behaviour of the photoresists AZ 2400 and AZ 1350J and relevant model compounds (naphthoquinone diazide derivatives) under lithographic conditions on lamp and high intensity excimer laser irradiation have been studied, both at room temperature and at low temperature (77–298 K). The time-resolved spectra were recorded in the spectral region from 300 to 500 nm at time delays from 10 ns to a few seconds. On photolysis of AZ 2400, two transients were observed and, on photolysis of AZ 1350J, three transients were observed. The medium-time-living transient is the ketene, as proved by IR spectra. On low temperature photolysis, two intermediates are observed. In both cases the first-formed intermediate was determined to be the ketene.

Dissolution inhibition mechanisms of naphthoquinone diazides

AbstractDissolution inhibition mechanisms of naphthoquinone diazides in novolak based positive photoresists were investigated from three different aspects: • Dipolar interaction. • Interfacial chemical reactions. • Chemical structures of naphthoquinone diazides. The results suggest that there exists a hydrogen bonding interaction between the compounds with the matrix novolak resin and that naphthoquinone diazides would crosslink the resin in contact with an alkaline developer, both of which contribute to dissolution inhibition mechanisms. However, there seems to exist another dissolution inhibition mechanism; namely, 1,2‐naphthoquinone diazide does not inhibit dissolution of the matrix novolak resin at all while a clear dissolution inhibition effect Is observed for its derivatives containing sulfonyl groups. In the present paper, three dissolution inhibition mechanisms of naphthoquinone diazides will be proposed.