Organic compounds -- part of the class 532-570 series – Organic compounds – Diazo or diazonium
Reexamination Certificate
2003-05-01
2004-03-30
Powers, Fiona T. (Department: 1626)
Organic compounds -- part of the class 532-570 series
Organic compounds
Diazo or diazonium
C534S564000, C430S170000, C430S270100, C430S326000
Reexamination Certificate
active
06713612
ABSTRACT:
This invention relates to novel sulfonyldiazomethane compounds, photoacid generators for resist compositions, resist compositions comprising the photoacid generators, and a patterning process using the same. The resist compositions, especially chemical amplification type resist compositions are sensitive to such radiation as UV, deep UV, electron beams, x-rays, excimer laser beams, gamma-rays, and synchrotron radiation and suitable for the microfabrication of integrated circuits and other electronic devices.
BACKGROUND OF THE INVENTION
While a number of efforts are currently being made to achieve a finer pattern rule in the drive for higher integration and operating speeds in LSI devices, deep-ultraviolet lithography is thought to hold particular promise as the next generation in microfabrication technology.
One technology that has attracted a good deal of attention recently utilizes as the deep UV light source a high-intensity KrF excimer laser, especially an ArF excimer laser featuring a shorter wavelength. There is a desire to have a microfabrication technique of finer definition by combining exposure light of shorter wavelength with a resist material having a higher resolution.
In this regard, the recently developed, acid-catalyzed, chemical amplification type resist materials are expected to comply with the deep UV lithography because of their many advantages including high sensitivity, resolution and dry etching resistance. The chemical amplification type resist materials include positive working materials that leave the unexposed areas with the exposed areas removed and negative working materials that leave the exposed areas with the unexposed areas removed.
In chemical amplification type, positive working, resist compositions to be developed with alkaline developers, an alkali-soluble phenol or a resin and/or compound in which carboxylic acid is partially or entirely protected with substituent groups that are eliminatable under the action of acid to change the solubility of a resin in an alkali developer (acid labile groups) is catalytically decomposed by an acid which is generated upon exposure, to thereby generate the phenol or carboxylic acid in the exposed area which is removed by an alkaline developer. Also, in similar negative working resist compositions, an alkali-soluble phenol or a resin and/or compound having carboxylic acid and a compound (crosslinking agent) capable of bonding or crosslinking the resin or compound under the action of an acid are crosslinked with an acid which is generated upon exposure whereby the exposed area is converted to be insoluble in an alkaline developer and the unexposed area is removed by the alkaline developer.
On use of the chemical amplification type, positive working, resist compositions, a resist film is formed by dissolving a resin having acid labile groups as a binder and a compound capable of generating an acid upon exposure to radiation (to be referred to as photoacid generator) in a solvent, applying the resist solution onto a substrate by a variety of methods, and evaporating off the solvent optionally by heating. The resist film is then exposed to radiation, for example, deep UV through a mask of a predetermined pattern. This is optionally followed by post-exposure baking (PEB) for promoting acid-catalyzed reaction. The exposed resist film is developed with an aqueous alkaline developer for removing the exposed area of the resist film, obtaining a positive pattern profile. The substrate is then etched by any desired technique. Finally the remaining resist film is removed by dissolution in a remover solution or ashing, leaving the substrate having the desired pattern profile.
The chemical amplification type, positive working, resist compositions adapted for KrF excimer lasers generally use a phenolic resin, for example, polyhydroxystyrene in which some or all of the hydrogen atoms of phenolic hydroxyl groups are protected with acid labile protective groups. Iodonium salts, sulfonium salts, and bissulfonyldiazomethane compounds are typically used as the photoacid generator. If necessary, there are added additives, for example, a dissolution inhibiting or promoting compound in the form of a carboxylic acid and/or phenol derivative having a molecular weight of up to 3,000 in which some or all of the hydrogen atoms of carboxylic acid and/or phenolic hydroxyl groups are protected with acid labile groups, a carboxylic acid compound for improving dissolution characteristics, a basic compound for improving contrast, and a surfactant for improving coating characteristics.
Bissulfonyldiazomethanes as shown below are advantageously used as the photoacid generator in chemical amplification type resist compositions, especially chemical amplification type, positive working, resist compositions adapted for KrF excimer lasers because they provide a high sensitivity and resolution and eliminate poor compatibility with resins and poor solubility in resist solvents as found with the sulfonium and iodonium salt photoacid generators.
Although these photoacid generators, especially sulfonyldiazomethanes having aryl groups are highly lipophilic and highly soluble in resist solvents, they have poor affinity to or solubility in developers so that upon development and/or resist removal, the photoacid generators can be left on the substrate as insoluble matter (consisting of the photoacid generator or a mixture thereof with the resin).
For example, upon development, the resist material which has poor affinity to or solubility in a developer deposits on developed spaces in the exposed area or on lines in the unexposed area as foreign matter. Also, bis(cyclohexylsulfonyl)diazomethane and bis(tert-butylsulfonyl)diazomethane having alkyl groups instead of aryl groups for reducing lipophilic property are used in resist materials as the photoacid generator, as disclosed in Japanese Patent No. 3,024,621. However, as long as we confirmed, the above diazomethanes having alkyl groups generate acids having a relatively low molecular weight which are more diffusible in the resist film and detract from resolution. When the diazomethanes are added in large amounts, the problem of insoluble matter upon development and/or resist film removal remains unsolved.
Aside from the countermeasure for foreign matter, JP-A 10-90884 discloses to introduce such an acid labile group as tert-butoxycarbonyloxy, ethoxyethyl or tetrahydropyranyl into disulfonediazomethane for the purpose of improving the contrast of positive resist material. We empirically found that these compounds are unstable and ineffective for eliminating the foreign matter upon development and resist film removal.
Searching for a countermeasure to the foreign matter problem, we already synthesized sulfonyldiazomethanes having an acyl group (e.g., acetyl) or methanesulfonyl group introduced therein and found that they were useful as the photoacid generator in chemical amplification type resist composition. See JP-A 2001-055373 and JP-A 2001-106669. However, these arylsulfonyldiazomethanes having an acyl group or methanesulfonyl group introduced therein lack stability under basic conditions. On account of the aryl group in the molecule, these diazomethanes are less transparent at 248 nm and serve to reduce the transparency of resist film itself.
It is known from JP-A 8-123032 to use two or more photoacid generators in a resist material. JP-A 11-72921 discloses the use of a radiation-sensitive acid generator comprising in admixture a compound which generates a sulfonic acid having at least three fluorine atoms upon exposure to radiation and a compound which generates a fluorine atom-free sulfonic acid upon exposure to radiation, thereby improving resolution without inviting nano-edge roughness and film surface roughening. JP-A 11-38604 describes that a resist composition comprising an asymmetric bissulfonyldiazomethane such as a bissulfonyldiazomethane having an alkylsulfonyl or arylsulfonyl group or a bissulfonyldiazomethane having an arylsulfonyl or alkoxy-substituted arylsulfonyl group and a polyhydroxy
Fujii Toshihiko
Hasegawa Koji
Kobayashi Katsuhiro
Maeda Kazunori
Ohsawa Youichi
Birch & Stewart Kolasch & Birch, LLP
Powers Fiona T.
Shin-Etsu Chemical Co. , Ltd.
LandOfFree
Sulfonyldiazomethanes, photoacid generators, resist... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Sulfonyldiazomethanes, photoacid generators, resist..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Sulfonyldiazomethanes, photoacid generators, resist... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-3210781