Positive type photoresist composition

[Detailed Description of the Invention]

Field of the Invention The present invention relates to photosensitive compositions for Edge line pattern formation, such as an integrated circuit, and it Open it in more detail to d lot type Odoresist constituent excellent in sensitivity and heat resistance. PRIOR ART what is called the dry etching and To be done in trouble to which etching "Culm using photoresist puts an integrated circuit board into a plasma generator with detailed-izing of an integrated circuit these days -- it is becoming like. Under the present circumstances, the photoresist formed in order to protect a substrate is also To be shaved off to plasma simultaneously. In the etching smell, although it is preferred that there is no photoresist in You can only scrape, it is [ the extent ] related to the heat treatment temperature of the photoresist before etching. Usually, if this temperature is high, photoresist will be hard to be deleted at the time of etching. 1 by which the pattern of the substrate after formed photograph Regist is not carried out as a design as for zeta This formation when heat treatment in the high temperature which Like this(ed) by carrying out and carrying out in - is performed! There were 11 subjects. in order [ for this reason, ] to lower heat treatment temperature and to carry out try etching on appearance or kana conditions -- processing ?' -- 11 To in which" 2 does not have A times -- That's it.. in order to solve such a problem, in JP,58-17112,A, it is shown that an apparent initial softening uses novolac resin of 110~145 degreeC, and it is [ come out and ]. However, the problem that sensitivity fell sharply depending on using resin with an only high apparent initial softening was not able to be solved. The problem which an invention tends to solve Even when alkali solubility resin of a high apparent initial softening is wholeheartedly used as a result of research that these artificers should solve the account fault of Navigation, Positive 7 (very high heat resistance and high sensitivity, ?jf To be finding out things this knowledge here [ ↓ ] (it is Arrival-] It was for completing the About present invention.)) which blended simultaneously the condensation thing and quinone diacid compound of a A IJ power roll and acetone [ Setting to +2 photoresist. ] The means for solving a problem By refusing the present invention -- getting twisted -- 200 -- positive-type-photoresist To which consists of the condensation thing and quinone diazide compound of alkali solubility resin, and the Biloca roll and acetone which carry out the apparent initial softening of 'C, with -1, A 1. As alkali solubility resin used for the present invention, the condensation thing of Alkyl phenol, such as phenol formaldehyde resin and Freresor, and formaldehyde should be mentioned. these may mix and use phenol and Alkyl phenol -- White -- catechol -- resorcinol -- polyhydric phenol and naphthol As like may be Co-condensation(ed) -- Pol J and Aldehy! Although aldehyde other than - can also be used, it is necessary to use acid as a catalyst in the case of condensation. Boris nil phenol, poly isopropenyl phenol, or these copolymers are also used. these resin has polymerized i times with condensation Also -- an apparent initial softening -- 2 0 the case where it does not reach more than 0"C -- here -- once -- good solvent t -- or [ adding a poor solvent, after dissolving ], It can be considered as the resin which has an apparent initial softening more than 200 degreeC by removing a low-molecular quantity portion by judgment by the method "don't be dropped at i solvent." as Arnaud J person soluble resin, the condensation thing of Freresor and Pol 11 aldehyde is preferred. although the condensation thing of Biloca jJ-Le of the present invention and acetone is shown [ the effect which Toward-1- make sensitivity ], in order not to reduce heat resistance -- an apparent initial softening -- 100 degreeC.tlr -- better -- To is good to use resin of 140degreeC, with"-. as quinone Diazi] and the compound of the present invention -- Hajime Nagamatsu thick part, Hideo Yuji, and "photosensitive polymers" Kodansha Sai 1 Tifi (1980), 117page~118A page; or the De Forest (1) e Forest work, and "Off t l-Regis l-.+ (Pl+o l.) ~3- oresist, 1975, and McGraw-Hill (IVlcGrow-ITi I l) + (Knee L-yoke) 50 -- A page -- it Sensitive to. A quinone diazide compound may be combined with some or all of Arc 1 Ha iI soluble resin. It is especially 2 and 3. The 0-naphth quinone diacid 5-Sour Von acid ester of Nzov enone or 2, and /1.6-Dricht 0 Xylbenzophenone is preferred to 4-trihydroxy. t41 Formation of alkali solubility resin (A) of the present invention, the condensation thing (I3) of A [Tugarol acetone, and a quinone diazide compound (C) is A 1 (places Q and B made into 1 0 weight section (t. 1~6 0 weight section and C can be 30~50 weight sections.)) The solid of MI Formation of" 2 account serves as photoresist in which Paint 11 is possible by dissolving in the organic solvent uniformly. as a solvent -- a proper tool -- butanol -- alcohols and methyl 1 Cilketone, methyliso butyl 1 1.A. -- cyclohexanone -- acetate ester, such as ketone, ethyl acetate, and acetic acid Futuu isoamyl acetate, and Tetra Hito -- " -- ring type ether, such as Rofran and dioxane, and Methylse [1 Sorb. Enalse -- 1 Sorb and Butylser -- * 1 Solh -- ethyl top 1J Sorb aceti]-, a butyl cellosolve acetate, and gamma-Petit [The 1 -- lactone -- Can be cited. xylene -- toluene -- it is also good to mix aromatic hydrocarbon. As for the content of a solid, about lO~40 % of the weight is usually used. The Regis l[l Acid of the present invention can form the resist film which has the thickness about [ which applies to a substrate by the rotation applying method, and forms a pattern by exposing and developing after - It was ] abbreviation IH.m. Paint 5 (it heat-treats at the temperature of 80~90 degreeC after D, and removes the solvent which remains.) Subsequently, a desired pattern is exposed with energy rays, such as ultraviolet rays and an electron beam. As a developing solution for the Regis II An adduct of the present invention, organic alkali, such as inorganic alkali, such as sodium hydroxide, a potassium hydrate, and metasilicic acid sodium, water oxidization tetramethylammonium, and Colin, is used. Amine, alcoholic ether, etc. can also be mixed and used. EFFECT OF THE INVENTION upsilon1 comb -- 4 and an invention -- getting twisted -- positive type Off A Treasest which was excellent in heat resistance and sensitivity as compared with conventional technology can be obtained. An example is given to below and the present invention is explained to it still more concretely. The part in an example, a comparative example, and a synthetic example and % are weight standards as long as there is no notice especially. an apparent initial softening -- the next -- it measured to -. the link, ball, and specimen of a statement are held to the 2207 petroleum-asphalt softening point test method 115 -- Jailbroken -- it prepares. The ring was filled up, putting a ring on pot plate 1-, and fusing and softening the resin to measure. It measured like JIS K 2207 except using for a product KF made from Shin-etsu Chemicals 54 silicone oil heat carrier. Synthetic example 1 Meta-cresol 144 g, 160 g of Parakou resol 96g and:7% formaldehyde, and Si: Do heating mantle"C heating of after putting L acid 2 hydrate 2.3g into a 1-liter separable flask and dissolving show acid (it was time-moved to tears and carried out the Numa style.). subsequently, after adding and agitating 200 g of 1111 acid cello Sorb, it part Si u carried out by settling -- a water layer -- it was made to incline and removed. next, I 11'' vacuum distillation apparatuses were attached, and about 100-g acetic acid cello Sorb was distilled with remaining water. It is the resin generated so that churning wings might not adhere 40 degrees (it cooled to :, acetone of 300 g was added, and it dissolved uniformly.) Agitating to 10-liter Tolcorn, the acetone solution of resin was dropped, depositing resin was filtered, and it vacuum dried. 180 g of Earnings, example 2 of - composition whose apparent initial softening of resin was 21()°C 80-g Piroka L1-Le is dissolved in acetone of /l F30 g, and after adding 3.0 g of phosphorus oxychloride and performing churning by 710 degreeC for 8 hours, if it is dropped while agitating a reaction thing in a lot of water, a solid will deposit. This was filtered, and it vacuum dried and obtained the Piroka roll and condensation thing 48.3g of acetone. The apparent initial softening was 161degreeC. Synthetic example 3 (15 The Piroka roll and condensation thing 92g of acetone were obtained like synthetic example 2 except having used l-Le, acetone of 200 HH, and phosphorus oxychloride 1.Og for the To *IJ power of l IH.) The apparent initial softening was 118degreeC. Synthetic example 4 gamma-isopropenyl phenol 4 (it dissolved in tetrahydro franc 300 g, and filled up with g [ 1 ] and 37 g of acrylonitrile the 1-liter crow bottle which carried out replacement by nitrogen gas.) Subsequently, azobis Isobuchi [J2I and Lil 0.50g were dissolved in a 50-g tetrahydro franc, and it poured into the crow bottle, and carried out the settlement polymerization in the constant temperature bath of 60 degreeC for 2 hours. After cooling the content of a glass bottle, it poured, while agitating to 2 liters of hexane, and filtered the precipitation thing. The precipitation thing was dissolved in 300 g of tetrahydro francs, and it flowed into 2 liters of hexane again, and vacuum dried the precipitation thing by 40 degreeC for 48 hours. 32 The copolymer of r-isopropenyl phenol of g and acrylonitrile was obtained. The apparent initial softening was 20.1degreeC. Synthetic example 5 After putting meta-cresol 144 g, rose cresol 96g, and 160 g of 37% Hol 11 aldehyde and oxalic acid dihydrate 2.3g into a 1-liter separable flask and dissolving oxalic acid, it was made to agitate and flow back by a heating mantle for 8 hours. Subsequently, after agitating, a vacuum distillation apparatus is taken and distillation under reduced pressure is carried out to 1] Over and 180'C15mm113, and the bat was immediately filled with the content and it was made to settle and to assimilate. It was Yield fft273g and apparent-initial-softening 135degreeC. Synthetic example 6 Under yellow light, they are 2, 13.0 g of 3.4-Licht [I Xishan CIF enone, and O-naphth quinone Diazi 1zeta-5-Sulfon acid chloride 2 B, Og was dissolved in 240 g of 1 and 4-dioxane, while warming to 40 degreeC, it agitated, and the mixed solution of 20.0 g of triethyl amine and 83.2 g of 1 and 4-dioxane was dropped over about 30 minutes. 1 more hour -- warming -- filtering reaction liquid and agitating Store liquor in 12 liters of 1% Cush:One acid water solution except for a precipitation thing, after continuing churning -- inside Poured. carrying out the depositing solid 73 exception and vacuum drying by 40 degreeC for 211 hours -- 2.:1./l-Triton roxyfin software -- non, 00~naphthoquinonediazide 5-Sour Von acid ester / 19.2g was obtained. Synthetic example 7 It is made to be the same as that of synthetic example 6 except having used 2.2', 4, 11 *-Tetra Hito l Fukizi benzophenone I11.Og, and 0-naphthoquinonediazide 5-Sour Von Sour [l Reid 28.0g, 2.2', and /l and 51.1 g of 0-naphthoquinonediazide 5-Sour Von acid ester of /I'-tetra-hydroxy Benz Phenone were obtained. Example 1~4. comparative example 1~3 It is the cyclohexanone in the case of Example 4 about materials j two forks at synthetic example 1~7, music dissolves in acetic acid cello Sorb -- after a spin code, and 85degreeC and the baking powder for 30 minutes -- 1.571-m film thickness -- 1+1 To be -- it is adjustment (combination of the resist solution Shop(ed) and obtained and the evaluation result of sensitivity and heat-resistant modification nature are shown in Table 1.) about concentration like In comparative example 2 which blended comparative example],;3, and alkali solubility resin with a low apparent initial softening which do not blend the condensation thing of pyrogallol and acetone, although it is improved only in or [ any of heat-resistant modification nature or sensitivity ] and -C Is not, in the present invention, it turns out that both are excellent. Sensitivity was measured by the following methods. Resist solution is applied to silicon One oxide film l Ha of 4 inch diameters, 85degreeC and prebaking for 30 minutes are performed, and the film of 1.5i rn is formed. passing the following Stomach and the step tablet mask by a Opt line company -- Gannon PLA-501F type Aligner- zeta This -- the ultraviolet rays of 80 mJ/cm2 (it measures in 405n m) -- =avb, Immersion development is carried out for 1 minute in 2.6% of tetramethylammonium high draw Kisai 18 solution. The film thickness of each step is measured, the logarithm of irradiation energy is taken along a horizontal axis, the film thickness of each step before developing negatives on a vertical axis which carried out Thickness standardization is taken, and Blower] and the Si Remaining film ratio curve are obtained. This curve made the horizontal axis sensitivity with Dawn and 1 energy of LJJ Point. Heat-resistant modification nature was evaluated as follows. As opposed to the regist layer of the silicon oxide film wafer formed in 1.571 m after 30degreeC and the baking powder for 30 minutes, 12 after irradiating with the ultraviolet rays of 3 times as much energy as sensitivity using PLA 50J F via the photomask which has a resolution pattern and carrying out one-molecule fll immersion development in 2.6% of Terramethyl ammonium Hyde °1 Koko side solution -- Bost bake is o'c and carried out for a 0 minute. Thus, the portion of a 5micron1 Rhine Anh 1zeta space is started from the wafer in which the resolution pattern of resist was formed, and it is ] from 130degreeC to 210degreedegreeC.

Trial 1 heat-treated at intervals of O degreeC for air oven 930 minutes is created. The fracture surface of the regist layer of the 5-micrometer line Anne space according to trial at given treatment temperature was observed with the scanning electron microscope, and the shape of the section considered it as heat-resistant modification nature with the highest heat treatment temperature that does not become round. Following space