EP0288533A4 - Procede et systeme d'inversion d'image. - Google Patents

Procede et systeme d'inversion d'image.

Info

Publication number
EP0288533A4
EP0288533A4 EP19870907391 EP87907391A EP0288533A4 EP 0288533 A4 EP0288533 A4 EP 0288533A4 EP 19870907391 EP19870907391 EP 19870907391 EP 87907391 A EP87907391 A EP 87907391A EP 0288533 A4 EP0288533 A4 EP 0288533A4
Authority
EP
European Patent Office
Prior art keywords
composition
accordance
light
layer
ester
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP19870907391
Other languages
German (de)
English (en)
Other versions
EP0288533A1 (fr
Inventor
Chava Gal
Giora Ben-Shushan
Eitan Shalom
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
MacDermid Inc
Original Assignee
MacDermid Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by MacDermid Inc filed Critical MacDermid Inc
Publication of EP0288533A1 publication Critical patent/EP0288533A1/fr
Publication of EP0288533A4 publication Critical patent/EP0288533A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/0226—Quinonediazides characterised by the non-macromolecular additives

Definitions

  • phenolic compounds such as mono, di, and trihydroxybenzophenone, resor ⁇ inol, 1,3 ,4-xylenol, hydroquinone, catechol, pyrogallol, phloroglu ⁇ inol, polymeric phenolic resins such as poly(vinylphenol), orcinol, 1,2,4-benzentriol, 4-methylcate ⁇ hol, 2-methylresorcinol, 2,2*4,4'-tetra- hydroxybenzophenone, picric acid, coniferyl alcohol, and the like; weak carboxylic acids such as abietic acid, cinnamic acid, 9-anthroic acid, 3-methyladipic acid, pimelic acid, 1-methyl-l-cyclohexane carboxylic acid, linolenic acid, and the like, and compounds containing both carboxylic and phenolic groups such as salicylic, protocatechuic, m-hydroxybenzoic, vanillic, p-hydroxy
  • the compositions of the invention are employed in the negative mode the requirement that there be development contrast still holds but in this case, as will be discussed in more detail below, the exposed image has been rendered substantially insoluble in the alkaline developers. Accordingly, in this mode, it is only necessary that the amount of organic solubilizing agent or agents be sufficient to render the unexposed areas of the composition completely soluble in conven ⁇ tional alkaline developers within a reasonable period of time, advantageously about 10 seconds to about 5 minutes and preferably about 1 minute for a thickness of film of the order of about 1 - 5 microns.
  • concentration of the above solubilizing agent or agents necessary to achieve such a degree of solubility can be readily determined in any given instance by a process of trial and error.
  • solubilizing agent or the total amount if two or more agents are used, is of the order of about 2 to about 20 percent by weight based on weight of phenolic resin present in the total composition.
  • phenolic resins convention ⁇ ally employed in positive photoresist compositions can be employed in the compositions of the invention.
  • Such resins are generally prepared by acid condensation of formaldehyde and phenol or an alkylsubstituted phenol under conditions described, for example, in Chemistry and Application of Phenolic Resins, Knop et al.. Chapter 4, Springer Verlag, New York, 1979.
  • a particularly preferred group of resins for use in the compositions of the invention is the group of novolak resins derived from m-cresol alone or from a mixture of phenols in which m-cresol is the major component, i.e., is present in an amount greater than 50 percent and preferably greater than about 90 percent by weight.
  • the resins employed, including the preferred group have average molecular weights in the range of about 600 to about 1600 and preferably from about 800 to about 1500.
  • the 1,2-quinonediazide sensitizers employed in the compositions of the invention can be any of those conven ⁇ tionally employed in positive photoresist compositions available in the art.
  • Such sensitizers comprise the esters and amides of naphthoquinone-(1,2)-diazide-(2)-4- sulfonic acid and naphthoquinone- (1,2)-diazide-(2)-5- sulfoni ⁇ acid.
  • the esters are generally those derived from polyhydric phenols such as 2,3,4 trihydroxybenzo- phenone, 2,4-dihydroxybenzophenone, 4-decanoylresor ⁇ in- ol, 4,4-bis(4-hydroxyphenyl)valeric acid butyl ester and the like.
  • a preferred group of such esters are the esters of the above two acids with 2,3,4-trihydroxy- benzophenone.
  • the amides of the above two acids which can be employed in the compositions of the invention are those derived from long chain aliphatic primary amines or from aromatic primary amines.
  • the proportion of such sensitizers employed in the compositions of the invention is advantageously of the order of about 2 percent to about 20 percent by weight and preferably about 2 to about 8 percent by weight, based on weight of total constituents of the composi ⁇ tions other than solvents.
  • the optimum proportion to employ in any given instance can be determined readily by a process of trial, and error.
  • the proportion of phenolic resin employed in the compositions of the invention is advantageously of the order of about 2 percent to about 45 percent by weight, and preferably about 2 to about 20 percent by weight, based on weight of total constituents of the composition other than solvents.
  • the compositions of the invention generally also comprise a solvent or a mixture of solvents.
  • the solvent or solvents employed are generally selected based on compatibility, volatility, inertness with respect to the components of the photoresist and like considerations.
  • ketones such as methylethylketone, methylisopropylke- tone, diethylketone and the like; chlorinated hydro ⁇ carbons such as trichloroethylene, 1,1,1-trichloroethane and the like; aliphatic alcohols such as ethanol, n-propyl alcohol, n-butyl alcohol, n-hexyl alcohol and the like; aliphatic esters such as n-butyl acetate, n-hexyl acetate, cellosolve acetate and the like; glycol ethers such as ethylene glycol monomethyl ether, propy- lene glycol monomethyl ether and esters thereof such as the acetates, propionates and the like; and aromatic hydrocarbons such as toluene, xylene and the like.
  • ketones such as methylethylketone, methylisopropylke- tone, diethylketone and the like
  • a preferred group of solvents are the aliphatic alcohols, aliphatic esters, glycol ether esters and aromatic hydrocarbons and mixtures of two or more such solvents.
  • the amount of solvent or mixture of solvents employed is generally such as to represent from about 50 to about 80 percent by weight, and preferably from about 60 to about 70 percent by weight, based on total weight of the compo ⁇ sitions of the invention.
  • the compositions of the invention may also com ⁇ prise other optional components conventionally employed in the art such as surfactants, adhesion-promoters, finely-divided pigments and the like.
  • compositions of the invention also comprise one or more cross-linking agents such as hexamethylolmelamine alkyl ethers, 2 , 6-bis (hydroxyl- ethyl) -4methylphenol, resoles, epoxy resins, and the like.
  • crosslinking agents may be employed in a concentration of about 0.5 to about 20 percent by weight, and preferably in a concentration of about 1 to about 10 percent by weight, based on total components other than solvents present in the 'compositions of the invention.
  • the optimum concentration for use in any given instance can be readily determined by a process of trial and error.
  • the substrate is coated with a layer of a photosensitive composition of the invention using any of the coating techniques conventional in the art. Illustrative of such techniques are spin-coating, spraying, dipping, roller coating and the like.
  • the substrate can be metallic such as aluminum, copper and the like or non- metallic such as reinforced epoxy resins, silicon wafers and the like.
  • the surface of the substrate is generally chemically pretreated, depending on the substrate material, by use of appropriate compositions such as hexamethyl disilizane and the like compositions conventionally employed in the art.
  • the thickness of the coating applied to the substrate is generally in the order of about 0.5 to about 10 microns but higher or lower thicknesses can be employed in any given instance.
  • the layer of photo ⁇ sensitive composition applied to the substrate in the above manner is then treated to remove the solvent present in the layer in any conventional manner. Generally speaking this step is achieved by baking the coated substrate at a temperature less than that which would result in decomposition of the sensitizer. A temperature of the order of about 90 to llO'Cis usually satisfactory and reduced pressures can be employed if desired in order to facilitate removal of solvent.
  • the acid function of the indene carboxylic acid produced in situ as shown above s believed to serve to catalyze cross-linking of the novolak resin in the exposed image portions of the photosensitive coating.
  • the cross-linking is facilitat ⁇ ed by the presence of the cross-linking agent or agents in the photosensitive compositions of the invention.
  • the unexposed portions of the photosensitive layer do not undergo cross-linking since no carboxylic acid has been produced in situ therein during imagewise exposure of the layer to actinic radiation. Accordingly, the unexposed portions of the photosensitive layer remain solubl e in alkal ine developer whereas the exposed portions become insoluble due to the exposure followed by post exposure baking.
  • a composition in accordance with the invention was prepared by dissolving the following components in the proportions shown in the solvent shown.
  • the resulting layer was baked at 80"C for
  • Example 3 The process . described in Example 1 is repeated using "a compos ition in accordance with the invention which had been prepared by dissolving the following components in the proportions shown in the solvent shown '
  • a composition in accordance with the invention was prepared by dissolving the following components in the amounts shown in 71 parts by weight of a mixture of propylene glycol monomethyl ether acetate, n-butanol, p-butylacetate and xylene.
  • Example 5 A composition of the invention was prepared in the same manner and using the same ingredients as in Example 4 with the exception that the amount of sensitizer was increased to 5 parts by weight.
  • Example 6 This Example illustrates the use of a typical composition of the invention to fabricate a positive resist image.
  • a silicon wafer was spin-coated at 5000 rpm with a layer of the composition of Example 4.
  • the average thickness of the coating was 1.35 microns.
  • the result ⁇ ing layer was baked at 110*C for 50 seconds on a hot plate to evaporate solvents before being cooled and exposed imagewise to UV light in a broad band contact exposure mode (150mJ/cm 2 ) using an Oriel printer.
  • the image was developed using a positive photoresist alka ⁇ line developer [MF-62: MacDermid Inc., Waterbury, Ct.] which had been diluted with water to 20 percent of the original concentration. The time required for complete clearing of the non-image areas was observed and the average loss in layer thickness of the image was measured after development was completed.
  • This example illustrates the use of a typical composition of the invention to fabricate a negative resist image employing a silicon wafer as a substrate.
  • the wafer was coated, baked, cooled, and exposed using the composition and method described in Example 6. After exposure, the wafer was baked at 130 ⁇ C for 20 minutes in an oven. The wafer was then developed by immers ion for one minute in an alkaline developed [MF- 62 ; diluted with water to 35% of the original concentration] . The resulting image was well-defined.

Landscapes

  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Materials For Photolithography (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Image Processing (AREA)
EP19870907391 1986-10-20 1987-10-16 Procede et systeme d'inversion d'image. Withdrawn EP0288533A4 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US92105686A 1986-10-20 1986-10-20
US921056 1986-10-20
US6773287A 1987-06-26 1987-06-26
US67732 1987-06-26

Publications (2)

Publication Number Publication Date
EP0288533A1 EP0288533A1 (fr) 1988-11-02
EP0288533A4 true EP0288533A4 (fr) 1989-02-06

Family

ID=26748203

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19870907391 Withdrawn EP0288533A4 (fr) 1986-10-20 1987-10-16 Procede et systeme d'inversion d'image.

Country Status (4)

Country Link
EP (1) EP0288533A4 (fr)
JP (1) JPH01501176A (fr)
AU (1) AU8173487A (fr)
WO (1) WO1988002878A1 (fr)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2598059B2 (ja) * 1987-03-27 1997-04-09 ホーセル グラフィック インダストリーズ リミッティッド 露光式石版の製造方法
EP0298393A3 (fr) * 1987-07-10 1990-06-20 Hoechst Celanese Corporation Procédé pour obtenir des images négatives à partir d'une photoréserve positive à base de curcumine et mélange photosensible contenant la curcumine
JPH02502312A (ja) * 1987-12-10 1990-07-26 マクダーミツド　インコーポレーテツド 像反転性乾燥フィルムホトレジスト
DE3935876A1 (de) * 1989-10-27 1991-05-02 Basf Ag Strahlungsempfindliches gemisch
DE3940965A1 (de) * 1989-12-12 1991-06-13 Basf Ag Strahlungsempfindliches gemisch und verfahren zur herstellung von reliefstrukturen
DE4017523A1 (de) * 1990-05-31 1991-12-05 Basf Ag Kondensationsprodukt und damit hergestelltes strahlungsempfindliches gemisch
JP3016231B2 (ja) * 1991-11-15 2000-03-06 ジェイエスアール株式会社 ネガ型レジスト組成物
EP0599779A1 (fr) * 1992-10-29 1994-06-01 OCG Microelectronic Materials AG Photoréserve négative à haute résolution ayant une latitude de traitement étendue
JPH06308729A (ja) * 1993-04-19 1994-11-04 Japan Synthetic Rubber Co Ltd 感放射線性樹脂組成物
EP0621508B1 (fr) * 1993-04-20 1996-09-25 Japan Synthetic Rubber Co., Ltd. Composition à base de résine, sensible aux radiations
JPH07104472A (ja) * 1993-10-05 1995-04-21 Matsushita Electric Ind Co Ltd 新規レジストおよび新規レジストを用いたパターン形成方法
GB9700877D0 (en) * 1997-01-17 1997-03-05 Horsell Graphic Ind Ltd Lithographic plates
US6077641A (en) * 1997-01-17 2000-06-20 Kodak Polychrome Graphics Llc Lithographic plates

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61141441A (ja) * 1984-12-14 1986-06-28 Tokyo Ohka Kogyo Co Ltd ポジ型ホトレジスト組成物

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Publication number Priority date Publication date Assignee Title
BE343251A (fr) * 1926-12-11
BE540225A (fr) * 1954-08-20
NL280959A (fr) * 1961-07-28
US4164421A (en) * 1972-12-09 1979-08-14 Fuji Photo Film Co., Ltd. Photocurable composition containing an o-quinonodiazide for printing plate
US3859099A (en) * 1972-12-22 1975-01-07 Eastman Kodak Co Positive plate incorporating diazoquinone
US4036644A (en) * 1973-03-16 1977-07-19 International Business Machines Corporation Photoresist process and photosensitive O-quinone diazide article with aliphatic carboxylic acid as adhesion promotor
US4007047A (en) * 1974-06-06 1977-02-08 International Business Machines Corporation Modified processing of positive photoresists
GB1494640A (en) * 1974-12-24 1977-12-07 Fuji Photo Film Co Ltd Image-forming on light-sensitive element containing a quinone diazide
DE2529054C2 (de) * 1975-06-30 1982-04-29 Ibm Deutschland Gmbh, 7000 Stuttgart Verfahren zur Herstellung eines zur Vorlage negativen Resistbildes
DE2547905C2 (de) * 1975-10-25 1985-11-21 Hoechst Ag, 6230 Frankfurt Lichtempfindliches Aufzeichnungsmaterial
US4148654A (en) * 1976-07-22 1979-04-10 Oddi Michael J Positive acting photoresist comprising diazide ester, novolak resin and rosin
JPS5560944A (en) * 1978-10-31 1980-05-08 Fuji Photo Film Co Ltd Image forming method
DE3039926A1 (de) * 1980-10-23 1982-05-27 Hoechst Ag, 6000 Frankfurt Lichtempfindliches gemisch, daraus hergestelltes lichtempfindliches kopiermaterial und verfahren zur herstellung einer druckform aus dem kopiermaterial
US4365019A (en) * 1981-08-06 1982-12-21 Eastman Kodak Company Positive-working resist quinone diazide containing composition and imaging method having improved development rates
US4439516A (en) * 1982-03-15 1984-03-27 Shipley Company Inc. High temperature positive diazo photoresist processing using polyvinyl phenol
DE3325023A1 (de) * 1983-07-11 1985-01-24 Hoechst Ag, 6230 Frankfurt Verfahren zur herstellung negativer kopien mittels eines materials auf basis von 1,2-chinondiaziden
DE3325022A1 (de) * 1983-07-11 1985-01-24 Hoechst Ag, 6230 Frankfurt Verfahren zur herstellung negativer kopien mittels eines materials auf basis von 1,2-chinondiaziden
MX170270B (es) * 1984-06-01 1993-08-11 Rohm & Haas Imagenes sobre una superficie y un metodo para formar imagenes positivas y negativas termicamente estables sobre una superficie
US4626492A (en) * 1985-06-04 1986-12-02 Olin Hunt Specialty Products, Inc. Positive-working o-quinone diazide photoresist composition containing a dye and a trihydroxybenzophenone compound
JPS6235350A (ja) * 1985-08-07 1987-02-16 インタ−ナショナル　ビジネス　マシ−ンズ　コ−ポレ−ション 像反転に有用な保存寿命の長いフオトレジスト

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61141441A (ja) * 1984-12-14 1986-06-28 Tokyo Ohka Kogyo Co Ltd ポジ型ホトレジスト組成物

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN, vol. 10, no. 338 (P-516)[2394], 15th November 1986; & JP-A-61 141 441 (TOKYO OHKA KOGYO CO. LTD) 28-06-1986 *
See also references of WO8802878A1 *

Also Published As

Publication number Publication date
JPH01501176A (ja) 1989-04-20
WO1988002878A1 (fr) 1988-04-21
AU8173487A (en) 1988-05-06
EP0288533A1 (fr) 1988-11-02

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