US3666648A - In-situ reclamation of master patterns for printing microcircuit images on reversely sensitized material - Google Patents

In-situ reclamation of master patterns for printing microcircuit images on reversely sensitized material Download PDF

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US3666648A
US3666648A US874178A US3666648DA US3666648A US 3666648 A US3666648 A US 3666648A US 874178 A US874178 A US 874178A US 3666648D A US3666648D A US 3666648DA US 3666648 A US3666648 A US 3666648A
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United States
Prior art keywords
image
silver
master
solution
gelatin
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Expired - Lifetime
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US874178A
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English (en)
Inventor
Daniel J Lasky
Harold C Weisel
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International Business Machines Corp
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International Business Machines Corp
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    • 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
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/54—Absorbers, e.g. of opaque materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/40—Chemically transforming developed images
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
    • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
    • G03C5/40—Chemically transforming developed images
    • G03C5/48—Mordanting
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/0002—Apparatus or processes for manufacturing printed circuits for manufacturing artworks for printed circuits

Definitions

  • ABSTRACT Master pattern silver emulsion images of microelectronic artwork are altered in situ so that they can be used as master patterns to provide photocopies of the reverse images.
  • the silver is dissolved out and the remaining gelatin relief is dyed to a threshold level of opaqueness by an absorbed dye to produce the reversed master pattern image. Results of unusually fine detail resolution and contrast quality are achieved with substantial cost savings.
  • master pattern occasionally also referred to simply as master refers to a photographic plate, film or other transparent support on which there is an image of microelectronic artwork reproduced with high accuracy from an original master drawing or specification.
  • masters are used as copying instruments to produce printed circuit devices or the like by photocopying processes.
  • the form of the image i.e. negative or positive, is not implied in the use of this term.
  • the invention concerns treatment of master patterns, which are formed in gelatin emulsions by suspended silver grains, .to effect in situ reversal of images thereon without loss of master quality.
  • In situ reversal of masters is useful either as a reclamation expedient adaptive to an unscheduled substitution of reversely sensitizedresist material as the object medium in which photocopies of the master image are being made, or as an extension of an automated light tracing process for constructing masters.
  • One type of change which is not infrequently made is reversal of the master artwork image to render opaque image elements transparent and transparent image elements opaque.
  • the purpose of such a change would be to adapt the master to print reverse artwork images after an unscheduled substitution of reversely sensitized material on the objects receiving the print exposures.
  • object material I of reverse sensitivity may arise when shipments of a particular photosensitive resist material originally used as the photocopying medium begin to deteriorate in quality and fortuitously only one other resist material of reverse photosensitivity is available as a substitute object medium fulfilling resolution and contrast quality requirements.
  • fine grain silver forming the opaque image areas is removed by dissolution of the immediately surrounding gelatin in a weak etch-bleach solution. This leaves a transparent gelatin relief image pattern which we dye by an absorption process to a threshold level of opaqueness in relation to the actinic light required to expose the reversed image in the modified photocopying process.
  • threshold level of opaqueness we mean a level of opaqueness which can be increased or darkened (i.e. up to a saturation level) by further exposure of the gelatin to the dye solution. At threshold level we obtain a beneficial darkening effect at image edges which results in improved detail resolution without loss of dimensional accuracy.
  • Electrodes in the etch-bleach vessel are excited by applied d.c. potentials to produce gaseous bubbles, which deftly dislodge dissolving charged waste products from the image surface of the processed master and to collect such products by electrophoretic attraction so that they do not interfere with the continuation of the dissolution process.
  • the electrode placement, geometry and excitation are designed to provide a uniform agitation of the dissolving agent at the opaque surface areas of the master image defined by the presence of suspended silver grains and less turbulent agitation of the agent at the transparent image areas. Thus risk of dissolution or detachment of the clear gelatin forming the transparent relief image is minimized.
  • the dye substance applied to the relief gelatin is absorbed from a solution by imbibition.
  • the dye color is selected to match (i.e. block) the actinic frequency of radiation to which the new substitute print receiving material is sensitive.
  • enhancement and improvement of the quality of the in situ reversal process by use of electrified electrode means to provide: (a) controlled agitation of the agent which is used to attack the silvered image areas on the master, by projection of gaseous bubbles in planar formation across the image surface during the attack process; and (b) prompt removal of the attack waste products from the image surface; further refinement of the process by quenching the attacking and dyeing operations with a water rinse of the master in gently flowing circulating water warmed to room temperature;
  • FIG. 1 illustrates the subject image reversal process in schematic sectional views of a master taken in progressive stages of reversal;
  • FIG. 2 is a flow diagram more completely characterizing the sequence of development, use reversal and continued use of reversed patterns as master patterns according to the invention
  • FIG. 3 contains before and after schematic views of a master plate handled according to the invention in which a thin layer of clear gelatin underlies the opaque areas of the artwork image defined by the presence of suspended silver grains in the overlying gelatin;
  • FIG. 4 is an enlarged vertical sectional view of apparatus for carrying out the etch-bleach operation by which the suspended silver is dissolved out of the opaque area portions of the master image;
  • FIG. 5 is a schematic front elevational view of a representative master image which could be reversed in accordance with the present invention
  • FIG. 6 is an enlarged view of a portion of the master image shown in FIG. 5 illustrating line width and line spacing dimensional tolerances which can be preserved when reversing a master image by the method of the present invention
  • v is a schematic front elevational view of a representative master image which could be reversed in accordance with the present invention
  • FIG. 7 indicates in a series of section views the reversal of a master in one combined etch and dye operation
  • F IG. 8 indicates before and after elevational views of a portion of a master image in the process of being reversed and dyed by a touch-up applicator in accordance with the subject invention.
  • FIG. 9 contains schematic light transmittance profiles of a transversely scanned line image element in a master photograph before and after reversal of the image element by subject technique. These are used to explain the edge sharpening phenomenon which we have observed.
  • a master such as I typically comprises a transparent substrate 2, in the exemplification an Ortho Type "I glass plate, which is covered by a layer 3 of silver halide emulsion useful to develop high resolution high contrast images. Results of desired quality are obtained from plates coated with Kodalith Ortho Type 3 or High Resolution type emulsions.
  • the layer 3 When exposed to a pattern of light and processed the layer 3 is transformed into contrasting opaque and transparent image areas 4 and 5 respectively contained in the master image la.
  • the opaque image areas are formed by finely divided grains of metallic silver suspended in the clear gelatin which also covers the transparent areas.
  • a resist material of one working type say positive type (i.e. unexposed areas develop into relief image), is found to be unsuited to a particular printing application; for example because of non-uniform properties in different shipments, or other defective conditions.
  • a new resist material is substituted as the object medium of printing. It is not always possible however to substitute a resist material of the same working type, and when a resist material of reverse working type is substituted it becomes necessary to provide a photographically reversed master image to obtain the correct image copies in the reversely sensitive substitute material.
  • the problem of consistently reversing master images in situ without loss of master quality in subsequent photocopying usage is addressed by the present invention.
  • old master plates can be treated in situ to reverse the images thereon consistently without intolerable loss of fidelity in the reversed image and in most instances with improvement in quality of image copies transferred to the substitute material.
  • the finished master plate la which carries the original fully developed silver grain in gelatin image is reversed in situ by removing the gelatin adjacent the silver grains, thereby also removing the silver grains, and dyeing the remaining gelatin.
  • the gelatin surrounding the silver in areas 4 is attacked by a weak etchbleach solution as described herein to form the remaining gelatin 5 into a relief image having the interim form 1b.
  • the master plate is also immersed in a dye 6 which is imbibed preferentially into the relief gelatin 5 and does not color the exposed substrate 2 thereby forming reversed master image lc.
  • Stages of the foregoing procedure are indicated more specifically in the flow chart of FIG. 2. It will be noted that one or more stages of rinsing in slow flowing circulating water at room temperature are used in the image reversal procedure to quench or terminate the etching and dyeing activities.
  • FIG. 4 Apparatus which is used to reverse the master image is indicated in FIG. 4. This apparatus is similar, save for materials used, to apparatus described in the above-mentioned co-pending United States patent application of D. J. Lasky.
  • Electrode 11 when excited by an applied negative d.c. potential undergoes an electrolysis reaction with the image attacking solution 14 which is especially intense along the lengthwise ridge 12. This reaction projects a continuous stream of gaseous bubbles 16 upward in a generally planar formation across the gelatinous image bearing surface 17 of master plate 1a, said surface being situated adjacent and parallel to the plane of the bubbles.
  • Electrodes 20 and 11 are adapted to be connected through not shown connection means to respective positive and negative terminals of a not shown supply of voltage.
  • the master image assumes the interim form lb of a transparent gelatin relief of the reverse master image shown in FIG. 1. Since the interaction of bubbles l6, waste matter 19 and etching fluid 14 is concentrated most intensely at the image areas 18 it will be seen that the fluid motion is most intense at these areas. Hence the attack is intensified uniformly in the dissolving areas 18 while the fluid adjacent the transparent gelatin areas such as 21 remains comparatively less turbulent. Thus the likelihood of dislocation or distortion of areas 21 is lessened.
  • the action of the solution 14 must be stopped so that the gelatin in the clear image areas 21 will not be weakened.
  • the interim relief image 1b is rinsed carefully in a slow flow of circulating water. We have found it desirable for this purpose to immerse the plate with interim image lb in a basin of cool circulating tap water which is replenished and drained continuously at a very slow rate. It is important to avoid direct contact with turbulent water either at the influent stream from the tap or at the effluent stream approaching the drain, in order to avoid placing unnecessary stress upon the more delicate elements of the relief gelatin image.
  • plate 1 in interim form 112 is immersed in a dye solution wherein a sufficient amount of dye substance is imbibed into the reliefed gelatin to produce a threshold level of opaqueness in image areas 21 to the actinic light associated with the object resist medium of reversed sensitivity as required to form the final reversed master image 10.
  • actinic light is in the visible blue wavelength
  • a red dye which transmits red light and absorbs blue light could be used.
  • the action to quench the dyeing process consists of gentle rinsing in slow flowing water as described previously.
  • the etch-bleach solution 14 and above-mentioned dye solution can be codispersed in the tank 10 and in effect simultaneously remove the silver bearing areas and dye the background clear gelatin to form the reversed master image 1c from the original master image 1a with less handling.
  • This sequence is illustrated in FIG. 7.
  • the stop action mentioned above, consisting of gentle rinsing in cool slowly circulating water then follows immediately after the combined etch and dye operation.
  • the time required to simultaneously etch and dye is about the same as the time required previously to perform the etching operation.
  • the spacing of the electrodes 11 and 20 is also material. In practice we employ approximately a 1-inch spacing between the image surface of the master plate and electrode 20 and we prefer to position the image surface parallel to and slightly displaced from the vertical plane intersecting ridge 12 on electrode 11. In practice the approximate dimensions of tank 10 used in processing 16 by 20 inch rectangular plates are: 18 inches by 21 inches by 2 inches.
  • edges have an uncertain or fuzzy" quality due to density gradient which can vary considerably in extent relative to exemplary-line width dimensions and tolerances (FIG. 6).
  • FOG. 6 exemplary-line width dimensions and tolerances
  • edges 53 (FIG. 3) of the relief are not absolutely vertical but have gradual slope relative to the image and substrate planes. This would tend to increase the width of fuzziness in the light transmittance profile at image edges.
  • a master photocopying pattern consisting of a gelatin emulsion photograph, in which there is formed by suspended silver grains a high resolution high contrast master image of microelectric artwork, so that said photograph can be used as a master pattern in photocopying said master image in reverse, the method comprising:

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
US874178A 1969-11-05 1969-11-05 In-situ reclamation of master patterns for printing microcircuit images on reversely sensitized material Expired - Lifetime US3666648A (en)

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US87417869A 1969-11-05 1969-11-05

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US (1) US3666648A (fr)
JP (1) JPS5036765B1 (fr)
DE (1) DE2054306A1 (fr)
FR (1) FR2071742A5 (fr)
GB (1) GB1324792A (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5866303A (en) * 1997-10-15 1999-02-02 Kabushiki Kaisha Toshiba Resist developing method by magnetic field controlling, resist developing apparatus and method of fabricating semiconductor device
EP2244283A1 (fr) * 2008-02-15 2010-10-27 Lion Corporation Composition nettoyante et procédé de nettoyage de substrat pour dispositif électronique

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50156931A (fr) * 1974-06-08 1975-12-18
JPS5155233A (en) * 1974-11-09 1976-05-14 Shaken Kk Karaamojikaado oyobi sonosakuseihoho
JPS5299170U (fr) * 1976-01-21 1977-07-26

Citations (17)

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US1245152A (en) * 1916-09-15 1917-11-06 Abel Boularan Dit Deval Process for improving photographic negatives.
US1525766A (en) * 1922-07-12 1925-02-10 Eastman Kodak Co Color photography
US1564753A (en) * 1925-12-08 John g
US1632740A (en) * 1927-06-14 Indttstrie axtiengesellschaft
US1857089A (en) * 1932-05-03 Ing cobpobation
US1962348A (en) * 1929-11-13 1934-06-12 Eastman Kodak Co Photographic reversal process
US1970869A (en) * 1931-01-17 1934-08-21 Agfa Ansco Corp Photographic reversal development
US2068879A (en) * 1933-09-09 1937-01-26 Cambridge Trust Company Photographic relief process
US2193023A (en) * 1938-04-06 1940-03-12 Eastman Kodak Co Photographic reversal process
US2500052A (en) * 1948-06-02 1950-03-07 Eastman Kodak Co Photographic reversal copying process
US2676101A (en) * 1950-12-21 1954-04-20 Rca Corp Method of reversal processing sound tracks
US2939787A (en) * 1957-03-01 1960-06-07 Rca Corp Exposure of photochemical compositions
US2984567A (en) * 1957-11-29 1961-05-16 Eastman Kodak Co Method for elimination of reversal reexposure in processing photographic films
US3244083A (en) * 1962-10-23 1966-04-05 Xerox Corp Xerographic device
US3268331A (en) * 1962-05-24 1966-08-23 Itek Corp Persistent internal polarization systems
US3271145A (en) * 1963-12-23 1966-09-06 Eastman Kodak Co Process for producing an electrostatic charge image
US3471387A (en) * 1965-08-02 1969-10-07 Carter S Ink Co Electrophoretic printing medium

Patent Citations (17)

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US1564753A (en) * 1925-12-08 John g
US1632740A (en) * 1927-06-14 Indttstrie axtiengesellschaft
US1857089A (en) * 1932-05-03 Ing cobpobation
US1245152A (en) * 1916-09-15 1917-11-06 Abel Boularan Dit Deval Process for improving photographic negatives.
US1525766A (en) * 1922-07-12 1925-02-10 Eastman Kodak Co Color photography
US1962348A (en) * 1929-11-13 1934-06-12 Eastman Kodak Co Photographic reversal process
US1970869A (en) * 1931-01-17 1934-08-21 Agfa Ansco Corp Photographic reversal development
US2068879A (en) * 1933-09-09 1937-01-26 Cambridge Trust Company Photographic relief process
US2193023A (en) * 1938-04-06 1940-03-12 Eastman Kodak Co Photographic reversal process
US2500052A (en) * 1948-06-02 1950-03-07 Eastman Kodak Co Photographic reversal copying process
US2676101A (en) * 1950-12-21 1954-04-20 Rca Corp Method of reversal processing sound tracks
US2939787A (en) * 1957-03-01 1960-06-07 Rca Corp Exposure of photochemical compositions
US2984567A (en) * 1957-11-29 1961-05-16 Eastman Kodak Co Method for elimination of reversal reexposure in processing photographic films
US3268331A (en) * 1962-05-24 1966-08-23 Itek Corp Persistent internal polarization systems
US3244083A (en) * 1962-10-23 1966-04-05 Xerox Corp Xerographic device
US3271145A (en) * 1963-12-23 1966-09-06 Eastman Kodak Co Process for producing an electrostatic charge image
US3471387A (en) * 1965-08-02 1969-10-07 Carter S Ink Co Electrophoretic printing medium

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5866303A (en) * 1997-10-15 1999-02-02 Kabushiki Kaisha Toshiba Resist developing method by magnetic field controlling, resist developing apparatus and method of fabricating semiconductor device
US6279502B1 (en) 1997-10-15 2001-08-28 Kabushiki Kaisha Toshiba Resist developing method by magnetic field controlling, resist developing apparatus and method of fabricating semiconductor device
EP2244283A1 (fr) * 2008-02-15 2010-10-27 Lion Corporation Composition nettoyante et procédé de nettoyage de substrat pour dispositif électronique
US20100319735A1 (en) * 2008-02-15 2010-12-23 Lion Corporation Cleaning composition and method for cleaning substrate for electronic device
EP2244283A4 (fr) * 2008-02-15 2012-01-04 Lion Corp Composition nettoyante et procédé de nettoyage de substrat pour dispositif électronique
US8809247B2 (en) 2008-02-15 2014-08-19 Lion Corporation Cleaning composition and method for cleaning substrate for electronic device

Also Published As

Publication number Publication date
GB1324792A (en) 1973-07-25
FR2071742A5 (fr) 1971-09-17
JPS5036765B1 (fr) 1975-11-27
DE2054306A1 (de) 1971-05-13

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