United States Patent (15) 3,650,744 Kunz Et Al
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United States Patent (15) 3,650,744 Kunz et al. (45) Mar. 21, 1972 54 ETCHING METHOD USING 3,346,384 10/1967 Gaynor...................................... 96/36 PHOTOPOLYMERIZABLE WAPORS AS 2,892,712 6/1959 Plambeck.................................. 96/48 THE PHOTORESIST 3,097,097 7/1963 Oster et al................................. 96/30 (72) Inventors: Charles O. Kunz, Ballston Lake; Parley C. Primary Examiner-Norman G. Torchin Long, Bridgewater, both of N.Y. Assistant Examiner-Edward C. Kimlin 73) Assignee: General Electric Company Attorney-Richard R. Brainard, Joseph T. Cohen, Paul A. Frank, Charles T. Watts, William A. Teoli, Frank L. Neu 22 Filed: Mar. 2, 1970 hauser, Oscar B. Waddell and Joseph B. Forman 21) Appl. No.: 15,678 57 ABSTRACT 52) U.S. Cl.................................................... 96/35.1, 96/36 An etching method is provided utilizing an organic solvent 5ll Int. Cl............................................................G03c 5/00 soluble photosensitive photopolymerized organic film on the 58) Field of Search.... .96/35. 1,36; 117/93.3 surface of an etchable substrate as a negative photoresist. The organic film is applied by effecting the ultraviolet surface 56) References Cited photopolymerization of a photopolymerizable organic materi al in vaporous form, such as hexachlorobutadiene at substrate UNITED STATES PATENTS temperatures below about 100 C. The method allows for the production of composites having continuous and imperforate 3,522,076 7/1970 Wright................................ 117/93.31 films having thicknesses as low as 500 Angstroms, which can 3,522,226 7/1970 Wright. ... 1 17/93.31 be employed as negative photoresists and also provide dielec 3,321,309 5/1967 Reichel...................................... 96/36 tric layers. 3, 188,21 1 6/1965 Kocsuta..................................... 96/36 3,013,956 12/1961 Hugle et al................................. 96/36 8 Claims, 8 Drawing Figures Patented March 21, 1972 3,650,744 2. Sheets-Sheet A/G / M2 AMGA/7 soarCE M% K1/ZZZZZZSaSaaS)ZZZZZZZ4 NYNNNNN ZZZZZZZZZ NYZZZZZZZ2 Ir wer, 6tors: CAdr-/es O. Auroz, oar-/ey C. A or 23, ay 22a-2 C2 - Jeae. 77 ef- 4&étor-rey. Patented March 21, 1972 3,650,744 2 Sheets-Sheet 2 A/G 2 A/G 3 2/ EVAPORATE METAL, ONTO SUBSTRATE (fig.19, 3a)20/ SS222222222222222 3. 0 2 DEPOST POLYMERC FILM ONTO 2/ METAL LAYER UNDER CONDITIONS TO FORMAN ACETONE SOLUBLE FILM (rig. 3b) 2227,222222222Š3 22 2/ RRADATE FILM WITH U W LGHT WHILE UNDER WACUUM USNG ETHER ZZZZZZZZZZZZZYZZZZZ CONTACT (QUARTZ) OR STENCL MASK (fig. 3c) K3ZZZZZZZZZZZZZZZZZ 22 22 2/ RNSE WITH ACETONE REMOVING ZZZZ Z/Z UNFIXED POLYMERC FM (fig. 3d) SSZZZZZZZZZZZZZZZZZ 20 22 ETCH EXPOSED METAL (fig.a 3e)Je/ 2S2S23, 32." 2 27 a REMOVE FIXED POLYMERC. FILM (fig. 3f) Z2ZZ2ZZ Irwerptors: C/drl/es O. Aura, ar/ey C. 4-org, by777eir-426torrey. 2%3 Q-A-4 3,650,744 1. 2 ETCHING METHOD USING PHOTOPOLYMERIZABLE about 10 torr without undue formation of gas phase polymer, WAPORS AS THE PHOTORESIST or "floc.' Methods for forming continuous films by the ultraviolet sur The present invention relates to a method of etching a sub face photopolymerization of various organic strate utilizing a negative photoresist derived from a photosen photopolymerizable materials in vaporous form are shown in sitive photopolymerized organic film. the copending applications of A. N. Wright, Ser. No. 530,971, Prior to the present invention, various substrates were now U.S. Pat. No. 3,522,226 filed Mar. 1, 1966, and A. N. readily etched in a patterned manner using a photoresist to Wright, Ser, No. 618, 132, now U.S. Pat. No. 3,522,076, filed protect specific areas of the substrate. Generally, a preformed Feb. 23, 1967, and assigned to the same assignee as the photosensitive organic polymer was initially applied onto the 10 present invention. These applications disclose methods for surface of the substrate by such techniques as spinning or dip making thin organic films by the surface photopolymerization coating. After the polymer was applied, a mask was placed on of a variety of photopolymerizable organic materials, etc., top of the film and the substrate was placed in an exposure sta tion. The substrate was then exposed to insolubilize the film in utilizing ultraviolet light at a wavelength of less than about a patterned manner. A wash step was then employed to 15 3,500 Angstroms at a pressure of up to about 8 torr. develop the substrate. A photoresist remained on the substrate The foregoing description of other features and advantages to allow for the etching of the substrate to a desired configura of the present invention will be apparent in the following and tion, leaving a negative of the masketched into the substrate more particular description of preferred embodiments of the upon removal of the photoresist. invention as illustrated in the drawings. Although such dip-coated or spun photosensitive preformed 20 FIG. 1 illustrates an apparatus useful in practicing the organic polymers can provide satisfactory mask reproduc method of the invention such as an evacuated chamber. tions, the use of such photosensitive polymers often does not FIG. 2 is a flow chart describing some of the preferred ways allow for the employment of high resolution masks. Dip-coat in which the method of the invention can be practiced. ing or spinning techniques are generally limited to the produc FIG. 3 adjoining FIG. 2 shows sectional views of the tion of films having thicknesses of greater than 2,000 Ang 25 description of FIG. 2. stroms to minimize the effect of film discontinuities due to the There is shown in FIG. 1 a chamber 10 having a water presence of the foreign matter, such as dust which can be cooled block 11 and ducts 12 and 13. A vacuum pump picked up. The development of microelectronic printed cir chamber 14 can provide for the evacuation of chamber 10 cuits also has increased the need for techniques for depositing through valve 15. Valve 16 allows for the introduction of photosensitive materials which can be employed in combina 30 vaporous organic photopolymerizable materials. A lamp 17 is tion with high resolution masks requiring pinhole free films used to effect the formation and exposure of organic film by having uniform thicknesses of 1,000 Angstroms or less. In light transmission through window 18. most cases, preformed photosensitive polymers applied by On cooling block 11, there is shown substrate 20 such as dip-coating or spinning are not suitable as dielectric or insulat glass onto which a metal layer 21 such as aluminum can be ing layers. It also is difficult to control the uniformity and 35 evaporated. A soluble photosensitive organic film 22 can be thickness of films made from preformed organic polymers. formed on the surface of the aluminum in accordance with the The present invention is based on the discovery that con invention. There also is shown a mask 23 making up the com tinuous imperforate photosensitive organic films soluble in a posite 20-23 which upon exposure to ultraviolet light while in variety of organic solvents can be deposited on various sub vacuum effects the insolubility of the photosensitive organic strates at thicknesses as low as 500 Angstroms by effecting the 40 polymeric film in a configurational manner. surface photopolymerization of a photopolymerizable organic FIG. 2 shows a flow chart illustrating the practice of the in monomer in vaporous form at substrate temperatures below vention. A metal, for example aluminum, copper, gold, etc., is 100° C. and at pressures below about 10 torr. The thickness of evaporated onto a substrate to produce a composite of the metal and the substrate. Suitable substrates which can be em the film is controlled by varying the deposition time. The films 45 made in accordance with the invention are continuous, imper ployed are glass, plastics such as polyethyleneterephthalate, forate, adherent and uniform, and can be employed as pho silicon, etc. ln instances where silicon is employed, a silicon toresists, and subsequently removed, or can be retained on the oxide coating can serve as the etchable substrate in place of substrate as dielectric films or insulators. the aforementioned evaporated metal. There is provided by the present invention, a method for 50 The metal-substrate composite is then placed into an evacu etching a substrate which comprises (1) effecting the deposi ated chamber as shown in FIG. 1. An organic monomer such tion of an organic solvent soluble organic film onto the surface as hexachlorobutadiene is introduced at a pressure between of the substrate to produce an organic film-substrate com about 0.05 to 10 torr. An ultraviolet light source is then em posite, (2) exposing a portion of the organic solvent soluble ployed emitting light at wavelengths between 1,800 Ang organic film to ultraviolet light rendering such exposed por 55 stroms to 3,500 Angstroms. The surface of the substrate is tions, insoluble in such organic solvent, (3) treating the or maintained at temperatures below 100° C. and preferably ganic film-substrate composite with organic solvent to effect between 25 C. to 80° C. Depending upon such factors as in the removal of soluble organic film, and (4) etching the ex tensity of the light, the vapor pressure of the organic monomer posed substrate surface with a chemical etchant, which in and the temperature of the substrate, satisfactory organic sol volves the improvement of effecting the deposition of the or 60 vent soluble film can be formed at a rate of about at least 10 to ganic solvent soluble film of step (1) onto the surface of the l,000 Angstroms per minute and preferably about 100 Ang substrate by photopolymerizing a photopolymerizable organic stroms per minute.