CA2010030C - Method for transferring patterns on silicone ladder type resin and etching solution used in such method - Google Patents
Method for transferring patterns on silicone ladder type resin and etching solution used in such methodInfo
- Publication number
- CA2010030C CA2010030C CA002010030A CA2010030A CA2010030C CA 2010030 C CA2010030 C CA 2010030C CA 002010030 A CA002010030 A CA 002010030A CA 2010030 A CA2010030 A CA 2010030A CA 2010030 C CA2010030 C CA 2010030C
- Authority
- CA
- Canada
- Prior art keywords
- photo
- ladder type
- resist layer
- resist
- silicone ladder
- 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.)
- Expired - Fee Related
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
-
- 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
- G03F7/075—Silicon-containing compounds
- G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
-
- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/308—Chemical or electrical treatment, e.g. electrolytic etching using masks
Abstract
A method for transferring patterns on a silicone ladder type resin, which comprises: applying onto a substrate a silicone ladder type resin to be represented by the following general formula (I) (I) (where: R1 denotes a phenyl group or a lower alkyl group, and two R1's may be the same or different kinds; R2 denotes hydrogen atom or a lower alkyl group, and four R2's may be the same or different kinds; and n represents an integer of from 5 to 1,000); drying the thus applied resin layer; thereafter applying onto the resin layer a cresol novolac type positive photo-resist; forming a predetermined pattern in the photo-resist layer;
subjecting the photo-resist layer to pretreatment; and finally etching the silicone ladder type resin.
An etching liquid for etching a silicone ladder type resin, which comprises an aromatic type solvent.
subjecting the photo-resist layer to pretreatment; and finally etching the silicone ladder type resin.
An etching liquid for etching a silicone ladder type resin, which comprises an aromatic type solvent.
Description
`~ 20 1 0030 This invention relates to a method for transferring patterns on a silicone ladder type resin, and to an etching solution used in such pattern transferring method.
In recent years, as a method for forming a passivation layer for a solid-state element, a stress-relaxing film, or an insulating layer, in the production of semiconductor devices, studies have been made as to a method for spin-coating of high polymer materials having excellent properties such as lower residual stress, better surface smoothness, and higher purity than those of inorganic materials. As the high-polymer materials, there have so far been used thermo-setting resins such as silicone ladder type resins, polyimide resins, and so on having heat-resistance of 450C or higher.
When the above-mentioned silicone ladder type resin is used as a passivation layer for a solid-state element, a stress-relaxing layer, or an insulating layer, it becomes necessary to subject these silicone ladder type resin layers to fine mach;n;ng in order to perforate through-holes for connecting them with the venting portions of the upper and lower conductor layers and with external lead wires.
For the purpose of subjecting a silicone ladder type resin film to fine mach;n;ng, Japanese Unexamined Patent ` 20 1 0~30 -Publication No. 49540/1981 discloses a wet-type etching process, in which use is made of hydrofluoric acid as the etching liquid. When the present inventors examined workability of this etching liquid, it was found that a silicone ladder type resin could not be etched with hydrofluoric acid.
Also, Japanese Un~x~ined Patent Publication No.
125855/1981 discloses the dry etching process with use of CF4 gas plasma, which was also found to be disadvantageous in that its etching rate was low, and, in the case of a thick film such as a stress-relaxing layer, a passivation layer, and so on, its etching time was prolonged.
Thus, there has so far been established no technique of stable pattern transfer onto the thick layer of the silicone ~
ladder type resin.
The present invention provides a wet type etching method capable of stable pattern transfer in a short period of time even on a layer of a thick-film, and an etching liquid to be used 20~0030 for this etching process.
According to the present invention, in one aspect of it, there is provided a method for transferring patterns on a silicone ladder type resin, which comprises:
applying onto a substrate a silicone ladder type resin to be represented by the following general formula (I) R~
R2 -si-o --R2 o (I) R2O \ Si-t --R2 Rl n (where: Rl denotes a phenyl group or a lower alkyl group, and two Rl's may be the same or different kinds; R2 denotes hydrogen atom or a lower alkyl group, and four R2's may be the same or different kinds; and n represents an integer of from 5 to l,000); drying the thus applied resin layer; thereafter applying onto said resin layer a cresol novolac type positive photo-resist; forming a predetermined pattern in said photo-resist layer;
subjecting said photo-resist layer to pre-etching treatment; and finally etching said silicone ladder type resin.
According to the present invention, in another aspect of it, there is provided an etching liquid for etching a silicone ladder type resin, which comprises an aromatic type solvent.
-The foregoing objects, other objects as well as the specific conditions for effecting the method for etching according to the present invention and the ingredient constituting the etching liquid for use in effecting the method according to the present invention will become more apparent and underst~n~hle from the following detailed description thereof, when read in conjunction with the preferred examples.
For effecting the etching method according to the present invention, there i5 used the silicone ladder type resin to be represented by the following general formula (I):
11 \
R20 1 i--O R2 I (I) R20 ~ R2 ~ 1 (where: R1 denotes a phenyl group or a lower alkyl group such as methyl group, ethyl group and so forth, and two Rlls may be the same or different kinds; R2 denotes hydrogen atom or a lower alkyl group such as methyl group, ethyl group and so on, and four R2's may be the same or different kinds; and n represents an integer of from 5 to 1,000, or preferably from 50 to 850).
This silicone ladder type resin is a well known one, ~i `~ ~o of which a relatively high molecular weight resin and its production method are dislosed in Japanese Patent Publication No.15989/1965, Japanese Unexamined Patent Publications No. 111197/1975, No. 111198/1975, and No.
18729/1982, and a relatively low molecular weight resin ~ is available from Owens-Illinois Glass Co., U.S.A. as a glass resin. Both these high and low molecular weight resins can be used for the purpose of the present invention.
The coating film to be obtained from the silicone ladder type resin represented by the above general formula (I) has a smaller residual stress, better surface smoothness, and higher purity than those of inorganic materials, on account of which the resin material is suitable as a passivation layer of a solid-state element, a stress-relaxing film, insulating layer, and so forth.
According to the method of the present invention, the silicon ladder type resin to be represented by the general formula (I) is first coated onto a substrate, and then the coated resin is dried to remove a solvent contained in it, thereby forming the resin film.
It is desirable that the silicone ladder type resin be mixed with a solvent such as benzene type solvents, alkoxybenzene type solvents, N-methyl pyrrolidone, and so on to adjust its viscosity to an order of from 2,000 to 5,000 cps., and that, after this adjustment, the resin solution be applied onto a substrate such as silicon - 6 - 2 ~ 003 wafers, etc. by a spin-coating method using a spinner.
While conditions for drying the resin solution as coated may differ from solvent to solvent, a preferred drying temperature range may be from 80 to 350C, at which temperature level the resin does not become cured. A
~ ~ more preferred condition may be from 100 to 200C for 15 to 45 min.. Thickness of the resin film may usually be in a range of from 1 to 30 ~um, although it may be varied depending on the purpose of its use.
In the next place, a cresol novolac type positive photo-resist is applied onto the above-mentioned dried, uncured resin film, and then a predetermined pattern is formed on this photo-resist layer.
As for the photo-resist layer, there is no particular limitation, and a cresol novolac type positive photo-resist available in general market may be used. Examples .. , . ~
of the positive photo-resist material are: "OFP~-800"
produced and marketed by Tokyo Ohka Kogyo K.K. (Tokyo Applied Chemical Industry Co. Ltd.), Japan, "AZ-1350"
produced and marketed by Shipley Co., and other generally available photo-resist materials.
The photo-resist patterns are formed by coating the above-mentioned phenol type positive photo-resist material onto the silicone ladder type resin by the spin-coating method in pursuance of the ordinary coatingprocedures, and, after close contact of a photo-mask, irradiating the ultra-violet rays onto the photo-resist acl~nlark ~ - 7 -layer, followed by developing the photo-resist pattern.
Subsequently, there will be effected the following pretreatment with a view to suppressing occurrence of cracks in the photo-resist layer due to increase in the residual stress within the photo-resist layer by ~ immersion into an etching liquid for the silicone ladder type resin at the time of its wet-etching by use of the etching liquid to be explained later, with the thus obtained photo-resist pattern as a mask.
Examples of the pre-treatments are as follows:
(i) the photo-resist is heated to a temperature of from 125 to 160C, or more preferably from 130 to 150C
for 15 to 60 min., or more preferably from 30 to 45 min., after which it is held at room temperature for three hours or longer, or more preferably for four hours or longer.
(ii) ultra-violet rays of 500 nm or lower, or more preferably from 300 to 500 nm are irradiated onto the entire surface of the photo-resist.
This pre-treatment was found out by the present inventors, as the results of their strenuous efforts, on the notion that the cracks to occur in the photo-resist layer might be suppressed by a method, in which a strength surpassing the internal stress of the photo-resist layer is imparted to it by the heat curing of the photo-resist layer, or a method, in which the photo-resist is liberated from its internal stress before it is 20~0~3~
immersed into the etching liquid.
The pre-treatment in the above (i), wherein the photo-resist layer is left at room temperature, was devised by the present inventors, who discovered, as the result of their studies on the pre-treatment of the phto-resist layer by the heat-treatment, that the conditions for occurrence of the cracks differed depending on length of time until it is immersed in the etching liquid after it is heated and then cooled to room temperature.
With the heating temperature in the pre-treatment of the above (i) being below 125C, the photo-resist layer does not become sufficiently cured, and the cracks tend to occur even when it is left to cool over a length of three hours or longer at room temperature after the heating. On the other hand, when the heating temperature exceeds 160C, the photo-resist layer tends to suffer from heat deterioration. The heating time should be such that the photo-resist layer becomes sufficiently cured, which depends on the heating temperature. Usually, an appropriate time is selected from a range of between 15 and 60 min.. With a length of time, during which the photo-resist layer is left at room temperature (that is, a length of time from its return to room temperature after the heat-treatment to its immersion into the etching liquid) being less than three hours, the suppression of the cracks to occur is insufficient.
The suppression of the cracks to occur in the photo-2~100:~0 ' g resist layer by leaving it at room temperature after theheat-treatment appears to be due to the stress to be generated in the photo-resist layer by the linear expansion coefficient between the heat-cured photo-resist layer and the silicone ladder type resin being relaxed by - ~ maintaining the photo-resist layer at room temperature.
When the wavelength of the ultraviolet rays in the pre-treatment of the above (ii) exceeds 500 nm, a sufficient effect of irradiation of the ultraviolet rays becomes unable to be obtained. On the other hand, with the wavelenght of the ultraviolet rays not reaching 300 nm, the effect of suppressing cracks to occur is not sufficient, even though the surface of the photo-resist layer becomes cured, hence, as is the case with the pre-treatment of the above-mentioned (i), it must be left at room temperature for at least 3 hours after the irradiation of the ultraviolet rays, whereby occurrence of the cracks can be suppressed.
While the quantity of irradiation of the ultraviolet rays depends upon the wavelength of the ultraviolet rays to be irradiated, a preferred intensity is 50 mJ/cm2 or above. With the ultraviolet rays having the wavelength of from 300 to 500 nm, the intensity of its irradiation should preferably be 100 mJ/cm2 or above. For suppressing the cracks to occur, the irradiating quantity of the ultraviolet rays should preferably be at such an intensity that the absorption peak in the vicinity of ZOlQ030 2120 cm~l to be derived from the diazide group in the infrared ray absorption spectrum will disappear, i.e., 50 mJ/cm2 or above. This appears to be due to the fact that the diazide group disappears by the irradiation of the ultraviolet rays, and, in particular, when the ultraviolet rays of the wavelength between 300 and 500 nm are irradiated, the diazide group is dissipated outside the photo-resist layer in the form of nitrogen gas to result in relaxation of the internal stress within the photo-resist layer, and it becomes softened.
As such, in the pre-treatment of the above (ii), by the irradiation of the ultraviolet rays having the wavelength of from 300 to 500 nm at its intensity of 100 mJ/cm2 or above, there will occur no cracks in the photo-resist layer, even when it is immersed in the etchingliquid immediately after the ultraviolet ray irradiation.
After the abovementioned pre-treatment, the silicone ladder type resin is etched with the photo-resist patterns as a mask.
The etching solution for the silicone ladder type resin should necessarily be those solvents which dissolve this resin but do not dissolve the phenolic type positive photo-resist layer. As the solvents for such resin, there have been known various types of solvents such as halogenated hydrocarbon type solvents, ether type solvents, benzene type solvents, alkoxybenzene type solvents, cyclic ketone type solvents, N-methylpyrrolidone, N,N'-dimethylformamide, and others (vide: Japanese Unexamined Patent Publication No.
94955/1980). As the results of making various studies on these solvents, the present inventors discovered that those aromatic type solvents such as benzene, = alkylbenzene (toluene, xylene, and so on), and alkoxybenzene (methoxybenzene, ethoxybenzene, and so on) were suitable as the solvents which did not dissolve the phenolic type positive photo-resist layer.
The rate of etching with these etching liquids should preferably be at an appropriate rate selected from a range between 1 and 10 ~m/min. so as to complete the etching of the silicone ladder type resin in a time period of from 30 to 150 sec.. The adjustment of the etching rate can be done easily by mixing, for example, xylene, etc., depending upon the molecular weight of the silicone ladder type resin.
Preferrred examples of the etching liquid are: a mixed solvent of alkoxybenenze and xylene with a volume ratio of the former being 18% or above, a mixed solvent of toluene and xylene with a volume ratio of the former being 20% or above, a mixed solvent of benzene and xylene with a volume ratio of the former being 25% or above, and others. The etching is usually done at a constant temperature level properly selected from a range between 20 and 28C.
In the following, the present invention will be explained more specifically with reference to its preferred examples.
To a silicone ladder type resin having a molecular weight of about 120,000, in which Rl shown in the aforementioned general formula (I) is a phenyl group, and R2 is hydrogen, there was added benzene to adjust the viscosity of the resin to 3,000 cps. Subsequently, the thus prepared solution was applied onto the surface of a silicon wafer by means of a spinner rotating at a rate of 2,000 rpm.
Thickness of the film as formed was 10 ~m.
The thus formed film layer was dried at a temperature of 150C for 30 min., after which a photo-resist material OFPR*-800 (a product of Tokyo Ohka Kogyo K.K.) was applied onto this resin layer by means of the spinner rotating at a rate of 2,000 rpm. Thickness of the photo-resist layer as formed was 2 ~m.
After drying the photo-resist layer at a temperature of 80C for 30 min., a photo-mask was closely contacted on this photo-resist layer. Then, ultraviolet rays was irradiated onto it by means of an ultra-high pressure *trademark 20~00:~0 mercury lamp, followed by immersing the same in a ` F~ developing liquid for "OFPR" for 60 sec. to thereby ~- dissolve the exposed portion on the photo-resist. The thus developed photo-resist layer on the silicon wafer was rinsed with pure water, and then dried at a -~~ temperature of 80C for 30 min...... As the result, there was formed a photo-resist pattern.
Thereafter, the photo-resist layer was heat-treated at a temperature of 130C for 30 min., followed by maintaining the same at room temperature for four hours.
Subsequently, the photo-resist layer was immersed in an etching liquid composed of a mixture of toluene and xylene with a volume ratio between them being 1/1 at 25C
for 60 sec., thereby etching the silicone ladder type resin. After the etching, the thus treated photo-resist layer was observed through a microscope. No cracks were found to have occurred.
Next, the photo-resist layer was removed with use of a photo-resist release agent, thereby obtaining a silicone ladder type resin film, on which a predetermined pattern had been transferred. The size of the opening on the resin film was 24 ~m square with a mask size of 20 ~m square. Also, observation through a scanning electron microscope indicated that the result of the treatment was satisfactory.
Benzene was added to the silicone ladder type resin rcll~ark 2010(~30 _ as used in Example 1 above to adjust the viscosity of the resin to 2,700 cps. The thus obtained resin solution was applied onto the silicon wafer by means of a spinner rotating at a rate of 2,000 rpm. Thickness o~ the layer as formed was 5 ~m.
The resin layer as formed was dried at a temperature of 150C for 30 min., and then, following the same procedures as in Example 1 above, the photo-resist pattern having a pattern size of 20 ~m square was formed.
After the heat-treatment at 140C for 30 min., the photo-resist pattern was held at room temperature for five hours. Subsequently, it was immersed in ethoxybenzene as the etching liquid at a temperature of 25C for 60 sec., thereby etching the silicone ladder type resin.
Next, the photo-resist layer was removed with use of a photo-resist release agent, thereby obtaining a silicone ladder type resin film, on which a predetermined pattern had been transferred. The size of the opening on the resin film was 23 ~m square with a mask size of 20 ~m square. Also, the shape of the pattern was satisfactory.
To a silicone ladder type resin having a molecular weight of about 150,000, in which Rl shown in the afore-mentioned general formula (I) is a phenyl group, and R2is hydrogen, there was added toluene to adjust the viscosity of the resin to 5,000 cps. Subsequently, the thus prepared solution was applied onto the surface of a silicon wafer by means of a spinner rotating at a rate of 2,000 rpm. Thickness of the film as formed was 20 ~m.
The resin layer as formed was dried at a temperature of 150C for 30 min., and then, following the same procedures as in Example 1 above, a photo-resist pattern having a pattern size of 20 ~m square was formed.
Thereafter, ultraviolet rays at an intensity of 300mJ/cm2 was irradiated over the entire surface of the photo-resist pattern by means of an ultra-high pressure mercury lamp, from which the rays of~a wavelength shorter than 300 nm had been removed. After this, the photo-resist pattern was immersed in a mixed solvent of methoxybenzene and xylene with a volume ratio between them being 1/2, at a temperature of 25C for 60 sec. to etch the silicone ladder type resin. In the next place, the photo-resist layer was removed with use of a photo-resist release agent, thereby obtaining the silicone ladder type resin, on which a predetermined pattern had been transferred.
The size of the opening on the resin film was 29 ~m square. Also, the shape of the photo-resist pattern was found satisfactory.
To a silicone ladder type resin having a molecular weight of about 100,000, in which Rl shown in the afore-mentioned general formula (I) is a methyl group and R2 is hydrogen, there was added benzene to adjust the viscosity 20~0030 of the resin to 2,900 cps. Subsequently, the thus prepared solution was applied onto the surface of a silicon wafer by means of a spinner rotating at a rate of 2,000 rpm. Thickness of the film as formed was 8 ~m.
The resin layer as formed was dried at a temperature of 140C for 30 min., and then, following the same procedures as in Example 1 above, the photo-resist pattern having a pattern size of 20 ~m sqaure was formed.
Thereafter, the photo-resist layer was heat-treated at a temperature of 150C for 30 min., followed by leaving the same at room temperature for ten hours.
Subsequently, the photo-resist layer was immersed in a mixed solution of methoxybenzene and xylene with a volume ratio between them being 1/3 at 25C for 60 sec., thereby etching the silicone ladder type resin. After the etching, the thus treated photo-resist layer was observed through a microscope. No cracks were found to have occurred.
Next, the photo-resist layer was removed with use of a photo-resist release agent to thereby obtain the silicone ladder type resin, on which a predetermined pattern had been transferred. The size of the opening on the resin film was 23 ~m square. Also, the shape of the photo-resist pattern was found satisfactory.
Benzene was added to the silicone ladder type resin as used in Example 4 above to adjust the viscosity of the resin to 2,400 cps. The thus obtained resin solution was applied onto a silicon wafer by means of a spinner rotating at a rate of 2,000 rpm. Thickness of the layer as formed was 3.0 ,um.
The resin layer as formed was dried at a temperature of 140C for 30 min., and then, following the same procedures as in Example 1 above, the photo-resist pattern having a pattern size of 10 ~m square was formed.
Thereafter, the ultraviolet rays at an intensity of 200mJ/cm2 was irradiated over the entire surface of the photo-resist pattern by means of an ultra-high pressure mercury lamp, from which the rays of a wavelength shorter than 300 nm had been removed. After this, the photo-resist pattern was immersed in ethoxybenzene at a temperature of 25C for 30 sec., whereby etching the silicone ladder type resin. In the next place, the photo-resist layer was removed with use of a photo-resist release agent to thereby obtain the silicone ladder type resin, on which a predetermined pattern had been transferred. The size of the opening on the resin film was 10.9 ~m square. Also, the shape of the photo-resist pattern was found satisfactory.
Benzene was added to the silicone ladder type resin as used in Example 1 above to adjust the viscosity of the resin to 2,800 cps. The thus obtained resin solution was applied onto a silicon wafer by means of a spinner 20~0030 rotating at a rate of 2,000 rpm. Thickness of the layer as formed was 6 ~m. Subsequently, following the same procedures as in Example 1 above, a photo-resist pattern having a size of 10 ,um square was formed, after which the ultraviolet rays at an intensity of 200mJ/cm2 were irradiated over the entire surface of the photo-resist pattern, and then it was maintained at room temperature for five hours.
Subsequently, the photo-resist pattern was immersed in a mixed solvent of toluene and xylene with a volume ratio between them being 2/3, as the etching liquid, at a temperature of 25C for 50 sec., thereby etching the silicone ladder type resin. After the etching, the thus treated photo-resist was observed through a microscope.
No cracks were found to have occurred.
Next, the photo-resist layer was removed with use of a photo-resist release agent to thereby obtain the silicone ladder type resin, on which a predetermined pattern had been transferred. The size of the opening on the resin film was 12.5 ~m square with the photo-resist pattern having a mask size of 10 ~m square.
A benzene solution of the silicone ladder type resin as used in Example 4 above was applied on a silicon wafer by means of a spinner rotating at a rate of 3,000 rpm.
Thickness of the resin layer as formed was 5.0 ~m.
The resin layer as formed was dried at a temperature of 140C for 30 min., and then, following the same procedures as in Example 1 above, the photo-resist pattern having a pattern size of 10 ~m square was formed.
Thereafter, the ultraviolet rays at an intensity of 250mJ/cm2 was irradiated over the entire surface of the photo-resist pattern by means of an ultra-high pressure mercury lamp, from which the rays of a wavelength shorter than 300 nm had been removed.
After this, the photo-resist pattern was immersed in a mixed solution of toluene and xylene with a volume ratio between them being 2/3, as the etching liquid, at a temperature of 25C for 50 sec., thereby etching the silicone ladder type resin. After the etching, there could be found no cracks occurred in the photo-resist pattern.
In the next place, the photo-resist layer was removed with use of a photo-resist release agent to thereby obtain the silicone ladder type resin, on which a predetermined pattern had been transferred. The size of the opening on the resin film was 13.0 ~m square with the photo-resist pattern having a mask size of 10 ~m square.
As has so far been described in the foregoing, according to the present invention, it is possible to etch the silicone ladder type resin in a short period of time with use of an aromatic type solvent, and to transfer a predetermined pattern with satisfaction.
In recent years, as a method for forming a passivation layer for a solid-state element, a stress-relaxing film, or an insulating layer, in the production of semiconductor devices, studies have been made as to a method for spin-coating of high polymer materials having excellent properties such as lower residual stress, better surface smoothness, and higher purity than those of inorganic materials. As the high-polymer materials, there have so far been used thermo-setting resins such as silicone ladder type resins, polyimide resins, and so on having heat-resistance of 450C or higher.
When the above-mentioned silicone ladder type resin is used as a passivation layer for a solid-state element, a stress-relaxing layer, or an insulating layer, it becomes necessary to subject these silicone ladder type resin layers to fine mach;n;ng in order to perforate through-holes for connecting them with the venting portions of the upper and lower conductor layers and with external lead wires.
For the purpose of subjecting a silicone ladder type resin film to fine mach;n;ng, Japanese Unexamined Patent ` 20 1 0~30 -Publication No. 49540/1981 discloses a wet-type etching process, in which use is made of hydrofluoric acid as the etching liquid. When the present inventors examined workability of this etching liquid, it was found that a silicone ladder type resin could not be etched with hydrofluoric acid.
Also, Japanese Un~x~ined Patent Publication No.
125855/1981 discloses the dry etching process with use of CF4 gas plasma, which was also found to be disadvantageous in that its etching rate was low, and, in the case of a thick film such as a stress-relaxing layer, a passivation layer, and so on, its etching time was prolonged.
Thus, there has so far been established no technique of stable pattern transfer onto the thick layer of the silicone ~
ladder type resin.
The present invention provides a wet type etching method capable of stable pattern transfer in a short period of time even on a layer of a thick-film, and an etching liquid to be used 20~0030 for this etching process.
According to the present invention, in one aspect of it, there is provided a method for transferring patterns on a silicone ladder type resin, which comprises:
applying onto a substrate a silicone ladder type resin to be represented by the following general formula (I) R~
R2 -si-o --R2 o (I) R2O \ Si-t --R2 Rl n (where: Rl denotes a phenyl group or a lower alkyl group, and two Rl's may be the same or different kinds; R2 denotes hydrogen atom or a lower alkyl group, and four R2's may be the same or different kinds; and n represents an integer of from 5 to l,000); drying the thus applied resin layer; thereafter applying onto said resin layer a cresol novolac type positive photo-resist; forming a predetermined pattern in said photo-resist layer;
subjecting said photo-resist layer to pre-etching treatment; and finally etching said silicone ladder type resin.
According to the present invention, in another aspect of it, there is provided an etching liquid for etching a silicone ladder type resin, which comprises an aromatic type solvent.
-The foregoing objects, other objects as well as the specific conditions for effecting the method for etching according to the present invention and the ingredient constituting the etching liquid for use in effecting the method according to the present invention will become more apparent and underst~n~hle from the following detailed description thereof, when read in conjunction with the preferred examples.
For effecting the etching method according to the present invention, there i5 used the silicone ladder type resin to be represented by the following general formula (I):
11 \
R20 1 i--O R2 I (I) R20 ~ R2 ~ 1 (where: R1 denotes a phenyl group or a lower alkyl group such as methyl group, ethyl group and so forth, and two Rlls may be the same or different kinds; R2 denotes hydrogen atom or a lower alkyl group such as methyl group, ethyl group and so on, and four R2's may be the same or different kinds; and n represents an integer of from 5 to 1,000, or preferably from 50 to 850).
This silicone ladder type resin is a well known one, ~i `~ ~o of which a relatively high molecular weight resin and its production method are dislosed in Japanese Patent Publication No.15989/1965, Japanese Unexamined Patent Publications No. 111197/1975, No. 111198/1975, and No.
18729/1982, and a relatively low molecular weight resin ~ is available from Owens-Illinois Glass Co., U.S.A. as a glass resin. Both these high and low molecular weight resins can be used for the purpose of the present invention.
The coating film to be obtained from the silicone ladder type resin represented by the above general formula (I) has a smaller residual stress, better surface smoothness, and higher purity than those of inorganic materials, on account of which the resin material is suitable as a passivation layer of a solid-state element, a stress-relaxing film, insulating layer, and so forth.
According to the method of the present invention, the silicon ladder type resin to be represented by the general formula (I) is first coated onto a substrate, and then the coated resin is dried to remove a solvent contained in it, thereby forming the resin film.
It is desirable that the silicone ladder type resin be mixed with a solvent such as benzene type solvents, alkoxybenzene type solvents, N-methyl pyrrolidone, and so on to adjust its viscosity to an order of from 2,000 to 5,000 cps., and that, after this adjustment, the resin solution be applied onto a substrate such as silicon - 6 - 2 ~ 003 wafers, etc. by a spin-coating method using a spinner.
While conditions for drying the resin solution as coated may differ from solvent to solvent, a preferred drying temperature range may be from 80 to 350C, at which temperature level the resin does not become cured. A
~ ~ more preferred condition may be from 100 to 200C for 15 to 45 min.. Thickness of the resin film may usually be in a range of from 1 to 30 ~um, although it may be varied depending on the purpose of its use.
In the next place, a cresol novolac type positive photo-resist is applied onto the above-mentioned dried, uncured resin film, and then a predetermined pattern is formed on this photo-resist layer.
As for the photo-resist layer, there is no particular limitation, and a cresol novolac type positive photo-resist available in general market may be used. Examples .. , . ~
of the positive photo-resist material are: "OFP~-800"
produced and marketed by Tokyo Ohka Kogyo K.K. (Tokyo Applied Chemical Industry Co. Ltd.), Japan, "AZ-1350"
produced and marketed by Shipley Co., and other generally available photo-resist materials.
The photo-resist patterns are formed by coating the above-mentioned phenol type positive photo-resist material onto the silicone ladder type resin by the spin-coating method in pursuance of the ordinary coatingprocedures, and, after close contact of a photo-mask, irradiating the ultra-violet rays onto the photo-resist acl~nlark ~ - 7 -layer, followed by developing the photo-resist pattern.
Subsequently, there will be effected the following pretreatment with a view to suppressing occurrence of cracks in the photo-resist layer due to increase in the residual stress within the photo-resist layer by ~ immersion into an etching liquid for the silicone ladder type resin at the time of its wet-etching by use of the etching liquid to be explained later, with the thus obtained photo-resist pattern as a mask.
Examples of the pre-treatments are as follows:
(i) the photo-resist is heated to a temperature of from 125 to 160C, or more preferably from 130 to 150C
for 15 to 60 min., or more preferably from 30 to 45 min., after which it is held at room temperature for three hours or longer, or more preferably for four hours or longer.
(ii) ultra-violet rays of 500 nm or lower, or more preferably from 300 to 500 nm are irradiated onto the entire surface of the photo-resist.
This pre-treatment was found out by the present inventors, as the results of their strenuous efforts, on the notion that the cracks to occur in the photo-resist layer might be suppressed by a method, in which a strength surpassing the internal stress of the photo-resist layer is imparted to it by the heat curing of the photo-resist layer, or a method, in which the photo-resist is liberated from its internal stress before it is 20~0~3~
immersed into the etching liquid.
The pre-treatment in the above (i), wherein the photo-resist layer is left at room temperature, was devised by the present inventors, who discovered, as the result of their studies on the pre-treatment of the phto-resist layer by the heat-treatment, that the conditions for occurrence of the cracks differed depending on length of time until it is immersed in the etching liquid after it is heated and then cooled to room temperature.
With the heating temperature in the pre-treatment of the above (i) being below 125C, the photo-resist layer does not become sufficiently cured, and the cracks tend to occur even when it is left to cool over a length of three hours or longer at room temperature after the heating. On the other hand, when the heating temperature exceeds 160C, the photo-resist layer tends to suffer from heat deterioration. The heating time should be such that the photo-resist layer becomes sufficiently cured, which depends on the heating temperature. Usually, an appropriate time is selected from a range of between 15 and 60 min.. With a length of time, during which the photo-resist layer is left at room temperature (that is, a length of time from its return to room temperature after the heat-treatment to its immersion into the etching liquid) being less than three hours, the suppression of the cracks to occur is insufficient.
The suppression of the cracks to occur in the photo-2~100:~0 ' g resist layer by leaving it at room temperature after theheat-treatment appears to be due to the stress to be generated in the photo-resist layer by the linear expansion coefficient between the heat-cured photo-resist layer and the silicone ladder type resin being relaxed by - ~ maintaining the photo-resist layer at room temperature.
When the wavelength of the ultraviolet rays in the pre-treatment of the above (ii) exceeds 500 nm, a sufficient effect of irradiation of the ultraviolet rays becomes unable to be obtained. On the other hand, with the wavelenght of the ultraviolet rays not reaching 300 nm, the effect of suppressing cracks to occur is not sufficient, even though the surface of the photo-resist layer becomes cured, hence, as is the case with the pre-treatment of the above-mentioned (i), it must be left at room temperature for at least 3 hours after the irradiation of the ultraviolet rays, whereby occurrence of the cracks can be suppressed.
While the quantity of irradiation of the ultraviolet rays depends upon the wavelength of the ultraviolet rays to be irradiated, a preferred intensity is 50 mJ/cm2 or above. With the ultraviolet rays having the wavelength of from 300 to 500 nm, the intensity of its irradiation should preferably be 100 mJ/cm2 or above. For suppressing the cracks to occur, the irradiating quantity of the ultraviolet rays should preferably be at such an intensity that the absorption peak in the vicinity of ZOlQ030 2120 cm~l to be derived from the diazide group in the infrared ray absorption spectrum will disappear, i.e., 50 mJ/cm2 or above. This appears to be due to the fact that the diazide group disappears by the irradiation of the ultraviolet rays, and, in particular, when the ultraviolet rays of the wavelength between 300 and 500 nm are irradiated, the diazide group is dissipated outside the photo-resist layer in the form of nitrogen gas to result in relaxation of the internal stress within the photo-resist layer, and it becomes softened.
As such, in the pre-treatment of the above (ii), by the irradiation of the ultraviolet rays having the wavelength of from 300 to 500 nm at its intensity of 100 mJ/cm2 or above, there will occur no cracks in the photo-resist layer, even when it is immersed in the etchingliquid immediately after the ultraviolet ray irradiation.
After the abovementioned pre-treatment, the silicone ladder type resin is etched with the photo-resist patterns as a mask.
The etching solution for the silicone ladder type resin should necessarily be those solvents which dissolve this resin but do not dissolve the phenolic type positive photo-resist layer. As the solvents for such resin, there have been known various types of solvents such as halogenated hydrocarbon type solvents, ether type solvents, benzene type solvents, alkoxybenzene type solvents, cyclic ketone type solvents, N-methylpyrrolidone, N,N'-dimethylformamide, and others (vide: Japanese Unexamined Patent Publication No.
94955/1980). As the results of making various studies on these solvents, the present inventors discovered that those aromatic type solvents such as benzene, = alkylbenzene (toluene, xylene, and so on), and alkoxybenzene (methoxybenzene, ethoxybenzene, and so on) were suitable as the solvents which did not dissolve the phenolic type positive photo-resist layer.
The rate of etching with these etching liquids should preferably be at an appropriate rate selected from a range between 1 and 10 ~m/min. so as to complete the etching of the silicone ladder type resin in a time period of from 30 to 150 sec.. The adjustment of the etching rate can be done easily by mixing, for example, xylene, etc., depending upon the molecular weight of the silicone ladder type resin.
Preferrred examples of the etching liquid are: a mixed solvent of alkoxybenenze and xylene with a volume ratio of the former being 18% or above, a mixed solvent of toluene and xylene with a volume ratio of the former being 20% or above, a mixed solvent of benzene and xylene with a volume ratio of the former being 25% or above, and others. The etching is usually done at a constant temperature level properly selected from a range between 20 and 28C.
In the following, the present invention will be explained more specifically with reference to its preferred examples.
To a silicone ladder type resin having a molecular weight of about 120,000, in which Rl shown in the aforementioned general formula (I) is a phenyl group, and R2 is hydrogen, there was added benzene to adjust the viscosity of the resin to 3,000 cps. Subsequently, the thus prepared solution was applied onto the surface of a silicon wafer by means of a spinner rotating at a rate of 2,000 rpm.
Thickness of the film as formed was 10 ~m.
The thus formed film layer was dried at a temperature of 150C for 30 min., after which a photo-resist material OFPR*-800 (a product of Tokyo Ohka Kogyo K.K.) was applied onto this resin layer by means of the spinner rotating at a rate of 2,000 rpm. Thickness of the photo-resist layer as formed was 2 ~m.
After drying the photo-resist layer at a temperature of 80C for 30 min., a photo-mask was closely contacted on this photo-resist layer. Then, ultraviolet rays was irradiated onto it by means of an ultra-high pressure *trademark 20~00:~0 mercury lamp, followed by immersing the same in a ` F~ developing liquid for "OFPR" for 60 sec. to thereby ~- dissolve the exposed portion on the photo-resist. The thus developed photo-resist layer on the silicon wafer was rinsed with pure water, and then dried at a -~~ temperature of 80C for 30 min...... As the result, there was formed a photo-resist pattern.
Thereafter, the photo-resist layer was heat-treated at a temperature of 130C for 30 min., followed by maintaining the same at room temperature for four hours.
Subsequently, the photo-resist layer was immersed in an etching liquid composed of a mixture of toluene and xylene with a volume ratio between them being 1/1 at 25C
for 60 sec., thereby etching the silicone ladder type resin. After the etching, the thus treated photo-resist layer was observed through a microscope. No cracks were found to have occurred.
Next, the photo-resist layer was removed with use of a photo-resist release agent, thereby obtaining a silicone ladder type resin film, on which a predetermined pattern had been transferred. The size of the opening on the resin film was 24 ~m square with a mask size of 20 ~m square. Also, observation through a scanning electron microscope indicated that the result of the treatment was satisfactory.
Benzene was added to the silicone ladder type resin rcll~ark 2010(~30 _ as used in Example 1 above to adjust the viscosity of the resin to 2,700 cps. The thus obtained resin solution was applied onto the silicon wafer by means of a spinner rotating at a rate of 2,000 rpm. Thickness o~ the layer as formed was 5 ~m.
The resin layer as formed was dried at a temperature of 150C for 30 min., and then, following the same procedures as in Example 1 above, the photo-resist pattern having a pattern size of 20 ~m square was formed.
After the heat-treatment at 140C for 30 min., the photo-resist pattern was held at room temperature for five hours. Subsequently, it was immersed in ethoxybenzene as the etching liquid at a temperature of 25C for 60 sec., thereby etching the silicone ladder type resin.
Next, the photo-resist layer was removed with use of a photo-resist release agent, thereby obtaining a silicone ladder type resin film, on which a predetermined pattern had been transferred. The size of the opening on the resin film was 23 ~m square with a mask size of 20 ~m square. Also, the shape of the pattern was satisfactory.
To a silicone ladder type resin having a molecular weight of about 150,000, in which Rl shown in the afore-mentioned general formula (I) is a phenyl group, and R2is hydrogen, there was added toluene to adjust the viscosity of the resin to 5,000 cps. Subsequently, the thus prepared solution was applied onto the surface of a silicon wafer by means of a spinner rotating at a rate of 2,000 rpm. Thickness of the film as formed was 20 ~m.
The resin layer as formed was dried at a temperature of 150C for 30 min., and then, following the same procedures as in Example 1 above, a photo-resist pattern having a pattern size of 20 ~m square was formed.
Thereafter, ultraviolet rays at an intensity of 300mJ/cm2 was irradiated over the entire surface of the photo-resist pattern by means of an ultra-high pressure mercury lamp, from which the rays of~a wavelength shorter than 300 nm had been removed. After this, the photo-resist pattern was immersed in a mixed solvent of methoxybenzene and xylene with a volume ratio between them being 1/2, at a temperature of 25C for 60 sec. to etch the silicone ladder type resin. In the next place, the photo-resist layer was removed with use of a photo-resist release agent, thereby obtaining the silicone ladder type resin, on which a predetermined pattern had been transferred.
The size of the opening on the resin film was 29 ~m square. Also, the shape of the photo-resist pattern was found satisfactory.
To a silicone ladder type resin having a molecular weight of about 100,000, in which Rl shown in the afore-mentioned general formula (I) is a methyl group and R2 is hydrogen, there was added benzene to adjust the viscosity 20~0030 of the resin to 2,900 cps. Subsequently, the thus prepared solution was applied onto the surface of a silicon wafer by means of a spinner rotating at a rate of 2,000 rpm. Thickness of the film as formed was 8 ~m.
The resin layer as formed was dried at a temperature of 140C for 30 min., and then, following the same procedures as in Example 1 above, the photo-resist pattern having a pattern size of 20 ~m sqaure was formed.
Thereafter, the photo-resist layer was heat-treated at a temperature of 150C for 30 min., followed by leaving the same at room temperature for ten hours.
Subsequently, the photo-resist layer was immersed in a mixed solution of methoxybenzene and xylene with a volume ratio between them being 1/3 at 25C for 60 sec., thereby etching the silicone ladder type resin. After the etching, the thus treated photo-resist layer was observed through a microscope. No cracks were found to have occurred.
Next, the photo-resist layer was removed with use of a photo-resist release agent to thereby obtain the silicone ladder type resin, on which a predetermined pattern had been transferred. The size of the opening on the resin film was 23 ~m square. Also, the shape of the photo-resist pattern was found satisfactory.
Benzene was added to the silicone ladder type resin as used in Example 4 above to adjust the viscosity of the resin to 2,400 cps. The thus obtained resin solution was applied onto a silicon wafer by means of a spinner rotating at a rate of 2,000 rpm. Thickness of the layer as formed was 3.0 ,um.
The resin layer as formed was dried at a temperature of 140C for 30 min., and then, following the same procedures as in Example 1 above, the photo-resist pattern having a pattern size of 10 ~m square was formed.
Thereafter, the ultraviolet rays at an intensity of 200mJ/cm2 was irradiated over the entire surface of the photo-resist pattern by means of an ultra-high pressure mercury lamp, from which the rays of a wavelength shorter than 300 nm had been removed. After this, the photo-resist pattern was immersed in ethoxybenzene at a temperature of 25C for 30 sec., whereby etching the silicone ladder type resin. In the next place, the photo-resist layer was removed with use of a photo-resist release agent to thereby obtain the silicone ladder type resin, on which a predetermined pattern had been transferred. The size of the opening on the resin film was 10.9 ~m square. Also, the shape of the photo-resist pattern was found satisfactory.
Benzene was added to the silicone ladder type resin as used in Example 1 above to adjust the viscosity of the resin to 2,800 cps. The thus obtained resin solution was applied onto a silicon wafer by means of a spinner 20~0030 rotating at a rate of 2,000 rpm. Thickness of the layer as formed was 6 ~m. Subsequently, following the same procedures as in Example 1 above, a photo-resist pattern having a size of 10 ,um square was formed, after which the ultraviolet rays at an intensity of 200mJ/cm2 were irradiated over the entire surface of the photo-resist pattern, and then it was maintained at room temperature for five hours.
Subsequently, the photo-resist pattern was immersed in a mixed solvent of toluene and xylene with a volume ratio between them being 2/3, as the etching liquid, at a temperature of 25C for 50 sec., thereby etching the silicone ladder type resin. After the etching, the thus treated photo-resist was observed through a microscope.
No cracks were found to have occurred.
Next, the photo-resist layer was removed with use of a photo-resist release agent to thereby obtain the silicone ladder type resin, on which a predetermined pattern had been transferred. The size of the opening on the resin film was 12.5 ~m square with the photo-resist pattern having a mask size of 10 ~m square.
A benzene solution of the silicone ladder type resin as used in Example 4 above was applied on a silicon wafer by means of a spinner rotating at a rate of 3,000 rpm.
Thickness of the resin layer as formed was 5.0 ~m.
The resin layer as formed was dried at a temperature of 140C for 30 min., and then, following the same procedures as in Example 1 above, the photo-resist pattern having a pattern size of 10 ~m square was formed.
Thereafter, the ultraviolet rays at an intensity of 250mJ/cm2 was irradiated over the entire surface of the photo-resist pattern by means of an ultra-high pressure mercury lamp, from which the rays of a wavelength shorter than 300 nm had been removed.
After this, the photo-resist pattern was immersed in a mixed solution of toluene and xylene with a volume ratio between them being 2/3, as the etching liquid, at a temperature of 25C for 50 sec., thereby etching the silicone ladder type resin. After the etching, there could be found no cracks occurred in the photo-resist pattern.
In the next place, the photo-resist layer was removed with use of a photo-resist release agent to thereby obtain the silicone ladder type resin, on which a predetermined pattern had been transferred. The size of the opening on the resin film was 13.0 ~m square with the photo-resist pattern having a mask size of 10 ~m square.
As has so far been described in the foregoing, according to the present invention, it is possible to etch the silicone ladder type resin in a short period of time with use of an aromatic type solvent, and to transfer a predetermined pattern with satisfaction.
Claims (7)
1. A method for transferring patterns on a silicone ladder type resin, which comprises:
applying onto a substrate an organic solution containing a silicone ladder type resin to be represented by the following general formula (I):
(I) wherein: each R1, independently, denotes a phenyl group or a lower alkyl group, each R2, independently, denotes a hydrogen atom or a lower alkyl group, and n represents an integer of from 5 to 1,000;
drying the thus applied resin layer;
thereafter applying onto said resin layer a cresol novolac type positive photo-resist;
forming a predetermined pattern in said photo-resist layer;
subjecting said photo-resist layer to pretreatment by heating said photo-resist layer at a temperature ranging from 125 to 160°C for 15 to 60 min., and maintaining said photo-resist layer at room temperature for three hours or longer, or by irradiating with ultraviolet rays having a wavelength of from 300 to 500 nm over the entire surface of said photo-resist layer;
etching said silicone ladder type resin; and removing said photo-resist layer by the use of a photo-resist release agent, to obtain a silicone ladder type resin film on which a predetermined pattern has been transferred.
applying onto a substrate an organic solution containing a silicone ladder type resin to be represented by the following general formula (I):
(I) wherein: each R1, independently, denotes a phenyl group or a lower alkyl group, each R2, independently, denotes a hydrogen atom or a lower alkyl group, and n represents an integer of from 5 to 1,000;
drying the thus applied resin layer;
thereafter applying onto said resin layer a cresol novolac type positive photo-resist;
forming a predetermined pattern in said photo-resist layer;
subjecting said photo-resist layer to pretreatment by heating said photo-resist layer at a temperature ranging from 125 to 160°C for 15 to 60 min., and maintaining said photo-resist layer at room temperature for three hours or longer, or by irradiating with ultraviolet rays having a wavelength of from 300 to 500 nm over the entire surface of said photo-resist layer;
etching said silicone ladder type resin; and removing said photo-resist layer by the use of a photo-resist release agent, to obtain a silicone ladder type resin film on which a predetermined pattern has been transferred.
2. The method according to Claim 1, wherein said pretreatment is effected by heating said photo-resist layer at a temperature ranging from 130 to 150°C for 30 to 45 min., and maintaining said photo-resist layer at room temperature for four hours or longer.
3. The method according to Claim 1, wherein the irradiating quantity of said ultraviolet rays is 50 mJ/cm2 or above.
4. The method according to Claim 3, wherein the irradiating quantity of said ultraviolet rays is 100 mJ/cm2 or above.
5. The method according to Claim 1, wherein said etching is effected at a temperature range of from 20 to 28°C.
6. The method according to Claim 1, wherein said etching is effected at a range of from 1 to 10 µm/min.
7. The method of any one of Claims 1 to 6 using an etching liquid selected from the group consisting of: a mixture, by volume, of at least 18% alkoxybenzene and xylene; a mixture, by volume, of at least 20% toluene and xylene; and a mixture, by volume, of a least 20% benzene and xylene.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1044326A JP2542075B2 (en) | 1989-02-23 | 1989-02-23 | Method for transferring pattern to silicone ladder resin and etching solution used therefor |
| JP44326/1989 | 1989-02-23 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2010030A1 CA2010030A1 (en) | 1990-08-23 |
| CA2010030C true CA2010030C (en) | 1997-01-21 |
Family
ID=12688379
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002010030A Expired - Fee Related CA2010030C (en) | 1989-02-23 | 1990-02-14 | Method for transferring patterns on silicone ladder type resin and etching solution used in such method |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US5087553A (en) |
| JP (1) | JP2542075B2 (en) |
| KR (1) | KR930003878B1 (en) |
| CA (1) | CA2010030C (en) |
| DE (1) | DE4005345C2 (en) |
| GB (2) | GB2228582B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2646289B2 (en) * | 1990-06-01 | 1997-08-27 | 富士写真フイルム株式会社 | Resist composition |
| JP2752786B2 (en) * | 1990-11-19 | 1998-05-18 | 三菱電機株式会社 | Color filter surface protective film |
| JP2547944B2 (en) * | 1992-09-30 | 1996-10-30 | インターナショナル・ビジネス・マシーンズ・コーポレイション | Method of forming sub-half micron pattern by optical lithography using a bilayer resist composition |
| JP2923408B2 (en) * | 1992-12-21 | 1999-07-26 | 三菱電機株式会社 | Method for producing high-purity silicone ladder polymer |
| TWI255957B (en) * | 1999-03-26 | 2006-06-01 | Hitachi Ltd | Liquid crystal display device and method of manufacturing the same |
| KR100633655B1 (en) | 1999-12-22 | 2006-10-11 | 미쓰비시덴키 가부시키가이샤 | Sensor device and method of manufacture thereof |
Family Cites Families (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5348947A (en) * | 1976-10-18 | 1978-05-02 | Oki Electric Ind Co Ltd | Photoethcing method for oxidized film |
| JPS5594955A (en) * | 1979-01-12 | 1980-07-18 | Hitachi Ltd | Film-forming coating solution |
| EP0021818B1 (en) * | 1979-06-21 | 1983-10-05 | Fujitsu Limited | Improved electronic device having multilayer wiring structure |
| JPS6046826B2 (en) * | 1979-06-21 | 1985-10-18 | 富士通株式会社 | semiconductor equipment |
| JPS5633827A (en) * | 1979-08-29 | 1981-04-04 | Seiko Epson Corp | Photo etching method including surface treatment of substrate |
| JPS56125855A (en) * | 1980-03-07 | 1981-10-02 | Fujitsu Ltd | Manufacture of semiconductor device |
| JPS56135928A (en) * | 1980-03-27 | 1981-10-23 | Fujitsu Ltd | Forming method for pattern of silicone resin |
| JPS57154830A (en) * | 1980-10-31 | 1982-09-24 | Fujitsu Ltd | Forming method for pattern and structure of laminating |
| US4409319A (en) * | 1981-07-15 | 1983-10-11 | International Business Machines Corporation | Electron beam exposed positive resist mask process |
| JPS59161827A (en) * | 1983-03-04 | 1984-09-12 | Nippon Telegr & Teleph Corp <Ntt> | Method for processing insulating film |
| JPS60262150A (en) * | 1984-06-11 | 1985-12-25 | Nippon Telegr & Teleph Corp <Ntt> | Intermediate layer for 3-layer resist material and method for using it |
| JPS6314432A (en) * | 1986-07-07 | 1988-01-21 | Nippon Telegr & Teleph Corp <Ntt> | Pattern formation |
| JPH0740547B2 (en) * | 1987-03-24 | 1995-05-01 | ウシオ電機株式会社 | Resist processing method |
| JPS63301521A (en) * | 1987-06-01 | 1988-12-08 | Nec Corp | Formation of pattern |
| JPS6424424A (en) * | 1987-07-21 | 1989-01-26 | New Japan Radio Co Ltd | Manufacture of semiconductor device |
| JP2608429B2 (en) * | 1987-11-09 | 1997-05-07 | 東レ・ダウコーニング・シリコーン株式会社 | Pattern forming material and pattern forming method |
-
1989
- 1989-02-23 JP JP1044326A patent/JP2542075B2/en not_active Expired - Lifetime
-
1990
- 1990-02-05 US US07/475,307 patent/US5087553A/en not_active Expired - Lifetime
- 1990-02-08 GB GB9002812A patent/GB2228582B/en not_active Expired - Fee Related
- 1990-02-14 CA CA002010030A patent/CA2010030C/en not_active Expired - Fee Related
- 1990-02-20 DE DE4005345A patent/DE4005345C2/en not_active Expired - Fee Related
- 1990-02-23 KR KR1019900002319A patent/KR930003878B1/en not_active IP Right Cessation
- 1990-07-24 GB GB9016212A patent/GB2237577B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| GB2228582A (en) | 1990-08-29 |
| DE4005345C2 (en) | 1995-06-29 |
| GB2228582B (en) | 1993-06-16 |
| DE4005345A1 (en) | 1990-08-30 |
| US5087553A (en) | 1992-02-11 |
| GB2237577A (en) | 1991-05-08 |
| KR930003878B1 (en) | 1993-05-14 |
| KR900013576A (en) | 1990-09-06 |
| GB2237577B (en) | 1992-11-04 |
| JPH02222537A (en) | 1990-09-05 |
| CA2010030A1 (en) | 1990-08-23 |
| GB9016212D0 (en) | 1990-09-05 |
| GB9002812D0 (en) | 1990-04-04 |
| JP2542075B2 (en) | 1996-10-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4615782A (en) | Intermediate layer material of three-layer resist system and method of forming resist pattern | |
| EP0043458B1 (en) | Process for forming a metallurgy interconnection system | |
| EP0114229B1 (en) | Method of forming a lift-off mask with improved oxygen barrier layer | |
| US5470693A (en) | Method of forming patterned polyimide films | |
| US4430153A (en) | Method of forming an RIE etch barrier by in situ conversion of a silicon containing alkyl polyamide/polyimide | |
| KR100682639B1 (en) | Photoresist removal process using forming gas plasma | |
| KR100893120B1 (en) | Top coat for lithography processes | |
| JP2997124B2 (en) | Photopaintable coating from hydrogensilsesquioxane resin | |
| JP4336310B2 (en) | Silicon-containing antireflection layer as hard mask layer and method for forming the same | |
| US6764812B1 (en) | Plasma deposited selective wetting material | |
| KR20040093742A (en) | Process For Producing Semiconductor Device And Semiconductor Device | |
| JPH0527444A (en) | Silica base material irreflexive planed layer | |
| CA2010030C (en) | Method for transferring patterns on silicone ladder type resin and etching solution used in such method | |
| US7056824B2 (en) | Electronic device manufacture | |
| GB2154330A (en) | Fabrication of semiconductor devices | |
| US4868096A (en) | Surface treatment of silicone-based coating films | |
| JPH0368904B2 (en) | ||
| KR100666023B1 (en) | Antireflective silicon-containing compositions as hardmask layer | |
| KR19990023964A (en) | Manufacturing method of insulating thin film | |
| JPH07311469A (en) | Removing solution for residue of resist after removal on polyimide resin film and production of pattern of polyimide resin film | |
| JPS6314432A (en) | Pattern formation | |
| JPH06275511A (en) | Forming method of polyimide pattern | |
| JPH0669186A (en) | Method of processing pattern of silica film | |
| JPH06196474A (en) | Polyimide resin film scum removing liquid and manufacture of polyimide resin film pattern | |
| JP2004157351A (en) | Method for manufacturing polymer optical waveguide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| MKLA | Lapsed |