CA1181627A - Radiation-sensitive composition containing an azide compound and an iodine compound - Google Patents
Radiation-sensitive composition containing an azide compound and an iodine compoundInfo
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- CA1181627A CA1181627A CA000455393A CA455393A CA1181627A CA 1181627 A CA1181627 A CA 1181627A CA 000455393 A CA000455393 A CA 000455393A CA 455393 A CA455393 A CA 455393A CA 1181627 A CA1181627 A CA 1181627A
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Abstract
Abstract:
The invention relates to a radiation-sensitive composition comprising a polymer and an iodine-containing azide compound, at least a part of which can be fixed substantially in the polymer by exposure to a radiation, or a radiation-sensitive composition comprising a polymer, an azide compound, and an iodine compound, at least a part of which can be fixed substantially in the polymer by exposure to a radiation. This composition can be subjected to dry development with oxygen plasma after the exposure to radiation followed by heating.
The invention relates to a radiation-sensitive composition comprising a polymer and an iodine-containing azide compound, at least a part of which can be fixed substantially in the polymer by exposure to a radiation, or a radiation-sensitive composition comprising a polymer, an azide compound, and an iodine compound, at least a part of which can be fixed substantially in the polymer by exposure to a radiation. This composition can be subjected to dry development with oxygen plasma after the exposure to radiation followed by heating.
Description
Radiation-sensitive cornposition and pattern-formation method usin~ the same The present invention relates to a radiation~sensitive composition and pattern-formation method using the same.
In conventional pattern-ormation methods, a coating film of a radiation-sensitive composition is exposed to radiation of a given pattern and then the coating film is immersed in a liquid developer (usually an organic solvent), or the liquid developer is sprayed over the surface of the coating film, to form a pattern by the wet development technique~ However, this wet development technique has a disadvantage in that the negative-working composition used in a system employing a crosslinking reaction becomes swollen by the developer. This constitutes a serious obstacle to the formation of an accurate developed image of the pattern.
A dry development technique has been proposed to overcome this disadvantage wherein plasma is used for ~evelopment. If dry development is effectea until a region of a negative working composition, i.e. an unexposed region, has been completely removed, the surface of the e~posed region that must remain is also etched to a considerable extent, and the normalized film remaining (the ratio of the thickness of the remaining film to the initial film thickness) is considerably reduced. Thus, if this method is to be employed in practice, many problems remain to be overcome.
Summary of the Invention -An object of the present invention is to provide a radiation sensitive composition suitable for dry development, and a pattern-forma~ion method using the same.
According to one aspect of the invention there is provided a radiation-sensitive composition comprising.
an azide compound selected from the group consisting of a compound of the general formula:
~A
Z Z
wherein A represents an element or a substituent selected from the group consisting of O, S, CH~, CH2CH2, SO2, S2, CO, COO, SO3, CH=CH and CH=CRCO, and X, Y and Z each represent an element or a substituent selected from the group consisting of an azido group, hydrogen, alkyl group, nitro group, halogen, amino group, monoalkylamino group, alkoxy group, hydroxyl group, sulfonic acid group, sulfonic acid ester group, carboxylic acid group and carboxylic acid ester group; and a compound of the general formula:
~3 ~
y wherein X, Y and Z each represent an element or substit-uent selected from the group consisting of an azide group, hydrogen, alkyl group, nitro group, halogen, amino group, monoalkylamino group, alkoxyl group, hydroxyl group, sul-fonic acid group, sulfonic acid ester group, carboxylic acid group and car~oxylic acid ester group; an iodine .
: :, compound at least a part of which can be fixecl substan tially in a polymer layer by exposure to a radiation;
and a polymer substantially having compatibility with the azide compound and the iodine compound.
According to ano~her aspect of the invention there is provided a method of forming a pattern character-ized by comprising the step,s of forming a coating film of a radiation-sensitive composition comprising an azide compound, an iodine compound at least a part of which can be fixed substantially in a poly-mer layer by exposure to a radiation and a polymer substantially having compatibility with the azide compound and the iodine compound, exposing the coating film to a radiation having a desired pat-tern, heating the coating film to remove the iodine compound from an unexposed region of the coating film and exposing the coating film to an oxygen-containing plasma to remove the unexposed part.
Other apsect~ of this invention are claimed in our copending Canadian patent application Serial No.
407,336 filed on July 15, 1982, of which the present application is a division.
Preferred embodiments of the present invention are described in the following with reference to the accompanying drawings, in which:
Fig. 1 is a graph showing the change in film thickness of certain compositions with exposure to plasma;
Fig. 2 and Fig. 3 are similar graphs for specific 0 compositions described in the examples.
- 2a -In the radiation-sensitive composition of the present invention an iodine-containing azide com-pound may be replaced with an azide compound and an organic iodine compound, at least a part of which can be fixed substantially in the polymer by exposure to radiation. Thus, the composition may comprise an azide compound, an organic iodine compound at least a part of which can be fixed substantially in a polymer layer by exposure to a - 2b -radiation and a polymer substantially having compatibility with the azide compound and the iodine compound.
The pattern-formation method involves the steps of forming a coating film of the radiation-sensitive composition, e~posing the coating film to radiation having a desired pattern, heating the coating film to remove the iodine-containing azide compound or iodine compound in the unexposed regions and exposing the coating film to an oxygen-containing plasma to remove the unexposed part~
The term "radiation" herein re~ers to visible light, ultraviolet light, X-rays, electron beams and ion beams in a broad sense.
As though the mechanisms of the reaction or decomposition of the azide compound caused by exposure to the radiation have not been elucidated yet, it is believed that at least an iodine-containing moiety of the compound is substantially fixed in the polymer layer. It is believed that by the presence of iodine, a non-volatile, oxygen-containing, plasma-resi~tant substance is formed on the surface layer in the oxygen-conta;ning plasma. This i5 a property peculiar to iodine compounds. Chlorine- or bromine~containing compounds do not have such a property.
The reason why an iodine-containing azide compound is substantially ixed in the polymer layer in the composition containing said compound is that said compound or a part thereof is directly linked with the polymer or, otherwise~ converted into its dimer or polymer and, there.ore, it is not dissipated even when heated.
When the composition containing the iodine compound and azide compound is used, there are two cases, i.e. (1) the azide compound is directly linked with both the iodine compound and the polymer (particularly when the azide compound is a d;azide compound) and (2~ a part of the azide compound is linked with the iocline compound, whereby the iodine compound is not dissipated even when heated and the other part of the azide compound is linked with the polymer to alter its solubility. The term "azide compound" includes also compounds formed by the photolysis and converted compounds. The mechanism described above is only an estimation and it does not exert any limitation on the scope of the invention~
The heating temperature of th~ coating film should be such that the iodine-containing azide compound, or the iod$ne compound, in the unexposed region is dissipated.
In other words, it should be higher than the sublimation temperature or boiling point of said compound. The heating temperature is, therefore, variable depending on the particular iodine-containing azide compound or iodine compound used If the coating film is placed under reduced pressure, the heating temperature can be reduced to some extent. The upper limit of the heating temperature should be below the decompositlon point of the polymer.
The term "polymer substantially compatible with the azide compound or iodine compound" refers to a polymer capable of forming a coating film including said compound and having a substantially homogeneous composition. Even if polymer Pl is incompatible with the compound, a mixture of polymer Pl with another polymer P2 compatible with polymer Pl may be used, if this mixture (Pl ~ P2) is compatible with said compound.
The polymer should preferably have very good film-forming characteristics~
As for the proportion of the polymer to the iodine-containing azide compound in the radiation-sensitive composition, ;t is preferred that the amount of the iodine-containing azide compound be 10-80 wt.%, particularly 30-60 wt.%, based on the weight of composition.
Fig~ l shows changes in film thickness observed when films having various proportions of the polymer and the azide compound were exposed to oxygen plasma. It should be taken into consideration that the initial thicknesses were different from one another and about 50~ of the coating film containing 20 wt.% of the azide compound (2 ,4 ,6 -triiodophenyl-4~-azido-benzoate) remained even after exposure to oxygen plasma for about 8 min, while a coating film containing only the polymer (polyvinylphenol~
disappeared after exposure to oxygen plasma for about 8 min. About 60% and 75% of coating Eilms containing 33 wt.% and 50 wt.%, respectively, of the same azide compound remained after exposure to oxygen plasma for 8 min. This fact indicates that the amount of film remaining (normal-ized film) is increased as the amount of the iodine-containing azide compound is increased. However, it will be apparent from the above description that a certain amount of the polymer is necessary for ixing the azide compound. Therefore, an amount in the above-mentioned range is preferred. The plasma irradiation conditions are shown in Example l given below.
The proportion of the polymer, organic iodine compound 3G and azide compound in the radiation-sensitive composition comprising these three compounds is preferably l:G.1-3:0.05-2, particularly 1:0.4-2:0.1-1, by weight.
Experimental data of the resis~ance of the composltion to oxygen plasma will be shown in Ta~le 1, which shows relative removal rates of films by oxygen pla~sma measured after hardenin~ of coating films comprising polystyrene, 3,3'-diaziododiphenyl sulfone and iodoform by light. It is apparent from Table 1 that oxygen plasma resistance is increased remarkably as the amount of iodoform (iodine compound) is increased. I~ can be seen, therefore, that the coating film can be used as an oxygen plasma-resisting mas~. The experimental conditions were the same as in Fig. 1.
Table 1 .
Polystyrene Diazide com- Iodoform Relative (part by wt.) pound (part by wt.) removal (part by w~.l rate of film 1 0.2 0 1.0 1 0.2 0.24 0.77 1 0.2 0 S~ Q.4~
l 002 1.53 0.33 , The followinq compounds can be used as the polymer:
poly-N-vlnyl-carbazole, polyacenaphthylene, polyvinylidene fluoride, poly-N-vinylpyrrolidone, polyglycidyl methacrylate, polystyrene, polyalkyl methacrylates, cyclic polyisoprene, poly-4-methylstyrene, poymethacrylonitrile, poly-4~vinylpyridine, poly-4-bromostyrene, polyvinyl-benzyl chloride, polybutadiene, poly-4-chlorostyrene, epoxidized polybutadiene, polyvinyi acetate, polyvinyl cinnamate, polyvinyl chloride, pvlychloroprene, poly-vinyl bromide, polyepichlorohydrin, polyvinylphenol, polyvinyl alcohol, polyvinylidene chloride, poly-acrylonitrile, poly-~methylstyrene, polymethyl isopropenyl ketone, polyacrylamide, polyvinyl meth~l ketone, polybu~ene-l sulfone, polystyrene sulfone, polyisobutylene, a phenolic resin such as novolak resin, styrene/maleic anhydride copolymer, cellulose acetate hydrogenphthala~e, polyvinyl hydroxybenzoate, polyvinyl hydroxvbenzal or acrylic resin. These poly-mers may also be used as components of copolymers.
Further, polymers other than those mentioned above having film-forming properties and compatibility with said compounds may also be used. These polymers may be used ~ither alone or in the form of a mixture of two or more of them.
Polymers containing a benzene ring or rubbery polymers are preferred from the viewpoint of their dry etching resistance.
When the pattern formation method of the present invention is carried out according to the dry development technique, the iodine-containing polymer cannot substantially be used as the polymer. The reason therefor is that even if it is attempted to remove the iodine-containing compound from the unexposed region of the coating film by heating, the iodine~containing polymer remains in the film, and it exhibits a resistance to oxygen plasma. However, it will be understood from, for examplel Table 1 given above that if the iodine content is low, the difference in the relative removal rate of film in this case from that of iodine-free film is insignificant. Since the iodine compound or iodine-containing azide compound is present in the exposed region, the total of iodine contained therein and that oontained in the polymer is relatively large and the relative xemoval rate of the film is reduced. Thus, even if the polymer contains only a small amount of iodine, a pattern may be formed in the coating film according to the dry development.
The following compounds of general formula (I) are given as examples of azide compounds containing iodine:
N3 ~ I
x (I) R y wherein Rx and Ry each represent an element or atomic group selected from the group consisting of hydrogen, an alkyl group, a nitro group, halogen, an amino group, a monoalkylamino group, an acyl group, a dialkylamino group, an alkoxyl group, a hydroxyl group, a sulfonic acid gro~p, a sulfonio acid ester group, a carboxylic acid gro~p and a carboxylic acid ester group.
The Eollowing are examples of these compounds:
p-azidoiodobenzene, 2,6-diiodo-4-nitroazido-benzene, 2-chloro-4-iodoazidobenzene, 2,6-dichloro-4-iodoazido-benzene, 2-bromo-4-iodoazidobenzene, 2,6-dibromo-4-iodoazidobenzene, 2-methyl-4-iodoazidobenzene and
In conventional pattern-ormation methods, a coating film of a radiation-sensitive composition is exposed to radiation of a given pattern and then the coating film is immersed in a liquid developer (usually an organic solvent), or the liquid developer is sprayed over the surface of the coating film, to form a pattern by the wet development technique~ However, this wet development technique has a disadvantage in that the negative-working composition used in a system employing a crosslinking reaction becomes swollen by the developer. This constitutes a serious obstacle to the formation of an accurate developed image of the pattern.
A dry development technique has been proposed to overcome this disadvantage wherein plasma is used for ~evelopment. If dry development is effectea until a region of a negative working composition, i.e. an unexposed region, has been completely removed, the surface of the e~posed region that must remain is also etched to a considerable extent, and the normalized film remaining (the ratio of the thickness of the remaining film to the initial film thickness) is considerably reduced. Thus, if this method is to be employed in practice, many problems remain to be overcome.
Summary of the Invention -An object of the present invention is to provide a radiation sensitive composition suitable for dry development, and a pattern-forma~ion method using the same.
According to one aspect of the invention there is provided a radiation-sensitive composition comprising.
an azide compound selected from the group consisting of a compound of the general formula:
~A
Z Z
wherein A represents an element or a substituent selected from the group consisting of O, S, CH~, CH2CH2, SO2, S2, CO, COO, SO3, CH=CH and CH=CRCO, and X, Y and Z each represent an element or a substituent selected from the group consisting of an azido group, hydrogen, alkyl group, nitro group, halogen, amino group, monoalkylamino group, alkoxy group, hydroxyl group, sulfonic acid group, sulfonic acid ester group, carboxylic acid group and carboxylic acid ester group; and a compound of the general formula:
~3 ~
y wherein X, Y and Z each represent an element or substit-uent selected from the group consisting of an azide group, hydrogen, alkyl group, nitro group, halogen, amino group, monoalkylamino group, alkoxyl group, hydroxyl group, sul-fonic acid group, sulfonic acid ester group, carboxylic acid group and car~oxylic acid ester group; an iodine .
: :, compound at least a part of which can be fixecl substan tially in a polymer layer by exposure to a radiation;
and a polymer substantially having compatibility with the azide compound and the iodine compound.
According to ano~her aspect of the invention there is provided a method of forming a pattern character-ized by comprising the step,s of forming a coating film of a radiation-sensitive composition comprising an azide compound, an iodine compound at least a part of which can be fixed substantially in a poly-mer layer by exposure to a radiation and a polymer substantially having compatibility with the azide compound and the iodine compound, exposing the coating film to a radiation having a desired pat-tern, heating the coating film to remove the iodine compound from an unexposed region of the coating film and exposing the coating film to an oxygen-containing plasma to remove the unexposed part.
Other apsect~ of this invention are claimed in our copending Canadian patent application Serial No.
407,336 filed on July 15, 1982, of which the present application is a division.
Preferred embodiments of the present invention are described in the following with reference to the accompanying drawings, in which:
Fig. 1 is a graph showing the change in film thickness of certain compositions with exposure to plasma;
Fig. 2 and Fig. 3 are similar graphs for specific 0 compositions described in the examples.
- 2a -In the radiation-sensitive composition of the present invention an iodine-containing azide com-pound may be replaced with an azide compound and an organic iodine compound, at least a part of which can be fixed substantially in the polymer by exposure to radiation. Thus, the composition may comprise an azide compound, an organic iodine compound at least a part of which can be fixed substantially in a polymer layer by exposure to a - 2b -radiation and a polymer substantially having compatibility with the azide compound and the iodine compound.
The pattern-formation method involves the steps of forming a coating film of the radiation-sensitive composition, e~posing the coating film to radiation having a desired pattern, heating the coating film to remove the iodine-containing azide compound or iodine compound in the unexposed regions and exposing the coating film to an oxygen-containing plasma to remove the unexposed part~
The term "radiation" herein re~ers to visible light, ultraviolet light, X-rays, electron beams and ion beams in a broad sense.
As though the mechanisms of the reaction or decomposition of the azide compound caused by exposure to the radiation have not been elucidated yet, it is believed that at least an iodine-containing moiety of the compound is substantially fixed in the polymer layer. It is believed that by the presence of iodine, a non-volatile, oxygen-containing, plasma-resi~tant substance is formed on the surface layer in the oxygen-conta;ning plasma. This i5 a property peculiar to iodine compounds. Chlorine- or bromine~containing compounds do not have such a property.
The reason why an iodine-containing azide compound is substantially ixed in the polymer layer in the composition containing said compound is that said compound or a part thereof is directly linked with the polymer or, otherwise~ converted into its dimer or polymer and, there.ore, it is not dissipated even when heated.
When the composition containing the iodine compound and azide compound is used, there are two cases, i.e. (1) the azide compound is directly linked with both the iodine compound and the polymer (particularly when the azide compound is a d;azide compound) and (2~ a part of the azide compound is linked with the iocline compound, whereby the iodine compound is not dissipated even when heated and the other part of the azide compound is linked with the polymer to alter its solubility. The term "azide compound" includes also compounds formed by the photolysis and converted compounds. The mechanism described above is only an estimation and it does not exert any limitation on the scope of the invention~
The heating temperature of th~ coating film should be such that the iodine-containing azide compound, or the iod$ne compound, in the unexposed region is dissipated.
In other words, it should be higher than the sublimation temperature or boiling point of said compound. The heating temperature is, therefore, variable depending on the particular iodine-containing azide compound or iodine compound used If the coating film is placed under reduced pressure, the heating temperature can be reduced to some extent. The upper limit of the heating temperature should be below the decompositlon point of the polymer.
The term "polymer substantially compatible with the azide compound or iodine compound" refers to a polymer capable of forming a coating film including said compound and having a substantially homogeneous composition. Even if polymer Pl is incompatible with the compound, a mixture of polymer Pl with another polymer P2 compatible with polymer Pl may be used, if this mixture (Pl ~ P2) is compatible with said compound.
The polymer should preferably have very good film-forming characteristics~
As for the proportion of the polymer to the iodine-containing azide compound in the radiation-sensitive composition, ;t is preferred that the amount of the iodine-containing azide compound be 10-80 wt.%, particularly 30-60 wt.%, based on the weight of composition.
Fig~ l shows changes in film thickness observed when films having various proportions of the polymer and the azide compound were exposed to oxygen plasma. It should be taken into consideration that the initial thicknesses were different from one another and about 50~ of the coating film containing 20 wt.% of the azide compound (2 ,4 ,6 -triiodophenyl-4~-azido-benzoate) remained even after exposure to oxygen plasma for about 8 min, while a coating film containing only the polymer (polyvinylphenol~
disappeared after exposure to oxygen plasma for about 8 min. About 60% and 75% of coating Eilms containing 33 wt.% and 50 wt.%, respectively, of the same azide compound remained after exposure to oxygen plasma for 8 min. This fact indicates that the amount of film remaining (normal-ized film) is increased as the amount of the iodine-containing azide compound is increased. However, it will be apparent from the above description that a certain amount of the polymer is necessary for ixing the azide compound. Therefore, an amount in the above-mentioned range is preferred. The plasma irradiation conditions are shown in Example l given below.
The proportion of the polymer, organic iodine compound 3G and azide compound in the radiation-sensitive composition comprising these three compounds is preferably l:G.1-3:0.05-2, particularly 1:0.4-2:0.1-1, by weight.
Experimental data of the resis~ance of the composltion to oxygen plasma will be shown in Ta~le 1, which shows relative removal rates of films by oxygen pla~sma measured after hardenin~ of coating films comprising polystyrene, 3,3'-diaziododiphenyl sulfone and iodoform by light. It is apparent from Table 1 that oxygen plasma resistance is increased remarkably as the amount of iodoform (iodine compound) is increased. I~ can be seen, therefore, that the coating film can be used as an oxygen plasma-resisting mas~. The experimental conditions were the same as in Fig. 1.
Table 1 .
Polystyrene Diazide com- Iodoform Relative (part by wt.) pound (part by wt.) removal (part by w~.l rate of film 1 0.2 0 1.0 1 0.2 0.24 0.77 1 0.2 0 S~ Q.4~
l 002 1.53 0.33 , The followinq compounds can be used as the polymer:
poly-N-vlnyl-carbazole, polyacenaphthylene, polyvinylidene fluoride, poly-N-vinylpyrrolidone, polyglycidyl methacrylate, polystyrene, polyalkyl methacrylates, cyclic polyisoprene, poly-4-methylstyrene, poymethacrylonitrile, poly-4~vinylpyridine, poly-4-bromostyrene, polyvinyl-benzyl chloride, polybutadiene, poly-4-chlorostyrene, epoxidized polybutadiene, polyvinyi acetate, polyvinyl cinnamate, polyvinyl chloride, pvlychloroprene, poly-vinyl bromide, polyepichlorohydrin, polyvinylphenol, polyvinyl alcohol, polyvinylidene chloride, poly-acrylonitrile, poly-~methylstyrene, polymethyl isopropenyl ketone, polyacrylamide, polyvinyl meth~l ketone, polybu~ene-l sulfone, polystyrene sulfone, polyisobutylene, a phenolic resin such as novolak resin, styrene/maleic anhydride copolymer, cellulose acetate hydrogenphthala~e, polyvinyl hydroxybenzoate, polyvinyl hydroxvbenzal or acrylic resin. These poly-mers may also be used as components of copolymers.
Further, polymers other than those mentioned above having film-forming properties and compatibility with said compounds may also be used. These polymers may be used ~ither alone or in the form of a mixture of two or more of them.
Polymers containing a benzene ring or rubbery polymers are preferred from the viewpoint of their dry etching resistance.
When the pattern formation method of the present invention is carried out according to the dry development technique, the iodine-containing polymer cannot substantially be used as the polymer. The reason therefor is that even if it is attempted to remove the iodine-containing compound from the unexposed region of the coating film by heating, the iodine~containing polymer remains in the film, and it exhibits a resistance to oxygen plasma. However, it will be understood from, for examplel Table 1 given above that if the iodine content is low, the difference in the relative removal rate of film in this case from that of iodine-free film is insignificant. Since the iodine compound or iodine-containing azide compound is present in the exposed region, the total of iodine contained therein and that oontained in the polymer is relatively large and the relative xemoval rate of the film is reduced. Thus, even if the polymer contains only a small amount of iodine, a pattern may be formed in the coating film according to the dry development.
The following compounds of general formula (I) are given as examples of azide compounds containing iodine:
N3 ~ I
x (I) R y wherein Rx and Ry each represent an element or atomic group selected from the group consisting of hydrogen, an alkyl group, a nitro group, halogen, an amino group, a monoalkylamino group, an acyl group, a dialkylamino group, an alkoxyl group, a hydroxyl group, a sulfonic acid gro~p, a sulfonio acid ester group, a carboxylic acid gro~p and a carboxylic acid ester group.
The Eollowing are examples of these compounds:
p-azidoiodobenzene, 2,6-diiodo-4-nitroazido-benzene, 2-chloro-4-iodoazidobenzene, 2,6-dichloro-4-iodoazido-benzene, 2-bromo-4-iodoazidobenzene, 2,6-dibromo-4-iodoazidobenzene, 2-methyl-4-iodoazidobenzene and
2-methoxy-4-iodoazidobenzene.
Further, azide compounds of the following general formula (II) may be mentioned as examples:
i~s ~ _ y - ~ i (II) wherein Y represents an atomic group selected from the group consisting of CH2~ COO, OOC, SO3 and O3S and Ri represents an element or atomic group selected from the group consisting of I, CH2I and CH2CH2I.
The following are examples of these comounds:
2-iodoethyl-4-azidobenzoate, iodomethyl-4 azidobenzoate, 4 azidophenyl iodoacetate ancl 4-iodomethylazidobenzene.
In addition, azide compounds of the following general formula (III) may be mentioned:
Further, azide compounds of the following general formula (II) may be mentioned as examples:
i~s ~ _ y - ~ i (II) wherein Y represents an atomic group selected from the group consisting of CH2~ COO, OOC, SO3 and O3S and Ri represents an element or atomic group selected from the group consisting of I, CH2I and CH2CH2I.
The following are examples of these comounds:
2-iodoethyl-4-azidobenzoate, iodomethyl-4 azidobenzoate, 4 azidophenyl iodoacetate ancl 4-iodomethylazidobenzene.
In addition, azide compounds of the following general formula (III) may be mentioned:
3 ~ ~ ~ y ~III) wherein X represents an element or atomic gro~p selected from the group consisting of S~, CH2, O, S, SO2, CO, COO, SO3, CH=CH and CH=CHCO and Rx and Ry have the same meaning as described above.
The following are examples of these compounds: 2 ,4 ,6 -triiodophenyl-4'-azidobenzoate, 3 -iodophenyl-4'-azidobenzoate, 4-azido-4'-iododiphenyl s~lfide and 4-azido-4'-iodobenzophenone.
In the above-mentioned, iodine-containing azide compoundsl those having one aromatic ring and those having the iodine atoms directly bonded to the henzene ring are preferred in view of their ease o~ dissipation by heat.
A combination of ~n azide compound containing a polar group, e.g. a carboxylic acid group, with a polymer having a polar group, e.g~ a polyvinylphenol, is not preferred, since dissipation of the azide compound by heat becomes difficult.
Examples of the iodine compounds that may be used in the present invention are diiodomethane, iodoform, iodoethane, l-iodobutane, l-iodohept~ne, l-iodopropane, 2-iodopropane, 1,2-diiodoetnane, 1,4-diiodobutane, iodotrimethylsilane, 2-iodo-1,1,1-trifluoroethane, iodomethyltrimethylsilane, iodoacetamide, iodoacetic acid, 3-iodopropionic acid, 2-iodoethanol, 2-iodoaniline, 3-iodoaniline, 4-iodoaniline, 4-iodo-anisole, 5-iodoanthranilic acid, o-iodobenzoic acid, m-iodobenzoic acid, p iodobenzoic acid, p iodobenzene-sulfonyl chloride, o-iodobenzyl alcohol, m-iodobenzyl alcohol, p~iodobenzyl alcohol, iodobenzene, o-diiodo-benzene, m-diiodobenzene, p-diiodobenzene, o-iodobenzyl chloride, l-iodo-2-nitrobenzene, 1-iodo-3-nitrobenzene, l-iodo-4-nitrobenzene, 2-iodophenol, 3-iQdophenol,
The following are examples of these compounds: 2 ,4 ,6 -triiodophenyl-4'-azidobenzoate, 3 -iodophenyl-4'-azidobenzoate, 4-azido-4'-iododiphenyl s~lfide and 4-azido-4'-iodobenzophenone.
In the above-mentioned, iodine-containing azide compoundsl those having one aromatic ring and those having the iodine atoms directly bonded to the henzene ring are preferred in view of their ease o~ dissipation by heat.
A combination of ~n azide compound containing a polar group, e.g. a carboxylic acid group, with a polymer having a polar group, e.g~ a polyvinylphenol, is not preferred, since dissipation of the azide compound by heat becomes difficult.
Examples of the iodine compounds that may be used in the present invention are diiodomethane, iodoform, iodoethane, l-iodobutane, l-iodohept~ne, l-iodopropane, 2-iodopropane, 1,2-diiodoetnane, 1,4-diiodobutane, iodotrimethylsilane, 2-iodo-1,1,1-trifluoroethane, iodomethyltrimethylsilane, iodoacetamide, iodoacetic acid, 3-iodopropionic acid, 2-iodoethanol, 2-iodoaniline, 3-iodoaniline, 4-iodoaniline, 4-iodo-anisole, 5-iodoanthranilic acid, o-iodobenzoic acid, m-iodobenzoic acid, p iodobenzoic acid, p iodobenzene-sulfonyl chloride, o-iodobenzyl alcohol, m-iodobenzyl alcohol, p~iodobenzyl alcohol, iodobenzene, o-diiodo-benzene, m-diiodobenzene, p-diiodobenzene, o-iodobenzyl chloride, l-iodo-2-nitrobenzene, 1-iodo-3-nitrobenzene, l-iodo-4-nitrobenzene, 2-iodophenol, 3-iQdophenol,
4-iodophenol, 5-iodosalicylic acid, o-iodotoluene, m-iodotoluene, p-iodotoluene, o-iodo-~ -trifluoro-toluene, 2 iodo-6-methyl-3-pyridinol, 2-iodo-3-pyri.dinol, 4-iodopyrazole, 2-iodothiophene, 3-iodothiophene, 2,6-diiodo-4-nitroaniline, 2,6-diiodo-4-nitrophenol, 3,5-diiodo-4-pyridone-N-acetate, 4-hydroxy-3,5-diiodo-benzoic acid, 2,4,$-triiodobenzoic acid, 3,4,5-triodo-benzoic acid and 2,4,6-triiodophenol. They may be used either alone or in the form of a m-xture of two or more compounds~ These iodine compounds do not have an azido group.
Examples of the azide compounds that may be used in the invention are those of the general formula:
Y~ ~ ~ ~ (IV) Z Z
wherein A represents an element or a substituent selected from the group ~onsisting of O, S, CH2, CH2CH2, SO2, S2, CO, COO, SO3, CH=CH and CH=CHCO, and X, Y and Z each represent an element or a sub-stituent selected from the group consisting of an azido group, hydrogen, al~yl group, nitro group, haLogen, amino group, monoalkylamino group, alkoxyl group, hydroxyl group, sulfonic acid group, sulfonic acid es~er group, carboxylic acid group and carboxylic acid ester gro~p, and those of the general formula:
~Z ~V) Y
X
wherein X, Y and Z have the same meaning as above.
Organlc azide compounds other than those shown above may also be used. The azide compounds may be used either alone or in the form of a mixture of two or more of them.
Some of ~he compounds wherein at least one of X, Y and Z represents iodine are the same as the a~ove-mentioned iodine-containing azide compounds.
These lodine-containing azide compounds may also be used in combination with the iodine compound, if they are remo~able from the coating film in an unexposed region by heating.
Particular examples of the azide compounds of general formula (IV) are 4,4'-diazidodiphenyl ether, 4,4'-diazidodiphenyl sulfide, 4,4'-diazidodiphenyl sulfone, 3,3'-dia2idodiphenyl sulfone, 4,4'-diazidodiphenylmethane, 3,31-dichloro-'7 4,4'-diazidodiphenylmethane, 4,4'-diazidodiphenyl disulfide t 4,4l-diazidobibenzyl, 2 ,4 ,6 -triiodo-phenyl-4' azidobenzoate, 3 -iodophenyl-4'-azidobenzoate, 4-azido-4'-iododiphenyl sulfide and 4-azido-4'-iodobenzo-phenone.
Particular examples of the azide compounds of general formula ~V) are p-azidoiodobenzene, 2,6-diiodo-4-nitroazidobenzene, 2-chloro-4-iodoazidobenzene, 2,6-dichloro-4~iodoazidobenæene, 2~bromo-4-iodoazidobenzene, 2,6-dibro~o-4-iodoazidobenzene, 2-methyl-4-iodoazidobenzene and 2-methoxyr4-iodoazidobenzene.
As representative of other azide compounds, 2-iodomethyl-4-azidobenzoate, for example, may be mentioned.
It is preferred to use diazide compounds as the azide compounds, since they fix the iodine compounds firmly.
Also in the radiation-s~nsitive ~omposition comprising the iodine compound, azide compound and polymer wherein the iodine compound contains a polar group, e.g. a carboxylic acid group, or wherein the azide compound contains iodine and a polar group, e.g. carbox~lic acid group, it is not preferred to use a polar gro~p-containing polymer such as polyvinylphenol, novolak resin, styrne/maleic anhydride copolymer, cellulose acetate hydrogenphthalate, polyvinyl hydroxybenæoate, polyvinylhydroxybenzalJ polymethacry~ic acid or poly-acrylic acid, because these compounds are difficult to dissipate by heating during dry development.
The sensitive composition of the present invention can also be used in an ordinary wet development technique~
In this case, it is preferred that the azide compound be a dia7ide compound or that when the azide compound is a monoazide compound, a polymer having a polar group e.y.
polyacrylic acid, particularly~ a polymer soluble in an aqueous alkali solution be used.
When other compositions, wherein the azide compound is a monoazide compound and the polymer contains no polar group, are used, the wet development technique should preferably not be employed.
Examples of the polymers soluble in an aqueous alkali solution are, for example, polyvinylphenol, novolak resin, styrene/maleic anhydride copolymer, cel].ulose acetate hydrogenphthalate, polyvinyl hydroxybenzoatel polyvinyl-hydroxybenzal/ polymethacrylic acid and polyacrylic acid.
When the wet development technique is employed, an unexposed part is removed with a solvent by an ordinary method after exposure to the radiation.
The radiation-sensitive composition of the present invention has very good resistance to oxygen plasma as described above and, therefore, it may be used for the production of a printing plate. In this technique, for example, a coating film of the composition of the pre~ent invention is formed on a nylon base, a desired pattern is formed thereon and the base is etched using oxygen plasma. Accordingly, the reduction of resolution due to the swelling of the base with a solvent can be prevented.
Any oxygen-containing plasma may be used, though it is preferred to use oxygen plasma per se.
The following Examples will further illustrate the present invention. First, processes for synthesizing the iodine-containing azide compounds will be described.
p-Iodoaniline (6g) was dispersed in a solu~ion comprising 25 cc of water and 7.5 GC of 36% hydro-chloric acid and c0012d with ice. Sodium nitrite (2.1g) was dissolved in 13 ml of water and the result-ing solution was added dropwise slowly to the dispersion to effect the diazotization reaction. A ~olution of 2.5g of sodlum azlde ln 18 ml of water was added drop-wise thereto and, ater stirring for one hour, the mixture was subjected to extraction with benzene.
After the dehydration with sodium sulfate, benzene was e~aporated to yield p-azidoiodobenzene.
ax~ 260 ~m, m.p. 33C
2,6-Diiodo-4 nitroazidobenzene:
.
2,6-Diiodo-4-nitroaniline (Sg) was dissolved in 20 ml of ~onc. sulfuric acid and cooled with iceO
Sodium nitrite previously ~acuum-dried was added to the solution in portions to effect the diazotization xeactio~ at 0-5C~ The reaction product was added dxopwise to ice-wa~er to dil~te the sulfuric acid.
A solution of 104g of sodium azide in 10 cc of water was added dropwise to the mix~ure, stirred for about one hour, filtered and washed with water. Af~er t~e rac~ystallization from ethanol followed by drying, 2,6-dilodo-4-nitroazidobenzene was obtained.
~max 302 nm, m.p. 82 C.
2_,4 ,6 -Triiodophenyl-4'-azidoben~oate:
p-~minobenzoic acid (13.7~) was dispersed in a solution of 100 cc of water and 30 cc of 30% hydro-chloric acid in an ordinary manner and the dispersion was cooled wi~h ice. A solution of 8.3g of sodium nitrite in S0 cc of water was added dropwise to the, dispersion to efEect the diazo-tization reaction.
A sollltion of lO.lg of sodium azide in J0 cc of water was added dropwise to the mixture, stirred lor about one hour, filtered and vacuum-dried to obtain p-azidobenzoic acid. The thus obtained p-azidobenzoic acid ~5~4g) was dissolved in 10 cc of dimethyl-formamide and 25 g of thionyl chloride was added dropwise to the solution. The mixture was stirred for about one hour and the product was added dropwise to ice~water.
After filtration followed by washing with water and ~acuum drying, p-azidobenzoyl chloride was obtained.
p-Azidobenzoyl chloride (0.9g) a~ 2,4g o~
2,4,6-triiodophenol were dissolved in 60 cc of dioxane.
The resulting solution was mixed with a solution of 0.2g of sodium hydroxide in 20 ml of water and the mixture was left to stand overnight and then poured into water. A solid matter thus formed was filtered out, washed with water and dried under vacuum to yield 2 ,4 ,6 -triiodophenyl-4'-azidobenzoate.
~max 278 nm, m-p- llS C.
3 -Iodo hen 1-4'-azidobenzoate:
__ P
3 -Iodophenyl 4-azidobenzoate was obtained by reacting azidobenzoyl chloride obtained as above with m-iodophenol in the same manner as above.
~max 278 nm.
Example 1 Polystyrene having a weight-average molecular weigh~ ~Mw) of about 270,000 was dissolved in chloro-benzene to form a 7 wt.% solution. Then, p-a7ido-iodobenzene was added to the solution to ob~ain a resist solution~ The mixing ratio of polystyrene to p-azidoiodobenzene was 1:0.6, by weight. The resist solution was applied ~o the surface oE a silicon wafer by ~eans of a spinner to form a film having a thickness of 0.6 ~m. After exposing the film to light from a Xe-Hg lamp via a test pattern mask for 20 sec, it was post-baked at 100C for 30 min to form a sample for the plasma development. The development was effected as shown below by means of an experimental apparatus con isting of a parallel-plate plasma reactor having a maximum output of 600 W and an electrode diameter of 60 mm. The sample was place~ on a lower elec-trode and, after degassing, oxygen gas was introduced there-in to control the pressure in the reactor to 0.5 Torr. A
high frequency power of 13.56 MHz was applied thereto and oxygen plasma was formed in the plasma reactor at an output of 55 W for 6 min. A~ter degassing in the reactor, the pressure was returned to atmospheric. The sample was taken out and subjected to microscopic examination to reveal that, unlike the product of the wet development method, the product thus obtained had a repetition pattern of line~ having a width of 1 ~m that were not swollen at all and were arranged at intervals of 1 ~m with high accuracy.
p-Azidoiodobenzene was added to a 10 wt.% solution of cyclic polyisoprene in xylene to obtain a resist solution.
The mixing ratio of cyclic polyisoprene to p-azidoiodo-benzene was 1:1, by weight. The resist solution was applied to the surface of a silicone wafer by means of a spinner to form a film having a thickness of about 0.9 ~m~ After exposing the film to light from a Xe Hg lamp, it wa.s post-baked at lOO~C for 30 min to form a sample for the plasma development. After efecting the development in ~he same manner as in Example 1, the product was subjected to microscopic examination to reveal that, unlike the product of the wet development method, the product thus obtained had the same, minute pattern as in Example 1.
The relationship between the exposure time and normal-ized film remaining is shown in Eig. 2. After the exposure for longer than about ~ sec, the normalized film remaining was higher than 50~
p-Azidoiodobenzene was added to a 6 wt.% solution of polymethyl methacrylate having a weight-average molecular weight (Mw) of about 600,000 in ethyl cellosolve acetate to form a resist solution. The mixing ratio of polymethyl methacrylate to p-azidoiodobenzene was 1:1, by weight.
The resist solution was applied to the surEace of a silicon wafer by means of a spinner to form a film having a thickness of about 0.5 ~m. After exposing the film to light from a Xe~Hg lamp via a test pattern mask for 20 sec, it was post-baked at 100C for 30 min to form a sample for the plasma development. After effecting the development with oxygen plasma ;n the same manner as in Example 1, the product was subjected to microscopic examination to reveal that, unlike the product of the wet development method, the product thus obtained had a repetition pattern of lines having a width of 1 ~m which were not swollen at all and were arranged at intervals of 1 ~m with high accuracy.
A resist solution having the same composition as in Example 1 having a mixing ratio of poly,tyrene to p-azido-iodobenzene of 1:1, by weight, was used. The resist solution was applied to the surface of a silicon wafer in the same manner as in Example 1. After the exposure followed by the post-baking, the development was efected with oxygen plasma. The normalized film remaining was superior to that obtained in Example 1. The sample was su~ected to microscopic examination to reveal that, unlike the product of the wet development method, the product thus obtained had a repetition pattern of lines having a width of 1~ m which were not swollen at all and were arranged at intervals o~ 1~ m with high accuracy.
Example 5 2 ,4 ,6 Triiodophenyl-4'-aæidobenzoate was added to a 20% solution of polyvinylphenol having a weight-average molecular weight (Mw) of about 3000 in methyl cellosolve acetate to form a resist solution. The mixing ratio o the polyvinylphenol to the a~ide compound was 1:1, by weight.
The resist solution was applied to the surface of a sili-con wafer by means of a spinner to form a film having a thickness of about 0.9~ m. After exposing the film to light from a Xe-Hg lamp via a test pattern mask for 20 sec, it was post-baked at 140C for 60 min to form a sample for the plasma development. After effecting the development with oxygen plasma in the same manner as in Example 1, the product was subjected to microscopic examination to reveal that, unlike the product of the wet development method, the product thus obtained had a repetition pattern of lines having a width of 1 ~m that were not swollen at all and were arranged at intervals of 1 ~m with high accuracy.
2,6-Diiodo-4-nitroazidobenzene was added to a 20 wt.%
solution of polyvinylphencl having a weight~average molec-ular weight (~w) of about 3000 in methyl cellosolve acetate to form a resist solution. The mixing ratio of polyvinyl-phenol to the azide compound was 1:0.5, by weight. The resist solution was applied to the surface of a silicon wafer by means of a spinner to form a film having a thick-ness of about 0.9~ m. After exposing the film to light from a Xe-Hg lamp via a test pattern mask for 20 sec, it was post-baked at 140C for 60 min ~o form a sample for plasma development. After effecting the development with oxygen plasma in the same manner as in Example 1, the product was subjected to microscopic examination to reveal that, unlike the product of the wet development method~
the product thus obtained had a repetition pattern oE lines having a width of 1~ m that were not swollen at all and were arranged at intervals of 1~ m with high accuracy.
Example 7 Polyvinylphenol having a weight-average molecular weight ~Mw) of about 5800 was dissolved in methyl cello-solve acetate to orrn a 20 wt.% solution. Then, 3,3'-diazidodiphenyl sulfone and 2,4,6-triiodophenol were added to the solution to form a resist solution. The mixing ratio of polyvinylphenol : 3,3'-diazidodiphenyl sulfone : 2,4,6-triiodophenol was 1:0.2:0~7, by weight. The resist solution was appl.ied to the surface of a silicon wafer by means of a spinner to form a film having a thickness of about 0.85 ~m. After exposing the film to light from a Xe-Hg lamp via a test pattern rnask for 20 ~ec, it was post-baked at 140C for 60 min to obtain a sample for plasma development. This sample was placed in the same plasma~orming apparatus as in Example 1 and oxygen plasma was formed for 8 min. After degassing in the reactor, the pressure was returned to atmospheric. The sample was taken out and subjected to microscopic examin-ation to reveal that the product had a repetition pattern of lines having a width of 1 ~m that were not swollen at all and were arranged at intervals of 1 ~m with high accuracy.
A resist solution was used having the same composition as in Example 7 except that the mixing ratio of polyvinyl~
phenol : 3,3'-diazidodiphenyl sulfone : 2,4,6-triidodi phenol was altered to 1:0.2:1, by weight. The resist solution was applied to a silicon wafer in the same manner as in Example 7. After the exposure followed by the post-baking, it was subjected to the development with oxygen plasma in the same manner as in Example 7. The exposure time and normalized film remaining were as shown in Fig.
3. The film was superior to that of Example 7 with respect to the remaining normalized filmO The product was subjec-ted to microscopic examination to reveal that it had a repetition pattern o~ lines having a width of 1~ m ~hat were not swollen at all and were arranged at intervals of 1~ m with high accuracy.
Example 9 Polystyrene having a weight-average molecular weight (Mw) of about 270,000 was dissolved in chlorobenzene to form a 7 wt.~ solution. Then, 3,3'-diazidodiphenyl sulfone and m-iodophenol were added to the solution to form a resist solution. The mixing ratio of polystyrene :
3,3'-diazidodiphenyl sulfone : ~-iodophenol was 1:0.2:0.5, by weight. The resist solution was applied to the surface of a silicon wafer by means of a spinner to form a film having a thickness of about 0.76 ~m. After exposing the film to light from a Xe-Hg lampl it was post~baked at 110C
for 85 min to obtain a sample for the plasma development.
After effecting the development with oxygen plasma in the same manner as in Example 7, the product was subjected to mlcroscopic examination to reveal that, unlike the product of the wet development method, the product thus obtained had the same, fine pattern as in Example 7.
Exam~e_10 Polystyrene having a weight-average molecular weight (Mw) of about 270/000 was dissolved in chlorobenzene to Porm a 7 wt.% solution. Then, 3,3'-diazidodiphenyl sulfone and m-diiodobenzene were added to the solution to form a resist solution. The mixing ratio of polystyrene : 3,3'-diazidodiphenyl sulfone : m-diiodobenzene was 1:0.2:0.5, by weight. The resist solution was applied to the surface of a silicon wafer by means of a spinner to form a film having a thickness of 0.86 ~m. After exposing the film to light from a Xe-H~ lamp, it was post-baked at 110C for 60 min to form a sample for the plasma developmentO After effecting the development with oxygen plasma in the same manner as in Example 7, the product was subjected to micro-scopic examination to reveal that, unlike the product of the wet development method, the product thus obtained had the same, fine pattern as in Example 7.
3~'7 Example 11 Polystyrene having a weight-average molecular weight ~Mw) of about 270,000 was dissolved in chlorobenzene to form a 7 wt D % solution. Then, 3,3'-diazidodiphenyl sulfone and iodoform were added to the solution to form a resist solution. The mixing ratio of polystyrene : 3,3'-diazido-diphenyl sulfone : iodoform was 1:0.2:0.5, by weight. The resist solution was applied to the surface of a silicon wafer by means of a spinner to form a film having a thick-ness of 0.86~ mO After exposing the film to light from aXe-Hg lamp, it was post-baked at 110C or 90 min to form a sample for the plasma development. After effecting the development with oxygen plasma in the same manner as in Example 1, the product was subjected to microscopic examin-ation to reveal that, unlike the product of the wet devel-opment method, the product thus obtained had the same, fine pattern as in Example 7 and was free of swelling.
When the iodine compounds or azido compounds used in above Examples 7-11 were replaced with other iodine com~
pounds or azido compounds, a fine pattern could also be obtained by dry development.
2,4,6-Triiodophenol (13 parts by weight) was added to 100 parts by weight of a solution comprising 20 parts by weight of poly-p~vinylphenol, 4 parts by weight of 3,3'-diazidodiphenyl sulfone and 80 parts by weight of cyclo-hexanone to form a resist solution. The resist solution was applied to the surface of a silicon wafer by means of a spinner and baked at 80C for 20 min in air to form a resist film having a thickness of 1.1~ m which was '7 used as an expo.sure sample~ After exposing the sample to light from a 600 W Xe-Hg lamp via a ~est pattern mask for
Examples of the azide compounds that may be used in the invention are those of the general formula:
Y~ ~ ~ ~ (IV) Z Z
wherein A represents an element or a substituent selected from the group ~onsisting of O, S, CH2, CH2CH2, SO2, S2, CO, COO, SO3, CH=CH and CH=CHCO, and X, Y and Z each represent an element or a sub-stituent selected from the group consisting of an azido group, hydrogen, al~yl group, nitro group, haLogen, amino group, monoalkylamino group, alkoxyl group, hydroxyl group, sulfonic acid group, sulfonic acid es~er group, carboxylic acid group and carboxylic acid ester gro~p, and those of the general formula:
~Z ~V) Y
X
wherein X, Y and Z have the same meaning as above.
Organlc azide compounds other than those shown above may also be used. The azide compounds may be used either alone or in the form of a mixture of two or more of them.
Some of ~he compounds wherein at least one of X, Y and Z represents iodine are the same as the a~ove-mentioned iodine-containing azide compounds.
These lodine-containing azide compounds may also be used in combination with the iodine compound, if they are remo~able from the coating film in an unexposed region by heating.
Particular examples of the azide compounds of general formula (IV) are 4,4'-diazidodiphenyl ether, 4,4'-diazidodiphenyl sulfide, 4,4'-diazidodiphenyl sulfone, 3,3'-dia2idodiphenyl sulfone, 4,4'-diazidodiphenylmethane, 3,31-dichloro-'7 4,4'-diazidodiphenylmethane, 4,4'-diazidodiphenyl disulfide t 4,4l-diazidobibenzyl, 2 ,4 ,6 -triiodo-phenyl-4' azidobenzoate, 3 -iodophenyl-4'-azidobenzoate, 4-azido-4'-iododiphenyl sulfide and 4-azido-4'-iodobenzo-phenone.
Particular examples of the azide compounds of general formula ~V) are p-azidoiodobenzene, 2,6-diiodo-4-nitroazidobenzene, 2-chloro-4-iodoazidobenzene, 2,6-dichloro-4~iodoazidobenæene, 2~bromo-4-iodoazidobenzene, 2,6-dibro~o-4-iodoazidobenzene, 2-methyl-4-iodoazidobenzene and 2-methoxyr4-iodoazidobenzene.
As representative of other azide compounds, 2-iodomethyl-4-azidobenzoate, for example, may be mentioned.
It is preferred to use diazide compounds as the azide compounds, since they fix the iodine compounds firmly.
Also in the radiation-s~nsitive ~omposition comprising the iodine compound, azide compound and polymer wherein the iodine compound contains a polar group, e.g. a carboxylic acid group, or wherein the azide compound contains iodine and a polar group, e.g. carbox~lic acid group, it is not preferred to use a polar gro~p-containing polymer such as polyvinylphenol, novolak resin, styrne/maleic anhydride copolymer, cellulose acetate hydrogenphthalate, polyvinyl hydroxybenæoate, polyvinylhydroxybenzalJ polymethacry~ic acid or poly-acrylic acid, because these compounds are difficult to dissipate by heating during dry development.
The sensitive composition of the present invention can also be used in an ordinary wet development technique~
In this case, it is preferred that the azide compound be a dia7ide compound or that when the azide compound is a monoazide compound, a polymer having a polar group e.y.
polyacrylic acid, particularly~ a polymer soluble in an aqueous alkali solution be used.
When other compositions, wherein the azide compound is a monoazide compound and the polymer contains no polar group, are used, the wet development technique should preferably not be employed.
Examples of the polymers soluble in an aqueous alkali solution are, for example, polyvinylphenol, novolak resin, styrene/maleic anhydride copolymer, cel].ulose acetate hydrogenphthalate, polyvinyl hydroxybenzoatel polyvinyl-hydroxybenzal/ polymethacrylic acid and polyacrylic acid.
When the wet development technique is employed, an unexposed part is removed with a solvent by an ordinary method after exposure to the radiation.
The radiation-sensitive composition of the present invention has very good resistance to oxygen plasma as described above and, therefore, it may be used for the production of a printing plate. In this technique, for example, a coating film of the composition of the pre~ent invention is formed on a nylon base, a desired pattern is formed thereon and the base is etched using oxygen plasma. Accordingly, the reduction of resolution due to the swelling of the base with a solvent can be prevented.
Any oxygen-containing plasma may be used, though it is preferred to use oxygen plasma per se.
The following Examples will further illustrate the present invention. First, processes for synthesizing the iodine-containing azide compounds will be described.
p-Iodoaniline (6g) was dispersed in a solu~ion comprising 25 cc of water and 7.5 GC of 36% hydro-chloric acid and c0012d with ice. Sodium nitrite (2.1g) was dissolved in 13 ml of water and the result-ing solution was added dropwise slowly to the dispersion to effect the diazotization reaction. A ~olution of 2.5g of sodlum azlde ln 18 ml of water was added drop-wise thereto and, ater stirring for one hour, the mixture was subjected to extraction with benzene.
After the dehydration with sodium sulfate, benzene was e~aporated to yield p-azidoiodobenzene.
ax~ 260 ~m, m.p. 33C
2,6-Diiodo-4 nitroazidobenzene:
.
2,6-Diiodo-4-nitroaniline (Sg) was dissolved in 20 ml of ~onc. sulfuric acid and cooled with iceO
Sodium nitrite previously ~acuum-dried was added to the solution in portions to effect the diazotization xeactio~ at 0-5C~ The reaction product was added dxopwise to ice-wa~er to dil~te the sulfuric acid.
A solution of 104g of sodium azide in 10 cc of water was added dropwise to the mix~ure, stirred for about one hour, filtered and washed with water. Af~er t~e rac~ystallization from ethanol followed by drying, 2,6-dilodo-4-nitroazidobenzene was obtained.
~max 302 nm, m.p. 82 C.
2_,4 ,6 -Triiodophenyl-4'-azidoben~oate:
p-~minobenzoic acid (13.7~) was dispersed in a solution of 100 cc of water and 30 cc of 30% hydro-chloric acid in an ordinary manner and the dispersion was cooled wi~h ice. A solution of 8.3g of sodium nitrite in S0 cc of water was added dropwise to the, dispersion to efEect the diazo-tization reaction.
A sollltion of lO.lg of sodium azide in J0 cc of water was added dropwise to the mixture, stirred lor about one hour, filtered and vacuum-dried to obtain p-azidobenzoic acid. The thus obtained p-azidobenzoic acid ~5~4g) was dissolved in 10 cc of dimethyl-formamide and 25 g of thionyl chloride was added dropwise to the solution. The mixture was stirred for about one hour and the product was added dropwise to ice~water.
After filtration followed by washing with water and ~acuum drying, p-azidobenzoyl chloride was obtained.
p-Azidobenzoyl chloride (0.9g) a~ 2,4g o~
2,4,6-triiodophenol were dissolved in 60 cc of dioxane.
The resulting solution was mixed with a solution of 0.2g of sodium hydroxide in 20 ml of water and the mixture was left to stand overnight and then poured into water. A solid matter thus formed was filtered out, washed with water and dried under vacuum to yield 2 ,4 ,6 -triiodophenyl-4'-azidobenzoate.
~max 278 nm, m-p- llS C.
3 -Iodo hen 1-4'-azidobenzoate:
__ P
3 -Iodophenyl 4-azidobenzoate was obtained by reacting azidobenzoyl chloride obtained as above with m-iodophenol in the same manner as above.
~max 278 nm.
Example 1 Polystyrene having a weight-average molecular weigh~ ~Mw) of about 270,000 was dissolved in chloro-benzene to form a 7 wt.% solution. Then, p-a7ido-iodobenzene was added to the solution to ob~ain a resist solution~ The mixing ratio of polystyrene to p-azidoiodobenzene was 1:0.6, by weight. The resist solution was applied ~o the surface oE a silicon wafer by ~eans of a spinner to form a film having a thickness of 0.6 ~m. After exposing the film to light from a Xe-Hg lamp via a test pattern mask for 20 sec, it was post-baked at 100C for 30 min to form a sample for the plasma development. The development was effected as shown below by means of an experimental apparatus con isting of a parallel-plate plasma reactor having a maximum output of 600 W and an electrode diameter of 60 mm. The sample was place~ on a lower elec-trode and, after degassing, oxygen gas was introduced there-in to control the pressure in the reactor to 0.5 Torr. A
high frequency power of 13.56 MHz was applied thereto and oxygen plasma was formed in the plasma reactor at an output of 55 W for 6 min. A~ter degassing in the reactor, the pressure was returned to atmospheric. The sample was taken out and subjected to microscopic examination to reveal that, unlike the product of the wet development method, the product thus obtained had a repetition pattern of line~ having a width of 1 ~m that were not swollen at all and were arranged at intervals of 1 ~m with high accuracy.
p-Azidoiodobenzene was added to a 10 wt.% solution of cyclic polyisoprene in xylene to obtain a resist solution.
The mixing ratio of cyclic polyisoprene to p-azidoiodo-benzene was 1:1, by weight. The resist solution was applied to the surface of a silicone wafer by means of a spinner to form a film having a thickness of about 0.9 ~m~ After exposing the film to light from a Xe Hg lamp, it wa.s post-baked at lOO~C for 30 min to form a sample for the plasma development. After efecting the development in ~he same manner as in Example 1, the product was subjected to microscopic examination to reveal that, unlike the product of the wet development method, the product thus obtained had the same, minute pattern as in Example 1.
The relationship between the exposure time and normal-ized film remaining is shown in Eig. 2. After the exposure for longer than about ~ sec, the normalized film remaining was higher than 50~
p-Azidoiodobenzene was added to a 6 wt.% solution of polymethyl methacrylate having a weight-average molecular weight (Mw) of about 600,000 in ethyl cellosolve acetate to form a resist solution. The mixing ratio of polymethyl methacrylate to p-azidoiodobenzene was 1:1, by weight.
The resist solution was applied to the surEace of a silicon wafer by means of a spinner to form a film having a thickness of about 0.5 ~m. After exposing the film to light from a Xe~Hg lamp via a test pattern mask for 20 sec, it was post-baked at 100C for 30 min to form a sample for the plasma development. After effecting the development with oxygen plasma ;n the same manner as in Example 1, the product was subjected to microscopic examination to reveal that, unlike the product of the wet development method, the product thus obtained had a repetition pattern of lines having a width of 1 ~m which were not swollen at all and were arranged at intervals of 1 ~m with high accuracy.
A resist solution having the same composition as in Example 1 having a mixing ratio of poly,tyrene to p-azido-iodobenzene of 1:1, by weight, was used. The resist solution was applied to the surface of a silicon wafer in the same manner as in Example 1. After the exposure followed by the post-baking, the development was efected with oxygen plasma. The normalized film remaining was superior to that obtained in Example 1. The sample was su~ected to microscopic examination to reveal that, unlike the product of the wet development method, the product thus obtained had a repetition pattern of lines having a width of 1~ m which were not swollen at all and were arranged at intervals o~ 1~ m with high accuracy.
Example 5 2 ,4 ,6 Triiodophenyl-4'-aæidobenzoate was added to a 20% solution of polyvinylphenol having a weight-average molecular weight (Mw) of about 3000 in methyl cellosolve acetate to form a resist solution. The mixing ratio o the polyvinylphenol to the a~ide compound was 1:1, by weight.
The resist solution was applied to the surface of a sili-con wafer by means of a spinner to form a film having a thickness of about 0.9~ m. After exposing the film to light from a Xe-Hg lamp via a test pattern mask for 20 sec, it was post-baked at 140C for 60 min to form a sample for the plasma development. After effecting the development with oxygen plasma in the same manner as in Example 1, the product was subjected to microscopic examination to reveal that, unlike the product of the wet development method, the product thus obtained had a repetition pattern of lines having a width of 1 ~m that were not swollen at all and were arranged at intervals of 1 ~m with high accuracy.
2,6-Diiodo-4-nitroazidobenzene was added to a 20 wt.%
solution of polyvinylphencl having a weight~average molec-ular weight (~w) of about 3000 in methyl cellosolve acetate to form a resist solution. The mixing ratio of polyvinyl-phenol to the azide compound was 1:0.5, by weight. The resist solution was applied to the surface of a silicon wafer by means of a spinner to form a film having a thick-ness of about 0.9~ m. After exposing the film to light from a Xe-Hg lamp via a test pattern mask for 20 sec, it was post-baked at 140C for 60 min ~o form a sample for plasma development. After effecting the development with oxygen plasma in the same manner as in Example 1, the product was subjected to microscopic examination to reveal that, unlike the product of the wet development method~
the product thus obtained had a repetition pattern oE lines having a width of 1~ m that were not swollen at all and were arranged at intervals of 1~ m with high accuracy.
Example 7 Polyvinylphenol having a weight-average molecular weight ~Mw) of about 5800 was dissolved in methyl cello-solve acetate to orrn a 20 wt.% solution. Then, 3,3'-diazidodiphenyl sulfone and 2,4,6-triiodophenol were added to the solution to form a resist solution. The mixing ratio of polyvinylphenol : 3,3'-diazidodiphenyl sulfone : 2,4,6-triiodophenol was 1:0.2:0~7, by weight. The resist solution was appl.ied to the surface of a silicon wafer by means of a spinner to form a film having a thickness of about 0.85 ~m. After exposing the film to light from a Xe-Hg lamp via a test pattern rnask for 20 ~ec, it was post-baked at 140C for 60 min to obtain a sample for plasma development. This sample was placed in the same plasma~orming apparatus as in Example 1 and oxygen plasma was formed for 8 min. After degassing in the reactor, the pressure was returned to atmospheric. The sample was taken out and subjected to microscopic examin-ation to reveal that the product had a repetition pattern of lines having a width of 1 ~m that were not swollen at all and were arranged at intervals of 1 ~m with high accuracy.
A resist solution was used having the same composition as in Example 7 except that the mixing ratio of polyvinyl~
phenol : 3,3'-diazidodiphenyl sulfone : 2,4,6-triidodi phenol was altered to 1:0.2:1, by weight. The resist solution was applied to a silicon wafer in the same manner as in Example 7. After the exposure followed by the post-baking, it was subjected to the development with oxygen plasma in the same manner as in Example 7. The exposure time and normalized film remaining were as shown in Fig.
3. The film was superior to that of Example 7 with respect to the remaining normalized filmO The product was subjec-ted to microscopic examination to reveal that it had a repetition pattern o~ lines having a width of 1~ m ~hat were not swollen at all and were arranged at intervals of 1~ m with high accuracy.
Example 9 Polystyrene having a weight-average molecular weight (Mw) of about 270,000 was dissolved in chlorobenzene to form a 7 wt.~ solution. Then, 3,3'-diazidodiphenyl sulfone and m-iodophenol were added to the solution to form a resist solution. The mixing ratio of polystyrene :
3,3'-diazidodiphenyl sulfone : ~-iodophenol was 1:0.2:0.5, by weight. The resist solution was applied to the surface of a silicon wafer by means of a spinner to form a film having a thickness of about 0.76 ~m. After exposing the film to light from a Xe-Hg lampl it was post~baked at 110C
for 85 min to obtain a sample for the plasma development.
After effecting the development with oxygen plasma in the same manner as in Example 7, the product was subjected to mlcroscopic examination to reveal that, unlike the product of the wet development method, the product thus obtained had the same, fine pattern as in Example 7.
Exam~e_10 Polystyrene having a weight-average molecular weight (Mw) of about 270/000 was dissolved in chlorobenzene to Porm a 7 wt.% solution. Then, 3,3'-diazidodiphenyl sulfone and m-diiodobenzene were added to the solution to form a resist solution. The mixing ratio of polystyrene : 3,3'-diazidodiphenyl sulfone : m-diiodobenzene was 1:0.2:0.5, by weight. The resist solution was applied to the surface of a silicon wafer by means of a spinner to form a film having a thickness of 0.86 ~m. After exposing the film to light from a Xe-H~ lamp, it was post-baked at 110C for 60 min to form a sample for the plasma developmentO After effecting the development with oxygen plasma in the same manner as in Example 7, the product was subjected to micro-scopic examination to reveal that, unlike the product of the wet development method, the product thus obtained had the same, fine pattern as in Example 7.
3~'7 Example 11 Polystyrene having a weight-average molecular weight ~Mw) of about 270,000 was dissolved in chlorobenzene to form a 7 wt D % solution. Then, 3,3'-diazidodiphenyl sulfone and iodoform were added to the solution to form a resist solution. The mixing ratio of polystyrene : 3,3'-diazido-diphenyl sulfone : iodoform was 1:0.2:0.5, by weight. The resist solution was applied to the surface of a silicon wafer by means of a spinner to form a film having a thick-ness of 0.86~ mO After exposing the film to light from aXe-Hg lamp, it was post-baked at 110C or 90 min to form a sample for the plasma development. After effecting the development with oxygen plasma in the same manner as in Example 1, the product was subjected to microscopic examin-ation to reveal that, unlike the product of the wet devel-opment method, the product thus obtained had the same, fine pattern as in Example 7 and was free of swelling.
When the iodine compounds or azido compounds used in above Examples 7-11 were replaced with other iodine com~
pounds or azido compounds, a fine pattern could also be obtained by dry development.
2,4,6-Triiodophenol (13 parts by weight) was added to 100 parts by weight of a solution comprising 20 parts by weight of poly-p~vinylphenol, 4 parts by weight of 3,3'-diazidodiphenyl sulfone and 80 parts by weight of cyclo-hexanone to form a resist solution. The resist solution was applied to the surface of a silicon wafer by means of a spinner and baked at 80C for 20 min in air to form a resist film having a thickness of 1.1~ m which was '7 used as an expo.sure sample~ After exposing the sample to light from a 600 W Xe-Hg lamp via a ~est pattern mask for
5 sec, it was immersed in a 0~95 wt.% aqueous solution of tetramethylammonium hydroxide used as a developer for 30 sec to effect the development of the resist film. The product was subjected to microscopic examination to reveal that the product thus obtained had a repetition pattern of lines having a width of 1 ~m which were not swollen at all and were arranged at intervals of 1 ~m with high accuracy.
Example 13 m,p-Cresol novolak resin (20 parts by weight), 6 parts by weight of 4 azido-4' methoxychalcone and 10 parts by weight of 2,4,6-triiodophenol were dissolved in 80 parts by weight of methyl cellosolve acetate to form a resist solution. The resist solution was applied to the surface of a silicon wafer and baked at 80C for 20 min to form a resist film having a thickness of 0.9 ~m. After exposiny the film to light from a 500 W ultra-high pressure Hg lamp via a test pattern mask for 2 sec, it was developed with an aqueous solution of tetramethylammonium hydroxide to form a repetit;on pattern of lines having a width of 1 ~m arranged at intervals of 1 ~m with high accuracy.
The films were exposed to light in the above examples.
Substantially the same effects were also obtained when visible light, X-rays, electron beams or ion beams were used,
Example 13 m,p-Cresol novolak resin (20 parts by weight), 6 parts by weight of 4 azido-4' methoxychalcone and 10 parts by weight of 2,4,6-triiodophenol were dissolved in 80 parts by weight of methyl cellosolve acetate to form a resist solution. The resist solution was applied to the surface of a silicon wafer and baked at 80C for 20 min to form a resist film having a thickness of 0.9 ~m. After exposiny the film to light from a 500 W ultra-high pressure Hg lamp via a test pattern mask for 2 sec, it was developed with an aqueous solution of tetramethylammonium hydroxide to form a repetit;on pattern of lines having a width of 1 ~m arranged at intervals of 1 ~m with high accuracy.
The films were exposed to light in the above examples.
Substantially the same effects were also obtained when visible light, X-rays, electron beams or ion beams were used,
Claims (10)
1. A radiation-sensitive composition comprising:
an azide compound selected from the group consisting of a compound of the general formula:
wherein A represents an element or a substituent selected from the group consisting of O, S, CH2, CH2CH2, SO2, S2, CO, COO, SO3, CH=CH and CH=CHCO, and X, Y and Z each represent an element or a substituent selected from the group consisting of an azido group, hydrogen, alkyl group, nitro group, halogen, amino group, monoalkylamino group, alkoxy group, hydroxyl group, sulfonic acid group, sulfonic acid ester group, carboxylic acid group and carboxylic acid ester group; and a compound of the general formula:
wherein X, Y and Z each represent an element or substit-uent selected from the group consisting of an azide group, hydrogen, alkyl group, nitro group, halogen, amino group, monoalkylamino group, alkoxyl group, hydroxyl group, sul-fonic acid group, sulfonic acid ester group, carboxylic acid group and carboxylic acid ester group;
an iodine compound at least a part of which can be fixed substantially in a polymer layer by exposure to a radiation; and a polymer substantially having compatibility with the azide compound and the iodine compound.
an azide compound selected from the group consisting of a compound of the general formula:
wherein A represents an element or a substituent selected from the group consisting of O, S, CH2, CH2CH2, SO2, S2, CO, COO, SO3, CH=CH and CH=CHCO, and X, Y and Z each represent an element or a substituent selected from the group consisting of an azido group, hydrogen, alkyl group, nitro group, halogen, amino group, monoalkylamino group, alkoxy group, hydroxyl group, sulfonic acid group, sulfonic acid ester group, carboxylic acid group and carboxylic acid ester group; and a compound of the general formula:
wherein X, Y and Z each represent an element or substit-uent selected from the group consisting of an azide group, hydrogen, alkyl group, nitro group, halogen, amino group, monoalkylamino group, alkoxyl group, hydroxyl group, sul-fonic acid group, sulfonic acid ester group, carboxylic acid group and carboxylic acid ester group;
an iodine compound at least a part of which can be fixed substantially in a polymer layer by exposure to a radiation; and a polymer substantially having compatibility with the azide compound and the iodine compound.
2. A radiation-sensitive composition according to Claim 1 wherein the weight ratio of the polymer : iodine compound :
azide compound is in the range of 1:0.1-3:0:05-2.
azide compound is in the range of 1:0.1-3:0:05-2.
3. A radiation-sensitive composition according to Claim 1 or 2 wherein the iodine compound is at least one compound selected from the group consisting of diiodomethane, iodoform, iodoethane, l-iodobutane, l-iodoheptane, l-iodopropane, 2-iodopropane, 1,2-diiodoethane, 1,4-diiodobutane, iodotrimethylsilane, 2-iodo-l,l,l-tri-fluoroethane, iodomethyltrimethylsilane, iodoacetamide, iodoacetic acid, 3-iodopropionic acid, 2-iodoethanol, 2-iodoaniline, 3-iodoaniline, 4-iodoaniline, 4-iodoanisole, 5-iodoanthranilic acid, o-iodobenzoic acid, m-iodobenzoic acid, p-iodobenzoic acid, p-iodobenzenesulfonyl chloride, o-iodobenzyl alcohol, m-iodobenzyl alcohol, p-iodobenzyl alcohol, iodobenzene, o-diiodobenzene, m-diiodobenzene, p-diiodobenzene, o-iodobenzyl chloride, l-iodo-2-nitro-benzene, 1-iodo-3-nitrobenzene, 1-iodo-4-nitrobenzene, 2-iodophenol, 3-iodophenol, 4-iodophenol, 5-iodosalicylic acid, o-iodotoluene, m-iodotoluene, p-iodotoluene, o-iodo- .alpha., .alpha., .alpha.-trifluorotoluene, 2-iodo-6-methyl-3-pyridinol, 2-iodo-3-pyridinol, 4-iodopyrazole, 2-iodothiophene, 3-iodothiophene, 2,6-diiodo-4-nitroaniline, 2,6 diiodo-4-nitroaniline, 2,6-diiodo-4-nitrophenol, 3,5-diiodo-4-pyridone-N-acetate, 4-hydroxy-3,5-diiodobenzoic acid, 2,4,5-triiodobenzoic acid, 3,4,5-triiodobenzoic acid and 2,4,6-triiodophenol.
4. A method of forming a pattern characterized by comprising the steps of forming a coating film of a radiation-sensitive composition comprising an azide compound, an iodine compound at least a part of which can be fixed substantially in a polymer layer by exposure to a radiation and a polymer substantially having compatibility with the azide compound and the iodine compound, exposing the coating film to a radiation having a desired pattern, heating the coating film to remove the iodine compound from an unexposed region of the coating film and exposing the coating film to an oxygen-containing plasma to remove the unexposed part.
5. A method of forming a pattern according to Claim 4 wherein the weight ratio of the polymer : iodine compound :
azide compound is in the range of 1:0.1-3:0.05-2.
azide compound is in the range of 1:0.1-3:0.05-2.
6. A method of forming a pattern according to Claim 4 or 5 wherein a heating temperature of the coating film is above a sublimation temperature or boiling point of the iodine compound.
7. A method of forming a pattern according to Claim 4 or 5 wherein the radiation is U.V. light.
8. A method of forming a pattern characterized by comprising the steps of forming a coating film of a radiation-sensitive composition comprising an azide compound, an iodine compound at least a part of which can be fixed substantially in a polymer by exposure to a radiation and a polymer substantially having compat-ibility with the azide compound and the iodine compound and a soluble in an aqueous alkaline solution on a base, exposing the coating film to a radiation having a desired pattern, subjecting the coating film to the development with the aqueous alkaline solution to remove an unexposed part, and exposing the coating film and the base to an oxygen-containing plasma to etch the base.
9. A method of forming a pattern according to Claim 8 wherein the polymer soluble in an aqueous alkaline solution is at least one polymer selected from the group consisting of polyvinylphenol, novolak resin, styrene/
maleic anhydride copolymer, cellulose acetate hydrogen-phthalate, polyvinyl hydroxybenzoate, polyvinylhydroxy-benzal, polymethacrylic acid and polyacrylic acid.
maleic anhydride copolymer, cellulose acetate hydrogen-phthalate, polyvinyl hydroxybenzoate, polyvinylhydroxy-benzal, polymethacrylic acid and polyacrylic acid.
10. A method according to Claim 4 or Claim 8 which comprises employing, as said azide compound, a compound selected from the group consisting of a compound of the general formula:
wherein A represents an element or a substituent selected from the group consisting of O, S, CH2, CH2CH2, SO2, S2, CO, COO, S03, CH=CH and CH=CHCO, and X, Y and Z each represent an element or a substituent selected from the group consisting of an azido group, hydrogen, alkyl group, nitro group, halogen, amino group, monoalkylamino group, alkoxy group, hydroxyl group, sulfonic acid group, sulfonic acid ester group, carboxylic acid group and carboxylic acid ester group; and a compound of the general formula:
wherein X, Y and Z each represent an element or substit-uent selected from the group consisting of an azide group, hydrogen, alkyl group, nitro group, halogen, amino group, monoalkylamino group, alkoxyl group, hydroxyl group, sul-fonic acid group, sulfonic acid ester group, carboxylic acid group and carboxylic acid ester group.
wherein A represents an element or a substituent selected from the group consisting of O, S, CH2, CH2CH2, SO2, S2, CO, COO, S03, CH=CH and CH=CHCO, and X, Y and Z each represent an element or a substituent selected from the group consisting of an azido group, hydrogen, alkyl group, nitro group, halogen, amino group, monoalkylamino group, alkoxy group, hydroxyl group, sulfonic acid group, sulfonic acid ester group, carboxylic acid group and carboxylic acid ester group; and a compound of the general formula:
wherein X, Y and Z each represent an element or substit-uent selected from the group consisting of an azide group, hydrogen, alkyl group, nitro group, halogen, amino group, monoalkylamino group, alkoxyl group, hydroxyl group, sul-fonic acid group, sulfonic acid ester group, carboxylic acid group and carboxylic acid ester group.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000455393A CA1181627A (en) | 1981-07-15 | 1984-05-29 | Radiation-sensitive composition containing an azide compound and an iodine compound |
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10933781A JPS5811930A (en) | 1981-07-15 | 1981-07-15 | Radiation sensitive composition and pattern forming method using it |
| JP109337/1981 | 1981-07-15 | ||
| JP75231/1982 | 1982-05-07 | ||
| JP57075231A JPS58192033A (en) | 1982-05-07 | 1982-05-07 | Radiosensitive composition and pattern formation using it |
| CA000407336A CA1176903A (en) | 1981-07-15 | 1982-07-15 | Radiation-sensitive composition including an iodine- containing azide compound |
| CA000455393A CA1181627A (en) | 1981-07-15 | 1984-05-29 | Radiation-sensitive composition containing an azide compound and an iodine compound |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000407336A Division CA1176903A (en) | 1981-07-15 | 1982-07-15 | Radiation-sensitive composition including an iodine- containing azide compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1181627A true CA1181627A (en) | 1985-01-29 |
Family
ID=27426355
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000455393A Expired CA1181627A (en) | 1981-07-15 | 1984-05-29 | Radiation-sensitive composition containing an azide compound and an iodine compound |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1181627A (en) |
-
1984
- 1984-05-29 CA CA000455393A patent/CA1181627A/en not_active Expired
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