DE2135482B2 - Photosensitive mixture for the production of photoresist layers - Google Patents

Description

C It is well known, e.g. B. from the British

Patent specification 1,179,776 that you can use the most diverse

Q light-sensitive polymers for the production of light-

crosslinkable layers and these for photomecha-

where X is a halo atom and R is an alkylene 3 ° niche reproduction purposes.
rest with 1 to 8 carbon atoms or a It is also known, for. B. from the German

Arylene radical means contains. Offenlegungsschrift 1 807 644, light-crosslinkable

2. Photosensitive mixture according to claim 1, layers, in particular those used for production characterized in that the N-halogenated of photoresist layers are used, adhesive cyclics Imide N-Bromosuccinimid, N-Jodoglutar- 35 \ detectors add to the adhesion of the layers imide or N-bromophthalimide. to improve on the substrate. A good

3. Photosensitive mixture according to claim 1. Adhesion of the photoresist layer to the support characterized in that the N-halogenated is the more important, the more active and the more active the etchant Imide in a concentration of bi '> to 10 is the image size smaller. So is z. B. at the main weight percentage, preferably from 0.5 to 3 weight position of microelectronic circuits percent based on the weight of the existing photographic route, which is the repro-polymers, is present. production of comparatively small pictures that

4. Photosensitive mixture according to claim 1, adhesion of the photoresist layer particularly critical, characterized in that it is used as an additional to the desired high image resolution and image adhesion improvement To achieve an organic 45 quality compound.

alkoxysilane, which is free of halogen atoms and from the USA.-Patent 3,520,083 it is for example

Epoxy and amino radicals is contains. wisely known as organoalkoxysilane adhesion promoters

5 Photosensitive mixture according to claim 4 to be used. However, it has been shown that the, characterized in that the organoalkoxy with the known adhesion promoters achievable effects silane two or three alkoxy radicals with 1 to 4 carbon 50 do not completely satisfy, ie that the achievable atoms and other silane substituents for effects many cases of use are still low in relation to alkyl, alkenyl, acyloxyalkyl or aryl radicals,
having. The object of the invention was therefore to provide a light-sensitive

6. Photosensitive mixture according to the Auffindliches mixture for the production of photo proofs 4 and 5, characterized in that 55 resist layers indicate which have improved adhesion the organoalkoxysilane from y-methacryloxypropyl on substrates of various types, instrimethoxysilane consists. special to those who are exposed to extreme exposure

7. Photosensitive mixture exposed to inactive caustic agents or on which comparative claims 4 to 6, characterized in that small resist images are produced, for example the Organoalkoxysilane in concentrations of 60 wise to the production of microelectronic 0.025 to 0.5 percent by weight, based on the substrates that can be used for circuits. Weight of the polymer mass. The invention was based on the knowledge that

8. A photosensitive mixture according to claim 1, which produces certain N-halogenated cyclic imides characterized in that the photosensitive excellent as an adhesion promoter in photoresist layers Polymers is a polyvinyl cinramate. 65 let use.

9. Photosensitive mixture according to claim 1, the subject matter of the invention is thus a light emitting device characterized in that it is an arylazide as a sensitive mixture for the production of photo-sensitizer contains. containing resist layers

(', ι an unsaturated acidic ester a> - polyol, a sensitized synthetic or natural rubber. e> n sensitized cyclized polyisoprene or a sensitive one. Styrene-isoprene copoly merisate as a film-forming solvent soluble in organic solvents. photosensitive polymer compound and

i2i one or more liability-improving connections.

(j.!> is characterized by it. that the photosensitive mixture acts as an adhesion-improving compound at least one N-halogenated cyclic * I mid der l 'formula

N-X

wherein X is a halogen atom and R is an alkylene radical having 1 to 8 carbon atoms or an arylene radical means contains.

In the specified ; n formula can X e.g. B. a chlorine. Be bromine or iodine and P is ethylene. Propylene, hexylene or octylene radical or an o-phenylene radical. with the proviso that the radicals may optionally be substituted, e.g. B. by alkoxy, aryloxy or nitro radicals or halogen atoms.

The iii photosensitive according to the invention N-halogenated cyclic imides contained in mixtures differ clearly on the adhesion Improving compounds suggested in German Offenlegungsschrift 2,063,571.

The invention improves the adhesion of Achieved photoresist layers on substrates. The improved adhesion not only extends to Supports of the type commonly used in photoresist materials, e.g. B. on a substrate made of copper, zinc, steel or chrome, but it becomes a beneficial improvement in adhesion also in the case of supports of the silicon dioxide type, in which the adhesion problems are particularly pronounced, their use in the microelectronic field, in which a good image resolution is required with richly detailed images is, but is particularly recommended.

The adhesion of a photosensitive mixture according to the invention to layer supports can be more advantageous Way can be further improved by adding organoalkoxysilanes to the mixtures, which are free of halogen atoms as well as epoxy and amino radicals can be added.

Those photosensitive mixtures have proven to be particularly advantageous, their photosensitive Polymers made from rubber sensitized with azides or from unsaturated acidic esters of Polymers containing hydroxyl groups, for example polyvinyl cinnamate, exist.

The use of the following N-halogenated cyclic imides er-N-bromosuccinimide has proven to be particularly advantageous.
N-chlorosuccinimide.
N-iodosuceinimide.
N-bromogluiarimide.
N-cliloroglutarimide.

N-iododutarimide.
N-Bro; nophthaliniid.
N-chlorophthalimide and
N-iodopruhalimide.

In the advantageous way, in addition, \ er \\ Organoalkoxysilanes are those that are free of halogen atoms and epoxy and Aino residues are. These organoalkoxysilanes preferably contain at least two and no more than three alkoxy groups, these alkoxy groups contain in a particularly advantageous manner 1 to 4 Kuhlenstoffatome, so that it is z. B. to methoxy. Ethoxy, propoxy or butoxy radicals can act.

The further substituents optionally present in such silanes are functional organic radicals, but not epoxy or amino radicals. Come as further substituents z. B. Alk> l radicals with 1 to 18 carbon atoms in

Question, for example ·. ·: Methyl-, ethyl-. Propvl-. Butyl. Hexyl, octyl, dodecyl or stearyl radicals. further Aralkylresia, e.g. B. Benzylreite. also alkoxyalkyl radicals having 1 to 12 carbon atoms, e.g. B. methoxyethyl, Ethoxyl or methoxypropyl residues. also alkenyl radicals. z. B. vinyl residues. also acyloxyalkyl radicals, whose acyl component is made from an alkylcarbonyl or alkenylcarbonylg. jppe exists, e.g. B. acetoxyethyl, Acryloxypropyl or methacryloxypropyl radicals, also aryl radicals, e.g. B. phenyl radicals, as well as alkaryl radicals, z. B. Tolyl residues.

Typical suitable organoalkoxysilanes are e.g. B. Methacryloxypropyltrimethoxysiur .. Phenyltrimethoxysilane, Benzyltrimethoxysilane, dimethyldimethoxysilane, methylphenyldimethoxysilane, diphenyldimethoxysilane, Vinyltrimethoxysilane, hexyltrimethoxysilane, stearyltrimethoxysilane, diphenyldiethoxysilane, dimethyldiethoxysilane, Methyltoluyl diethoxysilane, methylphenyldipropoxysilane and phenyltripropoxysilane.

The photosensitive compositions according to the invention can be the N-halogenated cyclic imides Contained in various concentrations. The use of the imides in concentrations has proven to be expedient of up to about 10 percent by weight, preferably from about 0.5 to 3 percent by weight based on the weight of the polymer present in the mixture. This means that the Coating compound used for coating thus up to about 2.5 percent by weight of N-halogenated May contain imide.

Particularly good results are achieved when the organoalkoxysilane in the light-sensitive Mixtures according to the invention in concentrations of up to about 5 percent by weight, based based on the weight of the polymer present in the blend. As very special It has proven advantageous to use the photosensitive mixtures according to the invention organoalkoxysilanes specified type in concentrations of about 0.5 to 2 percent by weight, based on the weight of the Polymers, to be incorporated, which is in an amount of about 0.025 to 0.5 percent by weight, based on the Total weight of the coating compound to be used, corresponds.

The light-sensitive mixtures according to the ermerisatc de, specified type s, nd are commercially available

finding can in the usual known manner ai: f die "haltli, ^ _Sensib jij _satO rcn turnable, in

Shichuras are brought up, z. B. by W irbel- Hei oen α * inlirhc ·· \ ₇ idpn h „, h

coating Fheßbe.chichtun ,. Immersion coating organic solution mtte η ^ J- / ™ _R ^ ^nd . ^elt

tuns or spray coatings. The choice of liclu- 5 it is Aryiaz.de οrzug> veise um B. ^ zide,

sensitive polymer, a suitable solution - e.g. around 4.4'-D.az.dosi.lben p-Phe ^ - ^ de.

medium, for the application of an "aeeWten layer- 4.4'- _{Diazidobenzo P} henon, 4,4-D.az.dod p. en ^ me-

iräeers so ' _A ie eines Wianetcn "coating awards. 4.4'-D.az, butalkon - ^ (4. ^ henzaIj-

Fahrcns depends on the intended use cyclohexanone or 2.6-D .- (4-azidobium) -4-methyl-

away. which to the "erzeu _a te resist image zueeführi, to cyclohexanone. In vorie.lhafter NN ei * χcnvendbar

As already stated, the light-sensitive are also Monoaz.de. z. B. p -.- ^ dobenzo-

borrowed mixtures according to the invention to all known. phenone.

Usually used support on aetraaen Typical, according to the invention by adding the adhesives, z. B. on foils made of metals, for example mediator modifiable photosensitive odors copper. Aluminum. Stole. Zinc and magnesium. 15 with a gel of m organic solutionMuteln also on layers of silicon dioxide in the form of soluble azides are e.g. B. from the b \ -v.-. atent of strips or plates as well as layer supports from writings 2 ^ 52 379 and 2 9 ^ 0 b ^ 3 as well as tu _; the glass, which can be coated with a metal. British patents 8b6 IDU and!>9_>. : e.g. with chromium, a Chromleaieruna, nickel. Stole. knows.
Silver, gold or platinum. 20 A second type of light; little gene! v-wn.

If the photosensitive mixture contains a üraano- which are used according to the invention, contain i'oK-

alkoxysilane. so Sorae should be aetrrien for it. kidneys with unsaturated groups, which are

that on the layer support surface to be coated naturally around light-sensitive I ol> only

aenus water is present, the alkoxy groups are concerned. However, mixtures of this type can also be used

to hydrate the silane. 25 sensitizers can be added to this water in order to

it is water of hydration, which increases the likelihood or its spectral response

Layer carrier surface is also present, able to modify. In particularly advantageous

when the layer substrate has been heated, what happens in the weaving \ erendbaren polymers of the specified us

Usually happens to become Tose bound water by esterification of hydroxyl group; · .-

jetting. "" 30 containing polymeric substances, e.g. Pcly \ in> l-

"The type of light alcohol or cellulose with a cinnamic acid halide used in the individual case,

sensitive mixture depends on various factors. B. the cinnamic acid chloride or m-nitrocinnamic acid

gate off, z. B. of the desired photographic chloride, as z. B. from the USA .-- Paient ^ chrift

Sensitivity and the desired properties 2 670 286 is known. Cinnamic acid ester from PoKmiivI-

of the resi ^ t image to be achieved. ^ 35 alcohol and cellulose with different acyl group

therefore the most diverse light-sensitive poly contents are z. B. by deacylation of practical

mers are used which can be produced for the production of fully esterified cinnamic acid esters.

Relief or stencil-like resist images suitable as z. See U.S. Patent 2,725,372

are. "" is described. Iaben as particularly advantageous

Typical suitable photosensitive compositions are solvent-soluble esters with a content e.g. those containing a polymer, from about 60 to 100 mole percent, preferably \ on which itself is not photosensitive, but which has been shown to contain about 87 to 100 mole percent vinyl cinnamate. Sensitizer can be added to the polymer with cinnamic acid esters of polyvinyl alcohol and light-sensitive by giving it the ability to cellulose "become" in organic solvents imparts, when exposed to visible or ultra-45 soluble esters, which make about 60 to 100 mole violet radiation insoluble. contain percent bound cinnamoyl ester groups.

Photosensitivities have proven to be particularly advantageous. This can be simple as well as

Lent mixtures proven to act on the polymers to mixed esters, z. B. to polyvinyl

Base \ on natural or synthetic rubbers, acetate cinnamate or cellulose acetate cinnamate, the

those with at least 60 mol% cinnamoyl ester groups soluble in organic solvents

Azides are sensitized. Typical acyl groups, different for the rest of the time

Suitable rubbers of this type are e.g. B. natural or unesterified or partly acyl groups

rubber, which is usually contained in the form of volcanized sulfur and is partly unesterified,

Barer rubber is referred to, also oxidized chewing die in the light-sensitive mixtures according to the

Tschuke, z. B. the amount of polymer and sensi-

known type, cyclized rubbers, e.g. B. the bilizer depends to a certain extent on their

U.S. Patents 2,371,736 and 2,381,180 Solubility in the solvent used, the

known type, and also under the term compatibility of the sensitizer with the light

Rubber covered rubber-like synthetic poly-sensitive polymers as well as of course from

merizates and copolymers, e.g. B. those from 60 depending on the intended use of the mixture. In the

1-Diolefins, for example 1,3-butadiene, isoprene will usually give good results when using

and neoprene can be produced, as well as polyisoprene, which contain mixtures containing up to about 25 weight

z. B. according to the in "Journal of Polymer Science", percent, preferably about 5 to 15 percent by weight

Part A, Vol. 2, No. 9 (1964). Pp. 3969 to 3985 and polymer included. The sensitizer can be found in

3987 to 4001. The method described can be produced 65 concentrations such as about 2 to 25 percent by weight,

is, as well as copolymers of butadiene with preferably from about 2 to 10 percent by weight,

various unsaturated compounds, e.g. B. based on the weight of the polymer, are present,

with styrene and isobutylene. Synthetic mixed poly- For special purposes, self-made

7 8

concentrations outside of the specified The specified solution was in three 100 ml

Areas are used. parts divided. One part remained unchanged

The photosensitive mixtures according to the enacted and used for comparison purposes, the

In addition, the usual known additives, the second portion was made with 0.18 g of N-bromosuccinimide

included, e.g. B. surfactants, coating 5 and the third part was with 0.37 g of N-bromosuccin

processing aids, antioxidants, fungicides, bakimide added. The specified three photoresist

tericides and thickeners. Certain such dimensions were then applied to stainless steel sheets

sentences, e.g. B. Antioxidants of certain types, steel tend to be applied in such a way that after drying

in addition to realizing layers with a layer thickness of 6.35 microns with certain organoalkoxysilanes

yaw, which is why the relevant jo was obtained in such cases.

Addition of the photosensitive coating compound The three photosensitive coating compounds obtained in this way

is added at the very end. Borrowed recording materials were then through

For making photoresist images using a transparent negative for 4 minutes under Verder Photosensitive mixtures according to the invention using a carbon arc lamp as a light source the substrate to be used is first exposed in 15 with about 2150 lux. To develop the treated in the usual known manner, in which z. B. Images became the unexposed areas of the resist Surface of a pretreatment with acids, coated with "Stoddard's solvent", i. H. one Cleaning agents or the like is subjected to the water-clear petroleum fraction (see H. Römpp, Clean surface. In the course of such a chemical encyclopedia, 6th edition, 1966, p. 6168), negotiated and wash ao when using certain shifts. Thereafter, the recording material became carriers the substrate surface can be rinsed with water for as long and then 15 minutes be heated until the remaining water or another, long post-hardened at 140 ° C. The etching of the layer at The retraction operation was carried out by immersing the remains of the record Fluid are driven off. On the materials in an etching solution of the following composite layers the coating compound is then calculated with the following:

Using one of the customary known methods of 37 to 38% hydrochloric acid 200 ml

brought. The level of protection depends on the _7Q . _{bjs? 1} ,, JJ _{6 Sa} , p. _acidic acid 175 ml

iy _{P of} the light-sensitive mixture used, iron (IIl) chloride solution of 42 ⁰ Be 2625 ml
as well as the intended use of the resist image to be produced. In most cases, the layer thicknesses of about 2.54 to 25.4 micron recording materials in the etching solution have proven to be suitable for determining the adhesive strength. leave until the resist layers of the etchant

The photosensitive recording effect obtained was no longer withstood. To determine material is then at a temperature of 60 whether the resist images or still resisted already heated to 130 ⁰ C for so long, have failed until the residual solvent 35, the recording materials were perimittel is removed. This pre-hardening also leads, up to and including the etching solution, rinsed with water to a certain extent to an improved and then an air stream of high pressure of the adhesion of the layer to the layer support. That exposed to 1.05 kg / cm ^2. The photosensitive recording material obtained was dried by the air stream, and in the event of failure the resist layer was then exposed imagewise to actinic radiation, the exposed areas of the photosensitive power of the airy layer sweeping over the surface hardened and insoluble be made. Stroms removed. If no failure occurred, the image could then be developed and the recording materials were repeated for a further period of time by washing with a liquid that was put back into the etching solution and the solvent testing for the unexposed, uncured 45 was repeated for that long until failure occurred. Represents polymers but is a nonsolvent. The comparative sample failed after 1/2 hour. The samples according to the invention for the poly present in the exposed areas, the resist compositions of which are mere so that the polymer composition was preferably mixed with N-bromosuccinimide, failed to be removed from the unexposed areas and only after one hour
exposed areas a relief image made of hardened 50.
Polymer remains. After developing the B e 1 s ρ 1 e I 2
Relief image is the adhesion of the resist image to the A photoresist composition based on a layer support was produced by a photosensitive polymer for about 5 to 15 minutes, which had the long-term post-heating of the recording material to the following composition:

a temperature of about 120 to 180 ° C improves 55 pdwinyl cinnamate 12.5 g

The resulting film can then be used as a resist image 1,2-benzanthraquinone 1 25 g

Hydroquinone 0.1 g is used

The following examples are intended to approximate the invention of benzoic acid 0 5g

B e 1 s ρ 1 e 1 1 60 methyl glycol acetate 125 ml

A photosensitive mixture was obtained based on the _{mass obtained λνυΓαβ in two} 5μ ml proportions

of a cychsierten polyisoprene the following _{compounds in Antdl} ^ _{6 not modified and served}

reduction prepared: _{as erg} v i _e self sample. The second stake were

Cyclized polyisoprene 45 g 65 0.3 g N-bromophthalimide added. The two

Xylene 255 ml photoresist masses were after the fluidized bed

2, o-Di- (4'-azidohenza!) - 4-methyl- process on copper substrate in the manner

cyclohexanone as a sensitizer ... 1.5 g worn and dried that layers with an im

dry state measured layer thickness of 7.62 microns were obtained. The photosensitive recording materials obtained were then exposed through a negative transparency for 1 minute at a distance of 1.22 m to the light of the white flame of a carbon arc lamp of 35 amps. To develop a resist image, the unexposed polymer areas were removed from the exposed recording material by washing in benzene with gentle stirring. The substrate was then etched by immersing the recording material into an iron (lll) -chIorid etching solution of 42 ° ^C Βέ at 54 C.

At a point in time when the resist image of the comparative sample had already failed, it still passed good adhesion between the copper layer support and the polymer mass according to the invention, to which N-bromophthalimide had been added, obtained resist image.

Example 3

The procedure described in Example 1 was repeated using a support from a silicon plate instead of the stainless steel support. There were correspondingly advantageous Get results.

Example 4

The procedure described in Example i was repeated using N-chlorosuccinimide instead of N-bromosuccinimide. Accordingly, favorable results have been obtained.

Example 5

The procedure described in Example 1 was repeated using N-iodoglutarimide instead of N-bromosuccinimide. Accordingly, favorable results have been obtained.

Example 6

This example shows that by using both silane and N-bromosuccinimide one can achieve one Improvement of the adhesive strength of rubber-like photoresist compositions on substrates stainless steel is achieved.

A coating compound of the following composition was prepared:

Cyclized polyisoprene 15 parts

Xylene 100 parts

2,6-Üi- (4'-azidobenzal) -4-methylcyclohexanone as

Sensitizer 0.53 parts

The polymer composition obtained was applied to a layer support consisting of a stainless steel plate Steel existed, applied and then dried. The obtained recording material became

ao exposed to a fine image pattern and then heated for 15 minutes at 150 ° C. in the specified "Stoddards Solvent" for development. The developed recording material was etched in an etching bath of the composition given in Example 1. The resist image failed after ¹ _1/2 hours.

A coating composition of the specified type was prepared, but with 0.1 part of γ-methacryloxypropyltrimethoxysilane had been transferred. The production of the photoresist material and the resist image was carried out according to the specified procedure. The resist image obtained withstood the action of the Etch bath for IV2 hours.

Another polymer composition of the specified type was prepared, but in addition to the Silane 0.5 part of N-bromosuccinimide was incorporated. A resist image was produced in specified way. The resist image obtained withstood the action of the etching bath for 3 hours.

Claims (1)

10. Use of the photosensitive patent claims: Mixture according to claim 1 for the production of Photoresist layers on layers of metal 1. Photosensitive mixture for the Her- or silicon,
position of photoresist layers. containing 5 11) an unsaturated acidic ester of a polyol. a sensitized synthetic or Na- turmeric rubber. a sensitized cyclized
PoK isoprene or a sensitized Stvrol isoprene copolymer as one in organic ^lo
Solvent-soluble, film-forming, photosensitive polymeric compound and ^The invention relates to a liquid-sensitive mixture for the production of photoresist layers ties. characterized in that the ^ (D an unsaturated acidic ester is a polyol, light-sensitive mixture ah, adhesion- ^improving emen sensitive synthetic or natural Compound of at least one N-halogenated evclic rubber, a sensitive cyclized poly- cal imide of the formula "isoprene or a sensitized Snrol-isoprene- _2Q copolymer as one in organic solution O medium-soluble, film-forming, light-sensitive polymeric compound and C (2) one or more liability improving _., .. bindunsen.