DE3346716A1 - Method of producing resist patterns and dry-film resist suitable for said method - Google Patents

Abstract

In the production of resist patterns by applying a radiation-sensitive, positive-working resist layer to a substrate, imagewise irradiation of the resist layer with actinic radiation and removal of the irradiated portions of the layer to develop the resist pattern, use is made of a radiation-sensitive resist layer based, in particular, on soluble poly(diacetylenes) containing sensitisers which can be activiated by the actinic radiation and which, after their activation, induce or accelerate the molecular decomposition of the poly(diacetylenes). The invention also relates to dry-film resists with a temporary, dimensionally stable layer base, a radiation-sensitive resist layer which is applied thereto and is based, preferably, on soluble poly(diacetylenes), and, optionally, to a top layer on the radiation-sensitive resist layer; the radiation-sensitive resist layer contains sensitisers which can be activated by actinic radiation and which, after their activation, induce or accelerate the molecular decomposition of the poly(diacetylenes).

Description

Process for the production of resist patterns and for this process

Suitable dry film resist The invention relates to a method for the production of imagewise structured resist patterns on a substrate on which a radiation-sensitive resist layer applied to the substrate Based on, in particular soluble, poly (diacetylenes) imagewise with actinic Radiation is irradiated, thereby causing a molecular breakdown of the poly (diacetylene) and enables selective removal of the irradiated areas of the resist layer is, then the irradiated areas of the resist layer are removed and the resist pattern obtained in this way is optionally aftertreated. The invention relates to furthermore a dry film resist suitable for use in this process with a solid, radiation-sensitive and under Application of pressure and optionally heat to a resist layer transferable to a substrate based on, in particular soluble, poly (diacetylenes).

Positive working, light-sensitive recording materials ftr the production of resist patterns, such as those used in the production of Conductor tracks, printed circuits, interlayer and multilayer circuits, electronic components, in semiconductor technology etc.

can be used are described several times in the literature.

Such positive-working resist materials are for example on Based on compounds containing o-quinonediazide groups, in particular o-quinonediazide groups containing polymers, which when irradiated with actinic light under Formation of alkali-soluble photolysis products react (see e.g. DE-A-20 28 903, DE-A-22 36 914, US-A-3 782 939, US-A-3 837 860 and US-A-4 193 797). Another Class of very advantageous, positive working photodegradable resist materials based on aromatic and / or heteroaromatic o-nitrocarbinol ester groups containing polymers, which after exposure to # aqueous alkaline developer solvents can be washed out (cf. e.g. DE-A-21 50 691 and DE-A-29 22 746).

The well-known, positive-working, photodegradable resist materials and dry film resists are in view of modern applications and high requirements always in need of improvement. For example, it is partly mechanical and chemical resistance of these resist materials for a variety of uses not yet satisfactory. A higher resolving power of the Resist materials required.

In EP-A-22 618, EP-A-77 577 and US-A-4,314,021 the use of monomeric diacetylenes for the production of photoresist layers described. In this case, layers of the diacetylenes are generally multilayered irradiated imagewise, whereby a photopolymerization in the irradiated areas is triggered. Then the non-irradiated areas of the resist layer removed with a developer solvent. These resist materials show at high Quantum yield high resolution and provide resist patterns of high mechanical and chemical resistance. The very cumbersome and time-consuming process is very disadvantageous Production of the photopolymerizable resist layers from the monomeric diacetylenes, which is preferably applied to the substrate using the Tangmuir-Blodgett technique will. These resist materials are also negative working. For many purposes however, positive-working resist materials are advantageous.

In the earlier German patent application P 33 42 829.8, a method for the production of resist patterns described in which one applied to a substrate Resist layer based on poly (diacetylenes) irradiated imagewise with actinic light molecular degradation of the poly (diacetylenes) takes place. After that, the exposed areas of the resist layer in a suitable manner, for example with a Developer 'solvent or a plasma gas. This positive working, photodegradable resist materials based on poly (diacetylenes) allow the production of very durable resist patterns with high resolution; But they are in terms of their processing and application properties Can still be improved.

The object of the present invention was to provide a new, positive working, to show radiation-sensitive resist material, which is suitable for the production of resist patterns in the process known per se with imagewise irradiation and development of the resist layer is suitable and, if the resolution is high, production of resist patterns with good application properties, in particular with good mechanical and chemical resistance, allowed. Object of the invention It is also to show such a resist material in which with actinic Radiation can be worked in as large a wavelength range as possible, which only requires the shortest possible exposure times and is easy and problem-free can be handled and processed.

It has now been found that this task can be achieved by radiation-sensitive, Resist layers based on poly (diacetylenes) that are degradable under the action of actinic radiation is solved, which can be activated by the radiation Sensitizers contain, which after activation by the irradiation, the molecular degradation of the Poly (diacetylene) induce or

accelerate.

The invention therefore relates to a method for production of resist patterns on a substrate, in which an applied to the substrate, radiation-sensitive resist layer based on, in particular soluble, poly (diacetylenes) image-wise irradiated with actinic radiation, thereby a molecular breakdown of the Poly (diacetylene) causes and selective removal of the irradiated areas the resist layer is made possible, then - optionally after tempering the resist layer - the irradiated areas of the resist layer are removed and the resist pattern obtained in this way is optionally aftertreated, which thereby is characterized in that the radiation-sensitive resist layer by the actinic Contains radiation-activatable sensitizers that are activated by the irradiation induce or accelerate the moleldilabban of the poly (diacetylenes).

The invention also relates to a dry film resist, in particular for use in semiconductor technology in the manufacture of printed circuits, Thin-layer or multilayer circuits, electronic components, etc., with a dimensionally stable support, a solid, laminatable, Radiation-sensitive resist layer based on, in particular soluble, poly (diacetr len) and preferably a cover layer on the radiation-sensitive resist layer, that of the radiation-sensitive resist layer without simultaneous removal of the temporary layer support is peelable, the dry film resist thereby is characterized in that the radiation-sensitive resist layer by actinic Contains radiation-activatable sensitizers which, after their activation Induce or accelerate the degradation of the molecules of the poly (diacetylenes).

According to the invention, the radiation-sensitive resist layers are based on poly (diacetylenes). It has been shown that the poly (diacetylenes) in solid Layers using actinic radiation in a very broad wavelength range with the help of sensitizers are so largely and completely degraded That this leads to a property differentiation that is sufficient for the development of the resist pattern is achieved between the irradiated and non-irradiated areas, so that resist patterns with sharp and exact contours and without residual layers on the development exposed areas of the substrate are obtained. That the poly (diacetylene) Suitable for radiation-degradable Resisuma materials, was among other things surprising in so far as than before Resist layers made from poly (diacetylenes) by photopolymerization of monomeric diacetylenes, i.e. through polymer build-up by means of actinic radiation, had been made. The addition of the sensitizers to the radiation degradable Poly (diacetylene) resist layers not only allow a considerable shortening of the Times for the imagewise exposure of the resist layers, but allows in particular also - depending on the choice of sensitizers - the use of different actinic Radiation for the imagewise exposure of the resist layers and thus a significant one Enlargement of the actinic radiation range for the method according to the invention, from the wavelength range of the far UV to the wavelength range of heat and infrared radiation. In addition, the addition of the sensitizers also the range of applications of the resist materials in manufacturing processes the resist pattern is enlarged. With the inventive, degradable by irradiation Resist layers based on poly (diacetylenes) can be used in the pattern-wise structuring high resolutions can be achieved, and resist patterns of high durability result.

Advantageously, for the formation of the radiation-sensitive according to the invention Resist layers, among other things because of their easier processability and manageability, soluble poly (diacetylenes) are used. The poly (diacetylenes) generally have an average molecular weight (weight average, determined by light scattering) im Range from 10,000 to 2,000,000, especially in the range from 50,000 to 1,000,000.

The poly (diacetylenes) to be used in the present invention are as such known and can be prepared by the per se customary and known processes will.

According to the invention, in particular those poly (diacetylenes) are used which have been prepared by polymerizing monomeric diacetylenes of the general formula (I) R1 - C a C - C # C - R2 (I) and correspondingly recurring structural units of the general formula (II ) contain In the formulas (I) and (II), R1 and R2 can be identical or different and independently represent an aliphatic, aromatic or mixed aliphatic-aromatic radical, generally with 1 to 50 carbon atoms, these radicals being saturated or unsaturated as well as optionally substituted and / or in particular also interrupted by heteroatoms or groups containing heteroatoms. Particularly suitable heteroatoms are oxygen, nitrogen and sulfur.

The radicals R1 and R2 preferably contain 10 or more carbon atoms. In particular Preferred are those radicals R1 and R2, the acid ester, acid amide, sulfonate, urethane and / or contain urea groups. With the common diacetylenes the radicals R1 and R2 are generally the same.

Typical representatives of the radicals R1 and R2 in the general formulas (I) and (II) for the soluble poly (diacetylenes) are: (i) - (CH2) 1l CH3 Corresponding soluble poly (diacetylenes) and their preparation are described, for example, in J.Pol.Sci. Polymer Letters Ed. 16: 607 (1978); J.Chem.Phys. 70: 4387 (1979); J.Pol.Sci. Polymer Letters Ed. 17: 203 (1979); Makromol.Chem. Rapid Communication 3, 231, 249 and 815 (1982).

It has proven to be particularly advantageous for production the use of such polydiacetylenes in the resist layers degradable by irradiation, in which those are generally still contained in the polymers after the polymerization unreacted monomeric diacetylenes, for example by reprecipitation of the polymers or Extraction with suitable solvents, e.g. acetone. The solvents for the soluble foly (diacetylenes) include methylene chloride, Chloroform, dimethylformamide, nitrobenzene, decalin, etc.

In the case of the poly (diacetylenes) to be used according to the invention, it can are both homopolymers of monomeric diacetylenes and copolymers of two or more different monomeric diacetylenes or copolymers of one or more monomeric diacetylenes with a minor amount other common comonomer building blocks. Those poly (diacetylenes) are preferred, which consist exclusively of diacetylene units. The poly (diacetylene) can for the production of the radiation-sensitive resist layer alone or also as a mixture are used together.

According to the invention are in the radiation-sensitive, by irradiation resist layer degradable with actinic radiation next to the poly (diacetylenes) Contain sensitizers or sensitizer systems caused by the irradiation are activated with actinic radiation and, in the activated state, the degradation of molecules induce or accelerate the poly (diacetylene). With those that can be activated by radiation Sensitizers can be those caused by actinic light: in particular in the wavelength range from about 180 to about 800 nm, can be activated, or including those caused by thermal radiation, in particular IR radiation of one wavelength greater about 0.8po, can be activated.

The light-activated sensitizers include those compounds, those under the influence of actinic light, especially the wavelength range mentioned above, form free, reactive radicals immediately.

An example of this is azobisisobutyronitrile. As light-activated However, sensitizers are also compounds with one or more absorption bands in the wavelength range of actinic light that occurs when irradiated with the actinic light into an excited, high-energy state, such as very common the triplet state, pass over and from this excited state the degradation of the Poly (diacetvlene) either through energy transfer and / or in particular via induce or accelerate radical reactions. To the light-activated Sensitizers in this category include, for example, xanthene dyes, of which i.a. Rhodamine 6G has provided particularly beneficial results; Thiazinium dyes, such as methylene blue, but also polynuclear quinones and their derivatives, such as in particular Anthraquinone or anthraquinone derivatives; and aryl ketones, here in particular Benzophenone or mixtures of benzophenone and Michler's ketone may be mentioned.

The heat-activatable sensitizers are generally to compounds that form free, reactive radicals in the heat and then over a radical reaction with the poly (diacetylenes) cause the molecule to break down. The heat-activatable sensitizers are therefore usually to remove radical compounds or compounds that decompose into free radicals under the influence of heat, which react with the poly (diacetylenes) in the heat. As heat-activated sensitizers those compounds are preferred which are under the influence of heat, in particular at temperatures in the range of about 40 to 200 ° C, form free radicals. For this include in particular the customary and known free radical polymerization catalysts. Azobisisobutyronitrile and benzoyl peroxide may be mentioned by way of example and representative.

The radiation-activatable sensitizers can be used in the inventive Resist layers based on poly (diacetylenes) alone or in a mixture with one another are present. Depending on the type of sensitizers or sensitizer systems used this results in a large variety of process and application technology options, which allow a broad design and variation of the method according to the invention. For example, it is possible to use a light-activated sensitizer, the one in the wavelength range from about 250 to 320 nm, i.e. for the most part in the range absorbed by the self-absorption of the poly (diacetylene). In this case, the photodegradation becomes the poly (diacetylenes) by the sensitizer by, for example, three to four times accelerated. In another embodiment, light-activating bare Sensitizers are used whose absorption maxima outside the self-absorption of the poly (diacetylenes) lie, for example in the wavelength range of about 400 up to 800 nm, as in the case of the dyes absorbing in the visible range. In this In this case, it is possible for the irradiation of the resist layers to be simpler and more problem-free to use light sources to be handled without impairing the quality of the obtained resist pattern must be accepted. The use of heat-activated Sensitizers, for example, makes the use of IR lasers for imagewise Irradiation of the resist layers possible. In a further embodiment, you can Mixtures of two or more light-activated sensitizers are used whose absorption maxima are in different wavelength ranges. This makes it possible, for example, to determine the emission spectrum of the light sources for actinic light to better and more fully exploit. In the radiation-sensitive Resist layer can also contain mixtures of light-activated sensitizers and heat-activated sensitizers may be included. This is among other things for the the method of multiple irradiation of the resist layers described below advantageous, since in this case only one photographic image template is used, their image areas for actinic radiation of different wavelengths in different Dimensions are permeable or impermeable, a multiple image-wise exposure the resist layer becomes possible. The sensitizers that can be activated by radiation are in the resist layer based on the poly (diacetylenes) generally in amounts of 0.001 to 10% by weight, preferably in amounts of 0.05 to 5% by weight, based on the entire, radiation-sensitive resist layer included.

In the radiation-sensitive, radiation-degradable resist layers Based on the poly (diacetylenes), in addition to the radiation-activated sensitizers also contain other additives and / or auxiliaries, such as plasticizers, Pigments, fillers, antioxidants, etc. As plasticizers, in particular Dibutyl phthalate, bis (2-ethyl-hexyl) phthalate and the like. proven. These additional and / or auxiliaries are in the radiation-sensitive resist layers in general in amounts not exceeding 40% by weight, in particular in amounts up to 30% by weight on the entire, radiation-sensitive resist layer.

Those according to the invention, by exposure to actinic radiation Degradable resist layers based on the poly (diacetylene) can be applied to the to be protected or substrates to be modified afterwards according to the customary and per se known Application techniques are applied. For example, the application of the radiation-sensitive ones is suitable Resist layer Solution in which a solution of the resist layer forming components, i.e. the poly (diacetylenes), the sensitizers and any other additives and / or auxiliaries used, in one suitable solvent, for example of the type mentioned above, in the wiluschten Layer thickness according to the known coating processes, e.g. by spin-coating, Pouring, dip coating, lip pouring etc., applied to the substrate, the The solvent is evaporated off and the resist layer is dried. This solution coating of the substrate is particularly recommended if the radiation-sensitive Resist layers should be kept very thin and their dry film thickness below about 0.5 to 2 mm, preferably in the range from 10 nm to 2 # nn.

For thicker resist layers, for example in the range from 0.5 to 100 # m, also the application of a dry, prefabricated resist layer on the substrate using pressure and, if necessary, heat according to the usual lamination processes very advantageous.

For applying solid, prefabricated radiation-sensitive The best way to apply resist layers to the substrate is to use a dry film resist from which the radiation-sensitive, Degradable resist layer based on the poly (diacetylene) contains applied. as The materials used for this purpose and known per se are used for the substrate, especially plastic films or foils> e.g. made of polyesters. The temporary, dimensionally stable layer support should have moderate adhesion the radiation-sensitive resist layer based on poly (diacetylenes), which is less than the adhesion of the radiation-sensitive resist layer to it the substrate after lamination. This ensures that the temporary Layer support after the radiation-sensitive resist layer has been laminated on the substrate, optionally before or after the imagewise exposure of the resist layer, can be peeled off from this without the resist layer being removed again Substrate is dissolved. The application of the radiation-sensitive resist layer Base of poly (diacetylenes) on the temporary, dimensionally stable substrate can in this case again according to the per se known and customary processes, in particular from solution, according to the application techniques mentioned above. The dry film resists contain advantageously, but not necessarily, on the free surface of the Radiation-sensitive resist layer also applied a top layer, which in particular the protection of the radiation-sensitive resist layer when handling the dry film resist serves. This cover layer, which is preferably made of thin plastic films or sheets such as polyethylene, polypropylene, and the like have a lower adhesion compared to the radiation-sensitive resist layer as the Temporary layer supports to allow them to be laminated on the resist layer on the substrate can be peeled off from the latter without any problems.

If necessary, between the top layer and the radiation-sensitive Resist layer, an intermediate layer can also be arranged on the resist layer remains, the peeling off of the cover layer facilitates and in which for the development the developer solvent used for the imagewise irradiated resist layer is.

When using the dry film resists, the lamination of the radiation-sensitive To facilitate resist layer on the substrate are preferred in this case Resist layers used that contain plasticizers. In a preferred variant of the method is done before the radiation-sensitive resist layer is laminated onto the Substrate this from the surface facing away from the temporary layer support, i.e. for a short time from the side that is laminated onto the substrate pre-irradiated over the entire area with radiation which is actinic for this layer. Through this is a shortening of the times for the subsequent imagewise irradiation of the Resist layer made possible without the imagewise exposure due to this full-area pre-irradiation Differentiation and structuring of the resist layer is adversely affected. Such pre-irradiation has proven to be particularly advantageous when if dry film resists with relatively thick, radiation-sensitive resist layers, e.g. in the range of a few ym and more, as in these cases otherwise comparatively long exposure times for an image structuring that is true to the original of the resist layer with well-defined contours and without residual layer components the substrate would be required.

The radiation-sensitive resist layers according to the invention The basis of the poly (diacetylenes) are, when they have been prepared from solution, partially crystalline. Because of their high mechanical and chemical, as well as - especially when solitary Use of light-activated sensitizers - including thermal resistance can compare the radiation-sensitive resist layers according to the invention be kept thin, their layer thickness generally in the range of about 10 nm to 100; im lies. The thickness of the radiation-sensitive resist layer is determined in a known manner according to the respective application. Be there very thin layers, for example in the range from about 10 nm to 2> m, as s they are used, for example, in the manufacture of thin-film circuits and multilayer circuits or can be used in semiconductor technology, from solution to the substrate upset. In contrast, thicker layers, for example in the range from to 10 »m or about how they are in addition to these areas of application, for example also in the production of circuit boards and printed circuits Find use, also applied dry to the substrate after the lamination process will.

As a substrate, the type of which is known to vary according to the respective user purpose of the resist pattern to be produced, those in this area come common and known substances into consideration. For example, for the Production of etching or electroplating resists, such as those used in the production of printed circuit boards or printed circuits are required, as substrates copper sheets or copper-clad Basic material used. For the production of single-layer or multilayer circuits in particular ceramic substrates with metallic or metal oxide Layers are coated, or semiconductor elements are processed. In semiconductor technology Often silicon, GaAs or InSb wafers are used as substrates; can be provided with an oxide or general insulating layer. Given no if it can be useful, the substrate before applying the radiation-sensitive Treat resist layer with an adhesion promoter.

This is particularly advantageous in semiconductor technology when as Substrate silicon or silicon oxide-modified wafers are used, with In this case, hexamethylene disilazane, for example, is particularly suitable as an adhesion promoter has proven itself.

After applying the radiation-sensitive according to the invention Resist layer based on the poly (diacetylene) on the substrate is the most radiation sensitive Resist layer for producing the image-wise structuring for the formation of the desired Resist pattern irradiated imagewise with actinic radiation. As actinic radiation depending on the sensitizers contained in the resist layer, both actinic light, especially in the wavelength range from about 180 nm to 800 nm, as well as thermal radiation> in particular IR radiation of one wavelength larger about 0.8 cm. The radiation source is advantageous based on the sensitizer. In the case of actinic light, these are preferred radiation sources used in the absorption range of the light-activated Sensitizer have the largest possible emission. With radiation sources that Emitting over a wide range of wavelengths, it is possible to adjust the radiation intensity better by using a suitable sensitizer or sensitizer system and to use it more fully than before.

On the one hand, radiant heaters are used as radiation sources, in particular IR emitters or IR lasers, on the other hand the usual radiation sources for actinic light in the UV and visible wavelength range, such as Incandescent lamps, halogen burners, mercury silver low, medium or -high pressure lamps, which may be used e.g.

can be doped with iron or gallium, xenon lamps, fluorescent tubes, superactinic fluorescent tubes, excimer lasers, UV lasers, etc. Image-wise irradiation the resist layer can be applied by means of an image-wise modulated laser beam or when using diffuse radiation using a suitable one, for example photographic image template, such as a photographic negative or positive, their Opaque areas are practically impermeable to the actinic radiation used.

The duration for the imagewise exposure of the resist layer depends on the composition of the radiation-sensitive resist layer, in particular the used poly (diacetylenes) and sensitizers, also from their layer thickness, the radiation intensity and the radiation source used. Because through the Exposure to actinic radiation causes molecular degradation of the poly (diacetylene) induced or accelerated and thereby a property differentiation between irradiated and non-irradiated areas of the resist layer is effected, the Irradiation duration chosen so that after the imagewise irradiation the irradiated Areas can be completely removed using a suitable developer medium can. The time for the imagewise irradiation is usually in the range from a few seconds to a few minutes, with the optimal irradiation conditions can easily be determined in a known manner on the basis of simple preliminary tests can. When using thermal radiation, it has proven to be useful that the image-wise irradiation of the resist layer to be carried out so that the irradiated areas to a temperature in the range of about 40 to 200in, but at least to one Temperature above the activation temperature of the heat-activated sensitizer, be heated. Is the radiation-sensitive resist layer before lamination briefly pre-irradiated over the entire surface of the substrate, as mentioned above, so can the duration for this pre-exposure to about 70% of the duration for the main imagewise exposure be. Full-area pre-irradiation and image-wise main irradiation can thereby be carried out with the same or with different radiation sources. Are, for example, both light-activatable in the radiation-sensitive resist layer as well as heat-activated sensitizers can be pre-irradiated over the entire surface for example by means of sIR radiation, whereas for the imagewise Main exposure actinic light can be used or vice versa.

After the imagewise exposure of the resist layer and before the development If desired, the resist layer can also be subjected to heat treatment of the resist pattern are subjected to, in which the resist layer is increased Temperatures, in particular in the range from about 50 to 200 * C, heated.

Such a tempering step can reduce the crystalline portion of the Poly (diacetylene) in the resist layer increases and thus the resistance of the resist layer be improved. Are heat-activated sensitizers in the resist layer included, it goes without saying that the temperature for such tempering are below the activation temperature of the heat-activated sensitizers got to. Such tempering of the resist layer is preferably carried out after the imagewise Irradiation is carried out when the resist layer does not have any heat-activatable sensitizers contains and high demands are placed on the resistance of the resist pattern, for example, even if the resist pattern is developed dry by means of a plasma gas shall be. The duration for such a tempering step is usually in the range from 10 to 2000 minutes and is essentially due to the desired property profile of the resist pattern.

After the imagewise irradiation of the resist layer and, if necessary, one subsequent tempering, the irradiated areas of the layer are under development of the resist pattern removed. This can be done, for example, by washing out the irradiated Areas with a developer solvent, such as acetone, are done. It can be washed out in the usual way, for example by spraying, rubbing out or brushing out the image-wise irradiated resist layer made with the developer solvent will. A particular advantage of the resist layers to be used according to the invention also lies in the fact that the development of the imagewise irradiated resist layer takes place with developer solvents also dry, for example by plasma or vacuum treatment, can be carried out. In the case of plasma development, the imagewise irradiated Resist layer, for example with plasma gases such as Ar, C2F2, C2F4, 0 and the like, treated and thereby the irradiated, degraded layer areas are removed. As such, this dry development by plasma treatment is fundamental known.

After developing the resist pattern by removing the irradiated The resist pattern obtained in this way can optionally also contain areas of the resist layer be treated afterwards. This includes in particular the drying of the resist pattern after washing out the irradiated layer areas with a developer solvent. As a follow-up treatment, however, e.g.

an annealing of the resist pattern into consideration, as already mentioned above as an intermediate step between imagewise exposure and development of the resist layer has been described. Although the tempering takes place in two steps, i.e. both after the imagewise irradiation as well as after the development, can be carried out, it has proven to be useful in practice proved the tempering to improve the resistance of the resist layer either after the imagewise exposure or after development, with post-development annealing of the resist pattern is preferably applied when developing the resist pattern is carried out with a developer solvent and / or, as described below, a multiple imagewise exposure and development of the resist layer provided is.

After the development of the resist pattern, the exposed areas can of the substrate in a known and customary manner, for example by metal deposition, Etching or doping, permanently modified. The process of imagewise irradiation and development of the resist layer can be repeated several times if desired, after each development step and before each further imagewise exposure the exposed areas of the substrate can be modified. Multiple irradiation thus allows a repeated, different modification of the substrate, E.g. the galvanic gold plating of plug contact strips or the production of Circuit boards that are galvanically reinforced with precious metals in the middle of the conductor tracks Have pressure point or sliding contact switches. A particular advantage of the invention, Radiation-sensitive resist materials lies in the fact that such multiple imagewise exposure of the resist layer with only one photographic one Artwork can be worked if the resist layer is a mixture of sensitizers which are activated with actinic radiation of different wavelengths can, and the various pictorial areas of the photographic original transparent for only one specific wavelength of actinic radiation or are impermeable.

The radiation-sensitive according to the described method with the radiation-sensitive Resist layers based on the poly (diacetylene) produced resist patterns are suitable suitable for all application purposes that are for image-wise structured resist layers are known, e.g. as etching and electroplating resist in the production of conductor tracks, printed circuits, for the production of thin-film or multi-layer circuits, electronic components, in semiconductor technology, etc. The inventively produced Resist patterns are characterized by good mechanical, chemical and - if none Heat-activated sensitizers are included - also thermal resistance the end. According to the invention, high resolutions can be achieved, so that the finest picture elements can be reproduced true to the original in the resist pattern obtained. There is also the fact that the resist layers to be used according to the invention are advantageous for exposure to actinic radiation in a very broad Wavelength range ideally suited, over the entire range of far UV to the IR range. This allows for a very broad and general Applicability of the radiation-sensitive resist materials according to the invention and allows great variation in the production of the resist patterns, despite show the partial crystallinity of the resist layers to be used according to the invention this a high optical transparency. For the application is also significant the fact that the image-wise exposed resist layers are developed dry can.

The invention is illustrated in more detail by the following examples. The parts and percentages given in the examples relate unless otherwise indicated on the weight.

Example 1 4,6-decadiyne-l, 10-diol-bis (n-butoxycarbo was treated by t-radiation (3 megarads of a 60Co-t source) polymerized. That obtained with a 30 percent yield Polydiacetylene (P3BCMU) consisted of structural units of the general formula (II) with R1 r R2 with the remainder given in the description under (a) for R1 and R2. The obtained polymer became the unreacted monomer by extraction removed with acetone. Metallic fibers were obtained which were dissolved in chloroform have been resolved. The solution was applied to a glass substrate by spin-coating, so that after drying a partially crystalline polymer layer about 10 nm thick resulted. This polydiacetylene layer was made with a high pressure triangle silver lamp HBO 200 W exposed for 4 minutes through a photographic original. The optical one The density of the layer at the wavelength of 550 nm decreased from 0.19 to 0.05. The exposed areas of the polydiacetylene layer could then be used be washed out with acetone. A resist pattern true to the original was obtained well-developed contours.

Example 2 The procedure described in Example 1 was followed, however with the difference that this time 1 total% anthraquinone to that dissolved in chloroform Polydiacetylene was added. The exposure time could be 3.25 min be lowered to the same decrease in optical density at one wavelength of 550 nm and a resist pattern of the same quality as in Example 1.

Example 3 The procedure described in Example 1 was repeated, however with the difference that this time to the polydiacetylene (P3BCMU) dissolved in chloroform 30 total% of the plasticizer bisC2-ethyl-hexyl) phthalate were added.

The exposure time this time was 7.5 minutes, with the same change to achieve the optical density at a wavelength of 550 nm, as in example 1.

Example 4 The procedure described in Example 3 was repeated, however with the difference that this time with the polydiacetylene dissolved in chloroform Plasticizer 1 wt.% Anthraquinone was added. The exposure time could decreased to 4.5 min to obtain the same change in optical density as in Example 1 described to achieve. A good quality resist pattern was obtained.

Example 5 The procedure described in Example 1 was repeated, however with the difference that this time P4BCMU was used as the polydiacetylene that in the general formula (II) the radicals R1 X R2 that in the description below (b) correspond to the remainder given. To a change at the wavelength of 535 nm To achieve the optical density of 0.30 to 0.13, the film had to be exposed for 3.75 minutes will. The resist pattern obtained was well formed.

Example 6 The procedure described in Example 5 was followed, with the The difference is that to the P4B dissolved in chloroform (> aJ 2% by weight Michler's ketone and 6 wt% benzophenone was added. To make the same change in visual Achieving density as described in Example 5 only took 3.25 minutes of exposure to become. The quality of the resist pattern was comparable to that of Example 5.

Example 7 The procedure described in Example 1 was repeated, however with the difference that this time PTS-12 was used as the polydiacetylene that in the general formula (II) the radicals R1 P R2 that in the description below (c) correspond to the remainder given. To at the wavelength of 490 nm one Change the optical density from 0.17 to 0.05 to achieve as it is for development of the resist pattern was required, exposure had to be carried out for 60 seconds, Example 8 Es the procedure was as described in Example 7, but with the difference that this time 1% by weight of anthraquinone was added to the PTS-12 dissolved in chloroform. the Exposure time could be reduced to 20 sec to get the same change in optical Achieve density as described in Example 7. The received, faithful to the original Resist pattern showed good quality.

Example 9 The procedure described in Example 7 was followed, but with the difference that the resist film is imagewise in the wavelength range above 495 nm was exposed. About the optical density of the polydiacetylene resist film at the wavelength from 490 nm from 0.17 to 0.11 had to be exposed for 25 minutes.

Example 10 The procedure described in Example 9 was repeated, however with the difference that to the PTS-12 dissolved in chloroform 0.12 z rhodamine 6G added # were added. To get the same change in optical density as in example 9, only had to be achieved for 4 minutes at a wavelength above 495 nm are exposed. A resist pattern corresponding to Example 8 was obtained.

Example 11 A solution of 1.3 g of P3BCMU (polymer from Example 1) and 1.6.10 2 moles of azobisisobutyronitrile in 1 1 of chloroform was divided into 4 parts. One part was 10 min, the second part 20 min, the third part 30 min and the fourth part tempered for 40 min at 450C. The originally reduced viscosity of the Solution of 1.09 l / g had increased in the first case to 0.72 l / g, in the second case 0.58 l / g, in the third case to 0.48 l / g and in the fourth case to 0.42 l / g. From each of the four solutions, a film of approx 10 nm thickness applied to an aluminum vapor-deposited glass substrate. One received on thus resist films with differentiated properties.

Example 12 The procedure was as in Example 1, but this time in addition to the polymer solution, 1.1.10 3 mol / l anthraquinone and 2.10 -5 mol / l rhodamine 6G added. This solution was used to spin-coat a 20 nm thick photoresist film manufactured. First of all, it became imagewise at one wavelength through a photomask exposed and developed at 546 nm. The image-wise exposed aluminum-coated Glass substrate was etched so that the glass could be exposed imagewise. the areas of the resist that had not yet been exposed were imagewise in a second Exposure step irradiated with ultraviolet light through a W mask and developed. After this second pictorial structuring, the aluminum surface could be independent treated again from the first etching step.

Claims (22)

Claims 1. A method for producing resist patterns a substrate in which a radiation-sensitive Resist layer based on, in particular soluble, foly (diacetylenes), imagewise is irradiated with actinic radiation, thereby a molecular degradation of the poly (diacetylene) causes and a selective removal of the irradiated areas of the resist layer is made possible, then, optionally after tempering the resist layer, the irradiated areas of the resist layer are removed and the resultant Resist pattern is optionally post-treated, characterized in that the radiation-sensitive resist layer which can be activated by actinic radiation Contains sensitizers which, after activation by the radiation, reduce the molecular degradation induce or accelerate the poly (diacet # lene). 2. The method according to claim 1, characterized in that the radiation-sensitive Resist layer based on poly (diacetylene) is partially crystalline. 3. The method according to any one of claims 1 or 2, characterized in that the poly (diacetylenes) repeating units of the general formula (II) contain, where R1 and R2 are: identical or different and independently of one another, an aliphatic, aromatic or mixed aliphatic-aromatic radical with preferably 1 to 50 e atoms, these radicals being saturated or unsaturated, optionally substituted and in particular also by heteroatoms or heteroatoms containing groups can be interrupted. 4. The method according to claim 3, characterized in that in the poly (diacetylenes) with the repeating units of the general formula (II) the radicals R1 and R2 Acid ester, acid amide> sulfonate, urethane and / or urea groupings contain. 5. The method according to any one of claims 1 to 4, characterized in that that the radiation-sensitive resist layer can be activated by actinic light Contains sensitizers and imagewise exposure the resist layer with actinic light, especially in the wavelength range from about 180 to 800 nm. 6. The method according to claim 5, characterized in that in the radiation-sensitive resist layer as light-activatable sensitizer compounds are included that are immediately free, reactive when irradiated with actinic light Radicals form or change into an excited, more energetic state which they found out via radical reactions with the poly (diacetylenes) with degradation of the Polymers come into reaction. 7. The method according to any one of claims 1 to 4, characterized in that that the radiation-sensitive resist layer heat-activated sensitizers contains and the imagewise irradiation of the resist layer with thermal radiation, in particular with IR radiation of a wavelength greater than about 0.8; irn> is carried out. 8. The method according to claim 7, characterized in that in the radiation-sensitive resist layer as heat-activated sensitizers under contain the influence of heat in free, reactive radicals decomposing compounds are. 9. The method according to any one of claims 7 or 8, characterized in that that by the thermal radiation, the irradiated areas of the resist layer on a Temperature in the range from about 40 to 200 ° C, but at least to one temperature above the activation temperature of the sensitizers. 10. The method according to any one of claims 1 to 9, characterized in that that the radiation-sensitive resist layer light- and heat-activated sensitizers contains. 11. The method according to any one of claims 1 to 10, characterized in, that after the first imagewise exposure and development of the resist layer remaining portions of the resist layer at least once more imagewise irradiated and the irradiated areas are removed, after each irradiation and Development process the exposed areas of the substrate can be modified. 12. The method according to any one of claims 1 to 11, characterized in that that the radiation-sensitive resist layer further additives and / or auxiliaries contains. 13. The method according to any one of claims 1 to 12, characterized in that that the radiation-sensitive resist layer as a solid, prefabricated layer under Application of pressure and optionally heat applied to the substrate and is briefly pre-irradiated over the entire surface before application. 14. Dry film resist with a dimensionally stable, temporary layer support, a solid, radiation-sensitive resist layer based thereon of, in particular soluble, poly (diacetylenes) and preferably a top layer on the radiation-sensitive resist layer, that of the radiation-sensitive The resist layer can be peeled off without removing the temporary layer support at the same time is, characterized in that the radiation-sensitive resist layer through actinic radiation contains sensitizers that can be activated after activation induce or accelerate the molecular breakdown of poly (diacetylenes). 15. Dry film resist according to claim 14, characterized in that the radiation-sensitive resist layer made up of the poly (diacetylenes) is partially crystalline is. 16. Dry film resist according to one of claims 14 or 15, characterized characterized in that the radiation-sensitive composed of the poly (diacetylenes) Resist layer contains further additives and / or auxiliaries. 17. Dry film resist according to one of claims 14 to 16, characterized characterized in that the poly (diacetylenes) have an average molecular weight (weight average) in the range from 10,000 to 2,000,000, in particular in the range from 50,000 to 1,000,000, own. 18. Dry film resist according to one of claims 14 to 17, characterized in that the poly (diacetylenes) recurring units of the general formula (II) contain, where R1 and R2 mean: identical or different and independently of one another, an aliphatic, aromatic or mixed aliphatic-aromatic # radical with preferably 1 to 50 carbon atoms, these radicals being saturated or unsaturated and optionally substituted and in particular also by heteroatoms or groups containing heteroatoms can be interrupted. 19. Dry film resist according to claim 18, characterized in that in the poly (diacetylenes) of the general formula (II) the radicals R1 and R2 acid ester, 5 Sureamide, sulfonate, urethane and / or urea groups contain. 20. Dry film resist according to one of claims 14 to 19, characterized characterized in that the radiation-sensitive resist layer by actinic light Contains sensitizers that can be activated and / or activated by thermal radiation. 21. Dry film resist according to claim 20, characterized in that the radiation-sensitive resist layer as light-activated sensitizers Contains compounds which, when exposed to actinic light, immediately free, form reactive radicals or change into an excited, high-energy state, from which they react via radical reactions with the poly (diacetylenes) can kick. 22. Dry film resist according to claim 20, characterized in that the radiation-sensitive resist layer as heat-activated sensitizers Contains compounds which decompose into free radicals under the influence of heat.