DE2224098C2 - Process for producing an image - Google Patents

Description

characterized,

15th

a) that an imaging material is used, which may be in the form of at least two stable physical states structure, wherein the material jefindet in one of these stable states' and the different stable! en Stfüfctürzustände substantially amorphous or crystalline,

b) that one can selectively apply energy in the form of electrical, electromagnetic energy to the desired parts of the layer. Heat, pressure, acoustic and / or particle beam energy act lets to move the desired parts of the layer from one steady state to the other toggle, and

c) in that then act on the layer as solvent, an oxidizing agent-containing, aqueous solvent, CS ₂ or methanolic bromine solution> äßt una to those parts of the layer SiCN \ a the one of the states are, with a factor of at least 2 dissolve faster than those parts of the layer that are in the other state.

2. The method according to claim 1, characterized in that an imaging material is used which is in contact with catalytic amounts of a structural change promoting promoter material, in particular light-dissociable or light-reducible salts.

3. The method according to claim 1 or 2, characterized in that an imaging material is used whose electrical conductivity in the one physical structural state differs from the electrical conductivity in the other physical structural state differs significantly.

4. The method according to any one of the preceding claims, characterized in that an imaging material is used which has at least one element from the group Te, Se and Po and the jumping from one state to the other by crossing a certain energy threshold Energy passes.

5. The method according to claim, characterized in that that a t> o containing tellurium and selenium Chalconide imaging material is used.

6. The method according to claim 4, characterized in that a tellurium and germanium containing chalconic imaging material is used. ^hi >

7. The method according to claim 4, characterized in that there is a tellurium and sulfur chalconic imaging material is used.

8. The method according to any one of the preceding claims, characterized in that a solvent for acting on the imaging material is brought, whose parts located in one of the states with a by a factor of 10 larger Speed than the parts in the other state.

9. The method according to claim 8, characterized in that a solvent for action on the imaging material is brought, the parts of which are in one of the states with a the factor! 00 higher speed than those in the other state Parts.

10. The method according to any one of the preceding claims, characterized in that the solvent Sodium hypochlorite solution is used.

11. Method according to one of the preceding Claims, characterized in that the solvent is a solution, the hydrogen peroxide contains is used.

12. The method according to any one of the preceding claims, characterized in that for dissolution the faster dissolving layer areas the imaging material in an electrolyte with electrical Direct current is applied.

13. The method according to any one of the preceding claims, characterized in that the imaging material is applied with laser beams as electromatic energy.

14. The method according to any one of the preceding claims, characterized in that the imaging material is applied with IR rays as electromagnetic energy.

15. The method according to claim 13 and 14, characterized in that the imaging material in two Levels, both with laser rays and with heat rays is applied.

16. Use of the method according to any one of the preceding claims for the production of active electrical components, in which the electrical components are formed by those layer areas that are not as strongly dissolved or detached by the solvent than the other parts of the layer.

17. Application according to claim 16, characterized in that the electrical components forming layer regions of the imaging material are applied to a carrier.

18. Application according to claim 17, characterized in that that an electrical semiconductor is used as a carrier.

The invention relates to a method for producing an image as described in the preamble of the claim 1 and to the application of the process for producing active electrical Components.

Such a method using a radiation-sensitive element is already known (DIvOS 19 14 762; US-PS 37 62 125). At the bckannien Procedure that is mainly used in l'hototcchnik bark, inorganic material, including metal selenides, such as arsenide, becomes electromagnetic!

shear energy is irradiated in such a way that the irradiated areas differ in terms of their chemical and physical Distinguish property from non-irradiated areas. Gradual changes in properties take place depending on the duration or intensity of the irradiation, as is the case with ordinary photography. With the help of a solvent such as ammonium hydroxide, Sodium sulfide and potassium carbonate are the chemical and physical properties of the radiation Properties changed areas solved, whereby it is also possible to do a negative lithographic Plate manufacture. It has been shown, however, that areas irradiated with only little energy retain their properties change so that often no great contrast can be achieved

In addition, it is known (DE-OS 20 15 615; US-PS 37 07 372) that the inorganic material that is used in Irradiation changes its chemical and physical properties successively before irradiation with one other material is provided, which the chemical and physical properties of the material modified by means of a chemical reaction. However, this procedure is based on special alternating reductions limited, where so-called converter materials, such as silver, bromine, iodine, copper nitrate and silver nitrate, must be present. This method, too, is unsatisfactory in terms of the richness of contrast that can be achieved.

For the production of relief images, a method is also known (FR-PS 15 43 662), in which a layer of a metal in a non-metallic cover layer is provided with a chemical compound, which reacts photochemically under the influence of electromagnetic radiation with the metal layer and creates a new one chemical compound forms. Typical metals that are used are silver and copper, while for the top layer arsenic trisulphide, arsenic pentasulphide or a reaction mixture of arsenic and sulfur and iodine are used.

In addition, it is known (FR-PS 15 67 526) to use arsenic sulfide or arsenic pentasulfide as the only layer use which is exposed to electromagnetic radiation. Here, too, the wealth of contradictions is not especially good.

A method is already known for producing a relief image photographically in silicate glasses (US-PS 34 73 927), in which light-sensitive glass in the form of a heavy plate is exposed to short-wave radiation creating a latent image. By subsequent heating b <s to a temperature in the Over a long period of time near the glass softening point, »crystallites of lithium silicate or alkali metal fluoride formed in the irradiated areas. These crystallites are then in an etching liquid solved. Here, too, the wealth of contrasts leaves something to be desired.

The invention is based on the object of providing the method of the type mentioned at the outset improve so that it allows sharp and high-contrast images. It is desirable with the help of a such a method to be able to produce electrical components with simple means, in which it a sharp separation of the areas of different physical properties is important.

The invention is characterized in claim 1 and further developments thereof are claimed in subclaims.

The invention is well suited for the production of relief images and related structures that are used for Manufacture of objects such as lithographic printing plates, glass pictures or slides, masks for photographic purposes, electronic components, printed circuits and in particular active electrical ones Components are suitable.

The invention can make use of the already known imaging material (DE-OS 20 25 767), which has the property of its physical structure, for example the amorphous starting structure, then suddenly into a different, in particular opposing physical structure, for example the crystalline state, to change when the energy, with which the relevant parts were applied, a

H exceeds certain energy threshold. This sudden structural change when a certain energy threshold is reached or exceeded prevents an energy below the energy threshold from already leading to a partial structural change and thus a change in the physical properties. Due to the sudden annoyance, the object of a better richness of contrast is achieved in the invention, since it has been found that when a certain solvent is used, the parts of the layer in one state dissolve at a much greater rate than the parts of the layer in the other state. The consequence of this application of an image material already known per se in connection with the special solvent is therefore also rich in contrast! e Delimitation of the two parts of the layer after treatment with the solvent, so that greater differences in relief can be achieved. Due to the action of energy above the threshold value mentioned, there is a considerable change in the solubility of the ^r energized areas for comparison with those areas that have not been exposed to the energy, and that imaging material is in those areas in which it has the greater solubility in one seiektiv solvent dissolved.

By the correct selection of the imaging or storage material and the type and energy and by the selection of suitable intensity levels of the energy and by controlling the duration of the effects of energy on the storage material, e ^{c is} possible, either a decrease or an increase in solubility in a given solvent in those areas of the memory material that have been exposed to the energy

Depending on the selection of the storage material, the working conditions and / or the solvent, you can positive or negative reproductions of an original produced by the method according to the invention will. Generally a positive image is obtained.

when the surfaces of the storage material subjected to the imaging effects of the energy. been were made more soluble in a given selective solvent than those surfaces who have not been subjected to inclination. A negative one Image is generally obtained when the surfaces of the spalling material have the imaging effects subject to energy, thereby reducing their solubility in a given selective solvent. If necessary, the layer can be used as a storage medium

material serve as an etching base for etching a lower layer with or without subsequent removal of the storage material in the undissolved areas.
Image or image used in the invention

Storage material is a material in which selected Parts are capable of a physical structural change to take place between at least two stable states. This material is usually in one of these states and is able to enter one to be transferred to another stable state due to the application of energy, e.g. B. of light, electron beams or other high-energy (energetic) particles, heat, an electric field, stress or the like. Or a combination of one or more of these types of energy. This physical Structural changes can e.g. B. conformational changes, configuration changes or changes in position be in the organization or arrangement of atoms or molecules in the storage material. Typical physical changes include changes from a generally amorphous state to a more ordered one or crystalline state or vice versa, anrial chemically to solvents according to the invention are applied more actively. The storage material can also contain catalysts that are used in Auxiliary or base materials or matrix materials dis-

: ■ are pergated. The catalysts can act as nucleating agents serve, so that the above-mentioned physical structural changes when energy is applied are initiated at these points. When the physical structure change is a form of crystallization includes, catalytic cores can act as moldings serve that affect the geometric shape of the crystal structure epitaxially. Many different Forms of kaialytic processes can be initiated by the applied energy, including chemical changes of the catalyst caused by photodissociation caused by components contained therein. Need such chemical effects not carried through the entire storage material

iere se ¹ .?. ', but only act as a core to create

crystalline form, changes in the degree of crystallinity. modification in the relative alignment of molecules or their segments, changes in the intermolecular Binding and the like .. Unfolding, wrapping, packing, stretching or otherwise changing the Shape or geometry of molecules, opening or closing of molecular ring structures and other splits of molecular chains, attachment of molecular chains, changes in the average length of formed Molecular chains, e.g. B. by rolling or unrolling, moving atoms or molecules from one place to another location, including reciprocal or non-reciprocal movement of neighboring ones Atoms or molecules, creation or elimination of defects in storage material, contraction or expansion the storage material, breaking or connecting bonds between atoms or molecules and combinations of one or more of the aforesaid changes. In addition to these physical Structural changes can consist of one or more components of a given storage material the material z. B. be precipitated in crystalline or amorphous form.

When energy is applied to certain types of storage materials, which contain long-chain polymers, especially those with low chemical crosslinking, are used the atoms or molecules can flow or diffuse and thereby have elastomeric properties demonstrate. The reduction or cessation of the applied energy directs the reduction of this flow or diffusion. The speed of this decline or the quenching speed is essential, since it is convenient that the atoms or molecules are frozen in their new positions, whereby a stable physical structural change before a significant relaxation of such storage materials in causing their previous condition. The applied energy can e.g. B. Bonds Between Atoms or breaking up molecules or Van der Waals or other forces between atoms or molecules diminish or produce the opposite effect of creating bonds or increasing such »· forces. The flow or diffusion of atoms or molecules can be applied directly through the Energy can be produced or can be produced by thermal lysis processes that are carried out by the absorption of the applied energy can be initiated. Broken ties, e.g. B. off Ketien fissures result, make the storage mate presentation the physical structure changes in the matrix of other substances in which the catalysts are dispensed.

Preferred storage materials are those in which a large amount of free carriers can be generated by the application of energy. If z. B. Photon energic When creating electron-hole pairs, it is desirable that these carriers remain viable and not rekombr ^ cren. long enough for atomic movement to take place during this time.

jo This essential parameter of storage materials is related to the relaxation time of carriers and atoms. Usually there is a certain barrier density and density of energy gaps in any given one Storage material, which is caused by the above

j5 th physical structural changes are changed can. This change in barrier density and energy gaps can exceed time while which such carriers stay alive and the atoms remain in a new location, thereby causing the freezing is supported in an unbalanced distribution of carriers.

According to one form of the invention, wherein nuclei or nuclei in the storage material as a result of the application formed by energy is only necessary. To create cores of a certain critical size, which are capable of any relaxation or recombination of carriers or atoms after removal of the applied energy to survive. These cores created in this way can act as a latent image, the can be amplified and developed through subsequent application of energy, either in <k.r the same shape as it was originally applied, or in one or more other forms as described above, causing the growth of crystals around causing such nuclei.

The imaging materials (storage materials) according to the invention, in which the physical Structural change accompanied by a transition between an amorphous and a crystalline state will, are able to operate in one or the other of these two states at ambient temperatures to exist in the range of room temperature. At these temperatures there is an energy barrier between these two states, which are in the form of a

b5 mechanical entanglement of molecules exist can. To overcome this barrier, it can be, for. B. to be necessary. To change molecular ring structures in molecular chains or to cross-link chemical, mechanical

shear or other structural type. One difference between storage materials and typical silicon oxide glasses is that the latter have high energy barriers, which result from highly cross-linked network structures which have the effect of resisting devitrification or crystallization. The energy which is necessary to overcome this barrier would have destructive effects on other properties of such silicon oxide glasses, e.g. B. an irreversible dielectric breakdown. On the other hand, storage materials are more easily bound and allow deviations in the configurations of the molecular chains and different atomic or molecular bonding forces. These changes are achievable at lower temperatures than with the strongly crosslinked glasses mentioned above and respond much more easily to activation through the application of energy. Such energy can be light energy which is able ^{to act even in the σ} £ Πί * ππ'.οπ tomnorature ranges in order to effectively lower the energy barrier between the amorphous and the crystalline state. The mobility of atoms or molecules at these temperature ranges is much greater in storage materials than in such strongly crosslinked silicon oxide glasses. This allows crystal growth in the storage materials to occur much faster and more controllably when a wide variety of processes, including thermal, chemically catalyzed and light-induced processes and the like, are used. In addition to the energy barrier that exists between the crystalline and amorphous states of the storage materials, there are similar energy barriers between the other states that are brought about by the changes in configuration, conformation and position mentioned above.

Another beneficial characteristic exhibited by many of the vitreous storage materials that According to the invention is used, is an easily obtainable exotherm above the transition temperature in the glass state and below the temperature at which the melting takes place. If this property is present in a storage material, it is usually accompanied by the ability to act as the energy barrier to reduce quickly and controllably between the two desired states of the storage materials.

So far it has been described that the storage material which can be used in the method according to the invention is, Jer is capable of a physical structural change to go from one state to at least one other state. The storage material usually lies in one of these states and is able to switch between these states upon the application of Energy above a certain threshold to be switched, this threshold being a specific one Peculiarity of the storage material. The application of energy below such a threshold does not switch the material. Accordingly, there is no protection against the imaging or storage material premature application of energy is required and there is no subsequent application of energy A fixation step is necessary, as is the case with the imaging materials of the prior art, with chemical reactions are used, is necessary Since there is still no fixation according to the method according to the invention is required, the storage material remains susceptible to a second application of energy for reproduction an additional picture. In the case of the starting material according to the method according to the invention usable storage material, as it is defined above, find a crystallization or other physical Changes useful for illustration purposes. only in those! - "laugh or areas where the storage material is actually subject to the energy will. Any area immediately next to these areas that has not been subjected to the action of energy, is not subject to physical changes. This and the extremely small size of the crystals or Crystallites, if the physical change is crystallization, create unsurpassed resolution and a faithful reproduction of even the most detailed images, as required in micro-reproductions is.

Other goals. Advantages and characteristics of the invention will be apparent to those skilled in the art from the following description and can be found in the claims and the drawings. It shows

F i g. 1 shows a schematic cross section of an initial structure from the energy-sensitive storage or Illustrative material obtained during the implementation of the method according to the invention is useful;

F i g. 2 shows a representation similar to FIG. 1, however the energy-sensitive storage material in selected areas as a result of the imaging action has been changed by energy;

F i g. 3 shows a representation similar to FIG. 2, but showing the changed parts of storage material are removed by dissolving in a suitable selective solvent;

F i g. 4 shows a schematic cross section through another structure used as a starting material for Implementation of the method according to the invention, this structure being composed of an energy-sensitive Layer consists of the storage material according to the invention on a layer support, which is essentially is not reactive with it;

FIG. 5 is a representation similar to FIG shows how the energy sensitive layer in selected areas as a result of the imaging effects the energy on these selected faces is changed;

F i g. 6 shows a representation similar to FIG. 5, the part Ie of the energy-sensitive storage material that have not been changed by the energy and removed by dissolving in a suitable selective solvent;

7 shows a schematic cross section through a Starting structure made up of three layers, which can be used when carrying out the method according to the invention and an energy-sensitive cover layer made of the storage material according to the invention, an intermediate layer made of a material of different chemical composition, which essentially corresponds to the Top layer is non-reactive and a layer carrier layer, made of yet another chemical composition consists;

F i g. 8 shows a representation similar to FIG. 7, which is the most energy sensitive Layer on selected surfaces as a result of the imaging effects of energy represents these places changed;

F i g. 9 shows a representation similar to FIG. 8, but the changed parts of the energy-sensitive deckf> 5 layers are shown removed by dissolving them in a suitable selective solvent;

F i g. 10 shows a representation similar to FIG. 9, however also remove those parts of the intermediate layer.

ίο

are placed under the openings in the Cover layer have been created by removing the soluble storage material;

FIG. 11 shows a representation similar to FIG. 10, but with the cover layer of storage material is completely removed;

F i g. 12 shows a representation similar to FIG. 8, being those parts of the top layer that are not subjected to the energy are shown removed, and those parts that are subject to the imaging effects of energy have been, are still present;

FIG. 13 is a view similar to FIG. 12 showing those Parts of the intermediate layer that lie under the openings made in the top layer by removing the Memory material of greater solubility has been created, shows removed;

FIG. 14 shows a representation similar to FIG. 13, but with the cover layer of storage material has been completely removed.

According to FIG. 1, the layer 20 consists of an energy-sensitive Imaging material, which is described in detail below and referred to as storage material will. The storage material of the layer 20 is in amorphous form. Selected areas of this Layer are subjected at 22 to electromagnetic radiation. As a result, the storage material on surfaces 24 and 24 'according to FIG. 2 shows a transition to a state of higher crystalline order In this embodiment of the invention, the layer support 30 is selected in such a way that it consists of a preparation exists, which does not significantly interact with the storage material under the reaction conditions of the invention

¹ J according to the procedure. The storage material in layer 28 is highly crystalline.

Selected locations of the layer 28 made of the storage material are exposed to electromagnetic radiation 31 at an intensity level and over a period of time that has a lesser degree of crystallinity on the irradiated areas 32 according to FIG. 5 brings forth.

This results in a decrease in the solubility in selected solvents in the case of the storage material located at the irradiated sites 32. During treatment with a suitable solvent, the areas 34 of the layer 28 of storage material are dissolved out because they have a greater solubility and immediately result in a negative image of the irradiation pattern, the raised areas being formed by the remaining parts of the storage material and the low areas 33 are formed by the bare substrate 30. By suitable choice of the storage material and the support, one of these materials can be made hydrophilic and the other can be made oleophilic, so that the structure of FIG. 6 can serve directly as a negative lithographic printing plate.
By suitable selection of the storage material of the

If in the layer 28 according to FIG. 4 an essentially amorphous storage material or a lower one Crystallinity with the ability to crystallize as a result of exposure to electromagnetic

completed. At the same time, the storage material has to the

selected points 24 and 24 'a significantly higher 30 layer 28 and the layer support 30 and achieved by the Ver-solubility in selective solvents. By using specially designed masks, treatment with a suitable selective hole, a structure according to FIG. 1, is as short as possible. 6, the storage material on the irradiated electronic component assembly is completely removed after the intended location 24, as a result of which a perforated application of contacts and conductors is generated and the surfaces 27 remain intact, 35,
as shown in Fig.3. The perforation 26
corresponds exactly to the pattern of the electromagnetic
Radiation and forms an image in layer 20
from the storage material. The structure shown on the left with the perforation 26 according to FIG. 3 can e.g. B. to increase radiation or another energy, od before photo mask or as a template. The like. Can be used. is seen, the situation is reversed

By applying the energy 22 'in less connection with the FIGS. 4-6 were shown. The solution when they were used to convert the amorphous material into the possibility of the surfaces 32 in FIG. 5 can about the solubility crystalline state through the entire layer 20 wedge of the surfaces 34 are increased to a significant extent is the bottom area 25, which is below the area difference in the solubility of the storage material 24 'and was not subjected to the energy than at the points 32 opposite the solubility of the still amorphous at the point, which in the direction of the material produce at the points 34. In the is opposite from which the energy is applied to the treatment with a suitable selective solution layer 20 occurs. If the structure of the action of the agent dissolve, the spots 32, while the spots 34 Is subjected to solvent, an impression 26'50 will remain intact and produce a positive relief image of layer 20 is produced, with a thinner bottom, which is layered together for the same purposes as this 25 made of amorphous storage material, the surfaces hang with the negative relief images of FIG. 6 resolves who had been subjected to the energy. was written, can serve.

By correct selection of the storage material, the In F i g. 7 is a layer 36 of memory material

Working conditions and / or solvents can result in an intermediate layer 38 made of a material with

The method can also be carried out in such a way that the storage material at those points of the layer 20, which have been subjected to electromagnetic radiation achieve a considerable decrease in solubility, compared to the places that were not subjected to electromagnetic radiation. In In this case, the rakes 24 and 24 '(Fig. 2) remain intact when treated with the selective solvent, and the rays 27 are released and immediately form a negative perforated structure or a relief image, like a negative photo mask.

In Fig. 4 shows a layer 28 of storage material, which is located on a layer support 30.

different chemical composition as the storage material in the layer 36 and a chemical one Composition such that it does not significantly interfere with the storage material of the layer 36 under the Reaction conditions reacts according to the method according to the invention, shown. The intermediate layer is again provided on a substrate 40 of yet another chemical composition. The intermediate layer 38 may e.g. B. be a metal that

ti practically not with the storage material in the layer 36 reacts like aluminum. Serving as a carrier substrate 40 can, for. B. a plastic film or paper be.

Selected areas of the layer 36 of storage material are inventively the imaging action of energy, z. B. electromagnetic radiation, such as light and / or infrared radiation 42 'at a level and for a period of time that are subject to increase the solubility of the material at the irradiated sites 42 (FIG. 8) of the storage material in selective Solvents sufficient and is significantly higher than the solubility of the storage material at the points 44, the not irradiated. This change in solubility of the irradiated storage material can be caused by a change in the morphology of the storage material can be brought about.

The layer 36 is then subjected to the action of a solvent for the storage material at the irradiated areas 42, the solvent being selected such that it does not substantially dissolve the storage material at the areas 44, but completely removes the storage material at the irradiated areas 42 and openings 46 produces in the layer 36 of storage material. The openings 46 extend up to the o; e intermediate layer 38, but not into this. Thereafter, a solvent for the intermediate layer 38, which is not a solvent for the storage material in the layer 36 and at the locations 44, is applied to the openings 46, which results in the dissolution and removal of the material of the intermediate layer at all of the locations under the Openings 46 are. This step results in a deepening of the openings or depressed areas of the relief image that was obtained in the first dissolution stage with the formation of deep openings 47, whereby the storage material of the layer 36 serves as an etching base. The remaining locations of the layer 36 of the storage material may optionally have a natural structure of the intermediate layer 38. The openings 50, which were formed in this way in the cover layer 36 of storage material, extend up to the intermediate layer 38, but not into it. Thereafter, in a second dissolution stage, the material of the layer 38 that is below <'. 2n openings 50 is subjected to the action of a second selective solvent for the material of the intermediate layer 38, which is not a solvent for the storage material at the locations 48. In this way, the openings 50 are deepened with the formation of openings 52 and the material of the layer 38 that lies under the openings 50 is removed down to the surface of the layer carrier 40 (FIG. 13). Depending c ^l he nature of the material of the intermediate layer 38, the solvent can physically or chemically affect. The storage material at the points 48 acts as an etching base. If necessary, the storage material can be removed at the points 48 by a solvent or by chemical or mechanical action and results in the structure of FIG. 14, in which the raised areas 54 of the relief image are formed by parts of the intermediate layer 38 and the deep areas 52 of the relief image are formed by the surface of the layer carrier 40.

So far, the storage material has been described as a layer of amorphous or crystalline material. According to Another embodiment of the invention can include a layer of memory material which is located in the

jo is in a physical structural state, can be applied to another layer of storage material, which is in a different physical structural state. For example, a thin Layer of amorphous storage material on a thick

by a third level of dissolution or mechanical, 35 ken layer of crystalline storage material or chemical agents are removed. When selected places of the thin in order to produce a relief image which is formed by the parts 49 of the intermediate layer 38 on the layer support 40

is formed. The image produced in this way is amorphous layer of energy who will be exposed to which they are crystalline. If the crystalline material is more soluble, treatment with a selective solvent brings about

a positive image, d. H. Openings have been made in all these solvent openings at the irradiated areas Representations formed by the electromagnetic in front, which are distinguished by the amorphous and by the crystalline Had been subjected to radiation. Extend through the layer so that a thicker image

The structure of FIG. 7 can also be used to form a layer. That which is not exposed to the energy the one used to create a negative image. This amorphous material acts as an etching base that the Purpose one chooses a storage material for the layer 45 areas of crystalline material that lie underneath, 36, the solubility of which is reduced if the image protects it from the action of the solvent, exposed to the effects of energy, such as electromagnetic Radiation. A suitable material can e.g. B. be a highly crystalline storage material, that when subjected to the energy becomes more amorphous and the crystallinity with a substantial drop the solubility lowers.

When selected locations of the structure modified in this way, e.g. B. electromagnetic radiation If subjected to sufficient intensity, treatment with a solvent results in an opening Structure similar to that in FIG. 8 through the entire layer of storage material except that the sites 42 are less soluble in selected solvents than the surrounding ones Locations 44 that were not previously exposed to radiation have become. Because the layer 36 of ω Storage material of the structure modified in this way under the action of a suitable selective Is subjected to solvent, the storage material is at the unirradiated areas 44 with the larger Solubility dissolved out and the structure of Fig. 12 65 is obtained, which the surfaces 48 of memory material! contains in those places that are subjected to irradiation had been, and that is on a continuous

A similar effect is achieved if only sufficient with a thick layer of storage material Energy is applied that only switches the surface of the layer in the acted upon places will. When the total mass is subsequently heated, the places under the switched over change Places are in the other physical structure state and become more soluble. The treatment

through.

The method according to the invention uses certain storage materials as an effective component. These materials are characterized by their property that they are physically capable of their Structure change from one state to another state when energy is above an energy threshold is applied. In the specific examples of the method according to the invention mentioned, the physical structural change as a morphological change from the amorphous to a crystalline state and of a crystalline in pinpn amnmhon

Condition described. Suitable imaging or storage materials that have these properties, are known per se (US-PS 32 71 591 and 3330 441).

The above-described physical change or conversion from one structural state to another structural state can be a change from a generally amorphous state to an at least partially crystalline state, or it can be a change from a general crystalline state to a general

catalytic substances in the manner just described is intended in the meaning of the expression "essentially not reactive ”, as brought up above, should be included.

In general, the transformation of storage materials from a physical structural state under the action of energy also causes one Change of the physical and especially the electrical properties of the storage materials. For

be my amorphous state. In other cases, the purposes according to the invention are only such storage

the change represents a transformation from one crystalline state to another crystalline structural state, or the change may be a combination of one or more of the specific physical change sets mentioned above.

As described above, these physical changes are threshold value reactions that are generated thereby that the storage material is exposed to energy. In general, these physical changes

chermaterialien useful, which as a result of the transformation or physical changes also a Produces significant change in the solubility of the material in a given selective solvent To obtain the best results in the Carrying out the method according to the invention should be the difference or the ratio of the rate of dissolution of the two forms of storage material in a given selective solvent

wrestling without chemical reaction with an outside 20 should be at least 2: 1. Most preferred are

so that, in accordance with the most preferred embodiments of the invention, the chemical constitution of the storage material η is essentially the same as the alternating physical forms or states. Acceptable exceptions to this rule are given below.

As mentioned, when transforming from one physical structure to another, a significant one occurs cbimic reaction with an outside one

those storage materials which, when subjected to the effects of sufficient energy, have a dissolution rate difference in a given solvent of at least 10: 1 to to 100: 1 or above.

Another desirable characteristic is that the storage material used as the starting material is useful in the material according to the invention, the ability has snow! of a physical structure material of different composition does not arise. 30 state to a different physical structure to-The transformation is more or less a physical state to change. Preferred are such storage meshes phenomena that take place inside the material the effects of energy takes place. This does not rule out the possibility that a component of the memory 35 material can precipitate in order to appear as a defined phase in the mixture with the storage material, although in this case the storage material undergoes a physical change into a different physical state has performed as previously explained. Or it can be a 40 or even below being cheapest for the best Material that is mixed with the storage material, feasible applications of the invention combine or recombine in order to form a storage material of the original chemical composition or a storage material of a different chemical composition in the course of the inverse transformation. This is especially true to materials that have been added in catalytic amounts to act as a catalyst or promoter to serve for the transformation. This catalytic Quantities of promoter substances may or may not enter into a chemical combination with the basic storage material during the transformation under the action of energy. It is believed that at least some of these catalysts act as nucleation centers for the transformation of the storage material into serve a more crystallized form. These catalytic amounts of a transformer promoter can also in the form of a thin intermediate layer under or on the layer as a storage material, from where

they can diffuse into the storage material to 60 material is exposed to a temperature above the transition or nucleation centers for the physical structure temperature or that energy in form change in the manner described above to a suitable electric current for producing it by subjecting it to a catalytic or promoting effect of the transformation. The latent exercise fect. These thin layers of catalyst image can e.g. B. represent cores which are formed by an ausreiwill but not intended for the purpose of forming the b5 chendc accumulation of carriers, so Solubility of the storage material alone with the help of that the subsequent treatment by application the chemical reaction taking place. The re-energy of the nuclei down to a crystalline size action of the storage material with the thin layers and density, which is sufficient to increase the

rials for which the transformation has been completed within no more than 30 seconds, if they are subjected to the effects of sufficiently high energy levels to undergo the transformations to bring forth. Most preferred are those storage materials in which the transformation into one second or less has elapsed completely, with times of one or more milliseconds

Procedures are. The quenching of the storage material after the application of energy or the fast one Cooling after the application of thermal energy is usually beneficial. It has been explained above that the Transformation of the storage material from one structural state or one layer into the other structural state or another layer must take place very quickly. This does not exclude the working method in which the storage material is exposed to light, for example, in order to immediately create what is known as a latent image, as described above, without forming substantial physical structural change of the memory material at that time. This initial exposure to energy is followed at a later convenient time by a stage at which the actual Transformation of the storage material e.g. B. "om amorphous in the crystalline or from the crystalline in the amorphous state takes place, e.g. B. in that the

to produce the desired difference in the solubility wedge for use in the method according to the invention.

According to another embodiment of the method according to the invention, a combination of Different forms of energy are applied to the desired instant transformation or physical Bring structural change of the storage material. An example of this operation includes * the step of exposing the layer of memory material to an electric field of a strength that is not is high enough to produce a significant physical structural change in the storage material as such. Selected areas of the storage material are simultaneously z. B. irradiation by visible Light exposed to UV radiation or infrared radiation or the acoustic or sound energy which, when added to the energy already supplied by the electric field, the desired instantaneous brings about physical structural changes in the selected areas of the storage material

The storage materials used in the method according to the invention do not, as mentioned above, require a fixation stage. They therefore retain their ability to form a new picture when selected areas selectively exposed to the energy a second time, e.g. B. to make changes or Corrections to the image or to create a second image to create special effects. So can z. B. the first time energy is applied Storage material are exposed to the energy and the areas exposed to the energy can be extracted, which is followed by a »Tiefätz«, z. B. the etching of an intermediate metal layer, to expose certain areas of the substrate serving as a support. When the remaining storage material A second time the energy is exposed, the solubility of the storage material in selected Areas can be changed again and allows the selective resolution of selected areas of the Storage material to expose the desired areas of the metal interlayer. That way a relief image with three levels of depth can easily be produced which has an image of the intermediate layer on one Has layer support on which another different image of storage material on this intermediate layer is superimposed. If necessary, a third and subsequent stage, in which the Storage material exposed to the energy is followed in an exposed sublayer in order to be multilayered to generate superimposed relief images. Depending on the choice of material in the different layers interesting combinations can be made, the wide application z. B. in manufacture complex arrangements of electrical components can be found, as described below will. This embodiment of the method according to the invention can also be used with particular advantage Cases are used in which the physical structural change of the storage material is reversible is and allows the achievement of special effects and results.

The storage materials which are useful in the process according to the invention are amorphous in their nature State of preferably glassy materials, which when applied to a substrate, excellent adhesion or show binding properties. For the aforementioned reasons, the common ones are silica glasses no storage materials and do not fall under the definition of a glassy storage material as here be used. It is only essential that the physical changes that occur under the action of energy take place, a sufficient change, in the solubility properties result in the necessary difference in the dissolution rate of the storage material that has been exposed to the imaging effects of the energy compared to ίο the storage material that is not exposed to the energy has been

The storage materials used as starting materials in Processes according to the invention are useful, are generally inorganic storage materials, generally Have properties that make them particularly suitable for the various end uses of the illustrations make, which are produced according to the invention. As the main element, they consist of one Chalcogen or contain it that is not oxygen These include the elements of group VI of the periodic table, which includes elements like selenium. Tellurium and Polonium and, in certain cases, sulfur. The chalcogens can in the storage material in elementary Form or in admixture and / or in chemical combination with many different other elements are present.

Most preferred preparations include certain glassy masses of germanium and Tellurium, which may also contain small amounts of other elements such as antimony or sulfur. Around to name just a few typical storage materials that work in the method according to the invention this z. B. Preparations from (parts by weight) 15 atomic parts germanium, 81 atomic parts Tellurium, 2 atomic parts of antimony and 2 atomic parts of sulfur, a preparation of 83 atomic parts of tellurium and 17 alom parts germanium, a preparation of 92.5 atom parts tellurium, 2.5 atom parts germanium, 2.5 atomic parts silicon and 2.5 atomic parts arsenic, a preparation of 95 atomic parts tellurium and 5 atomic parts Silicon, a preparation of 90 atomic parts of tellurium. 5 atomic parts germanium, 3 atomic parts silicon and 2 atomic parts of antimony, a preparation of 85 atomic parts of tellurium. 10 atomic parts of germanium and 5 atomic parts Bismuth, a preparation of 85 atomic parts tellurium, 10 atomic parts germanium, 2.5 atomic parts indium and 2.5 atomic parts of gallium, a preparation of 85 atomic parts Tellurium, 10 atomic parts of silicon, 4 atomic parts of bismuth and 1 atomic part of thallium, a preparation 80 atomic parts tellurium, 14 atomic parts germanium, 2 atomic parts bismuth, 2 atomic parts indium and 2 atomic parts of sulfur, a preparation of 70 atomic parts of tellurium, 10 atomic parts of arsenic, 10 atomic parts of germanium and 10 atomic parts of antimony, a preparation of 60 atomic parts of tellurium, 20 atomic parts of germanium, 10 atomic parts selenium and 10 atomic parts sulfur, a preparation of 60 atomic parts tellurium, 20 atomic parts Germanium and 20 atomic parts of selenium, a preparation of 60 atomic parts of tellurium, 20 atomic parts of arsenic, W) 10 atomic parts of germanium and 10 atomic parts of gallium, a preparation of 81 atomic parts of tellurium, 15 atomic parts Germanium, 2 atomic parts sulfur and 2 atomic parts indium, a preparation of 90 atomic parts selenium, 8 atomic parts germanium and 2 atomic parts thallium, a preparation of 85 atomic parts selenium, 10 atomic parts Germanium and 5 atomic parts of antimony, a preparation of 85 atomic parts of selenium,! 0 atomic parts of tellurium and 5 atomic parts of arsenic, a preparation of 70 atomic

share selenium, 20 atomic parts germanium, 5 atomic parts thallium and 5 atomic parts antimony, a preparation 70 atomic parts selenium, 20 atomic parts germanium

to bring about the difference in the ability to work of the method according to the invention is required, many different forms of energy can be used will. A particularly cheap source of energy is electromagnetic radiation of various types, such as visible light, UV radiation and / or infrared radiation. A suitable energy producer of this kind can be found among the flashlights available on the market, namely of the flashlight type or the electron lamp flashes, which give excellent results with extremely short flash times of the order of magnitude of one or a few milliseconds or less or more in combination with many Storage materials according to the invention. The images can be generated with this type of radiation by that an image mask between the radiation source and the storage material, which is provided with an image should be switched on. The mass can be positive or negative, depending on the desired ef-

10

15th

the end

and 10 atomic parts of bismuth and a preparation of 95 atomic parts of selenium and 5 atomic parts of sulfur.

The above list of examples of storage materials is only a small selection of the large ones Number of storage materials that operate in accordance with the invention and when carrying out the invention Procedure can be used.

In addition to the foregoing characteristics, it is also desirable that the memory material be used as Starting material to be useful in the process according to the invention is capable of being easily converted into an amorphous Condition to be brought to suit it on a support if so desired is, can be applied. The storage material can be applied to the support in any convenient manner be applied, e.g. B. by applying in the form

a solution followed by evaporation of the solder, depending on the type and variety of the material used sunesmittel. by spraying on or by vacuum storage material, as explained below, divorce proceedings. The electromagnetic radiation can be used to manufacture

As mentioned above, according to one embodiment, a latent image is used which is uniform of the process according to the invention amorphous early or after a suitable later time in the Storage material differed by energy in a crystalline form in selected areas transferred Since solubility is transferred in the comparator according to the invention, through application drive images are generated, is the dissolution of heat and / od-jr electrical energy to the of utmost importance. The preferred storage - storage material in an energetic state upper materials according to the invention are those that bring the Kri- half of its transition temperature, at welstalle or produce crystallites of very small size, e.g. B. 30 rather the spontaneous transformation of the material instead of Range from 5 or 10 μπι to not more than 100 μιη finds. Other sources of electromagnetic energy. The like are strong incandescent lamps, infrared lamps,

In addition to the group of storage materials, the laser beams. Particle beams and the like. These energies as examples of starting materials for the inven- ting swelling can be used with or without modulation and with or according to the method, can be used without scanning in order to use the desired other preparations and substances. Image in selected areas of the storage material if they meet the above requirements. to generate in that areas of different These include z. B. Storage materials that are small
Amounts of at least one photo-dissociable or photo-reducible salt in the mixture
with or in contact with the storage material. These substances produce a stable one with light
Core, which acts as a crystallization center for the amorphous material added or in contact with it
in the case of simultaneous or consecutive 45
Application of energy, such as by heating, is used.
Light reducible or dissociable salts that
which may be used in the photosensitive phase include such salts as e.g. B. thallium halides, silver halides, copper halides and mercury 53
Overhalides, especially in combination with catalytic amounts of other nucleating or crystallization-promoting substances. It should be noted that the
just mentioned systems of dissociated by light

40

Solubility can be brought about in the storage material.

It is also possible to use electricity as the energy source, e.g. B. by using a probe on a gilter with an oscillator that takes over the generation of the image or through use a combination of several contacts and devices for controlling the current.

Other forms of energy that are useful in the method of the present invention include heat in form of radiant heat or heat generated by touching e.g. B. by hot pressing with a tool in The shape of the desired image is transferred. Often mechanical work such as labeling the Storage materials with the typewriter or the various methods of making impressions by stamping etc. required for the transformation of the memory material to the selected one Provide required energy to areas in a state of different solubility.

The method according to the invention is based on the selective application of energy to selected areas

or reducible salts with an amorphous
Material as starting materials in the invention
Processes are only useful when the transformation is from the amorphous to the crystalline state
or vice versa from the crystalline state to the amorphous state or any of the other physical properties of the storage material in order to cause a physical change in structure of the storage materials within the material which has been subjected to the action of energy. Since the physical changes generally represent a threshold value reaction, the energy used must be above the threshold Ie. It follows from this that the areas of the memory material in which no physical structural change is desired have an energy below that of an

the short period of time mentioned takes place. Accordingly, the salts mentioned are particularly favorable, also in combination with the above-mentioned glassy, non-silicate storage materials according to the invention.

To change the physical structure of the Storage material to create a significant solution

reversible threshold can be exposed without

a change takes place. Accordingly, where in this specification the application of none Energy is referred to in certain areas, including that in these areas energy may be used provided it is of an intensity or is provided in an amount that does not physical structural changes of the storage material brings about the 'description and claims are to be understood as serving prerequisites. This is true especially in the event that a mask in! Combination, ζ. B. with a flashlight is used. In the transparent or permeable parts of the mask, the energy essentially passes through the mask with full strength, vouching that the physical structural changes in the corresponding areas of the Storage material take place. The energy usually does not become complete in the opaque areas of the mask cut off, but a certain amount of energy also goes through the opaque or opaque Areas to the corresponding areas from the

ΙΙίαΐΛ »! ! dl. St. VJwl

Mask is the intensity and / or amount of the passing through However, energy is reduced significantly below the corresponding value of the unimpeded energy. Hence, the decreased intensity and / or amount of energy passed through the opaque parts goes through, not out, the physical change in the structure of the corresponding areas of the storage material to bring forth. In this way, the selectivity of the application of energy is retained, though Energy is also applied to the non-imaging areas where none physical structural change is sought or achieved.

As previously explained, the method according to the invention is used in the same way for the production of positives and negative relief images. In many cases, the storage material with the higher degree of crystallinity will dissolve faster in a given solvent for the material than the storage material with the lower degree of crystallinity. If, therefore, in these cases one were to use an essentially amorphous material emanates and selected areas of this material of exposure to energy at a level and above exposes a period of time that is sufficient to bring the storage material in these areas into the crisis-line state to transfer, a positive image is obtained on treatment with the selective solvent.

Certain storage materials, e.g. B. the above preparations of germanium and tellurium result negative images when the amorphous material is exposed to the effects of energy because that remains unchanged amorphous material dissolves at a higher rate than the crystalline material. Because the reversible nature of the physical structural changes in these substances it is also possible to have a positive one Create a relief image directly with the same type of materials and with the same solution επ ·! Ίtteln. To achieve this, you can, for. B. the entire storage material by suitable application of Energy, e.g. B. by simple heating, converted into the crystalline form. When energy is subsequently expended will, e.g. B. the radiation from a flashlight, on selected areas of the storage material, e.g. B. through a mask, the irradiated crystalline areas become more amorphous, with the desired difference in solubility is produced. Since the amorphous material dissolves in the solvent at a higher rate, a positive relief image is obtained on treatment with the solvent.

As mentioned above, in a third group of storage materials, in which the reversible behavior not a major factor is the energy induced crystallization of the amorphous material from accompanied by a chemical rearrangement of the atomic structure be, so that the storage material in the irradiated selected areas of higher crystallinity chemically from the amorphous storage material in the unchanged areas that do not receive radiation, different is' .. In this case a wider range of solvents is usually available. A solvent can be selected that the crystalline

is material dissolves in the areas that were exposed to the imaging effect of the energy, creating a positive relief image. Alternatively, a solvent can be selected that dissolves the amorphous material in the areas that were not etched out for the imaging effects of the energy, *%, _n A "w ^ U om nnnitmef ΟβϋαΓΚίΜ aria.int % t, \ wA ΛΙΛα

ITUUUlVIl Will HVgHHIVd I XW IIWI Vl IX «VJlC-XaUgL VTIlVl. TTIW

Obviously, the new process according to the invention creates a wide range of materials and solvents to generate positive or negative relief images, as desired

The type of solvents used in the process according to the invention depends on the type and composition the storage materials that are used. In those cases where the solubility difference based solely on the difference in the internal molecular arrangement, generally solves a solvent for the crystalline material does not essentially affect the amorphous material and vice versa. at Storage materials that contain significant amounts of selenium are usually carbon disulfide (carbon disulfide) an excellent selective solvent. For other storage materials, a solution of Bromine in methanol can be used. Excellent results are usually obtained with this solvent received if it is z. B. 25 to 75 wt .-% bromine dissolved ii. Contains methanol. Usually the crystalline dissolves Material in this type of solvent at a faster rate than the amorphous material. By modifying the concentration of bromine can control the selectivity of the solvent over a wide range will.

In the case of the germanium preparations mentioned above and tellurium, in which the crystallization of the amorphous compound results in the production of free tellurium

w caused in the crystalline phase, aqueous solvents containing small amounts djkiive solvent This type were contain an oxidising agent for the storage material, an excellent "found by solvent dissolves commonly, the amorphous material having a higher speed than the ^kristaii:... ne material and produces thus generally negative images

bo of the storage material can contain up to 6% available chlorine or more.

Various aqueous solutions of other oxidizing agents such as hydrogen peroxide and nitric acid Concentrations and changing proportions can also be used as a selective solvent for the storage material can be used according to the method according to the invention. By changing the concentration the solution and by changing the ratio

From oxidant to nitric acid, a wide range of solvent strengths are available to help adapt the solvent to the requirements of each situation in order to counter the difference in solubility and to take advantage of it. A similarly effective system comprises saturated sodium hypochlorite solutions, which in terms of their solvent power and selectivity by adding varying amounts of Water and alkali metal hydroxides can be adjusted.

In general, the selective solvent is provided or adjusted so that it is preferably one Form of the storage material dissolves and not or not significantly the other more difficultly soluble form or State of the storage material dissolves. The solvent action can be physical alone or they can be a chemical reaction between at least one component of the solvent and the storage material include. Other solvents can be used for other storage materials.

An interesting phenomenon has been made in connection with the aqueous solutions of oxidizing agents observed. For example, a sodium hypochlorite solution that is repeated to dissolve the amorphous Material from the layer of storage material has been used at a certain saturation point reverse the solvent action, so that from here on the crystalline material is preferentially dissolved will. In this way, a positive relief image can be obtained from a storage material-solvent combination which usually produces negative relief images. In this way becomes another way created to control the type of image ultimately obtained.

By dissolving the storage material in the areas where it is soluble at a higher rate is. obtained images can be further processed in various ways to produce many useful end products to create. The storage material can be used as a resistor or an etching base for the etching of the substrate or an intermediate layer are used in the usual way to produce a deeper relief image or the like. To Completing this additional etching step, the memory material can be in place and in the raised parts It may be left in place to perform some function on the final product, or it may be by mechanical means or z. B. can be removed by a suitable solvent. In a similar way, the storage material, that remains in the selected areas after the first level of resolution, also called resistance or Etching base for a subsequent plating in the usual Plating solutions serve or it can form the basis for plating on this material.

The actual resolution run for the formation of the series image According to the invention, the storage material can also be in an electrical low-voltage direct current field be effected. For this purpose, a counter electrode is placed opposite the layer of storage material intended. In this case, the storage material is preferably on a metallic layer carrier or applied to a metallic intermediate layer The counter electrode and the metallic Layer supports are connected to a direct current source and the electrode and the storage material are immersed in a liquid electrolyte, each a clectrolytic etching is obtained according to the polarity or electroplating. Standard galvanizing solutions can be used for electroplating or electrolytic plating be used. For the electrolytic etching, any of the above-mentioned solvents can be used be used. When the solvent itself is not an electrolyte, an electrolyte, e.g. B. a metal net, can be added.

In the memory material used in the present invention, the crystalline parts of the material generally have a greatly increased electrical conductivity compared to the amorphous material. Hence will be

ίο by dissolving the crystalline storage material in one electric field and in the presence of an electrolyte small differences in solubility of the amorphous and of the crystalline storage material is strongly reinforced by the differences in conductivity. According to this Embodiment of the method according to the invention are excellent images even in the cases in which the difference in the dissolution speed of the substances is otherwise not sufficiently large would be to produce the desired images. These embodiments of the invention The method therefore greatly expands the usefulness of the method and enables an even greater one Selection of storage materials as starting material. As above in connection with the discussion of the Drawings has been carried out, the energy-sensitive storage material is preferably on a layer support arranged. It is general for making relief images or other structures in accordance with the invention expedient to bring the storage material in the form of a thin layer, which can be flat, d. H. in In the form of a layer, or which can be cylindrical or any other desired shape. The layer or film of memory material can be provided in a wide range of thicknesses.

J5 For most applications according to the invention In the process, the layer of storage material preferably has a thickness of up to ΙΟμΓη up to a few z. B. 0.127 mm. Best results are general obtained with layers of storage material, which from about 'Λόμπι to a few μπι preferably up to 5 μιτι or are thick.

Depending on the desired end use, the layer of storage material can be on many different substrates, such as metal, plastic, fibrous cellulose material. such as paper or cardboard, ceramic or glass or a combination of two or more of these substances. In general, the nature of the substrate will materially affect the feasibility of the process so that many different products can be made for many different end uses. In the event that infrared radiation or heat are used as a means for transforming the storage material, the type of substrate has some influence in that high thermal conductivity of the substrate requires a greater application of heat energy to achieve the same effect. The thermally non-conductive or less conductive carrier materials also generally give better resolution.
An embodiment of the method according to the invention has been described, according to which the storage material is in an essentially amorphous state or in a highly crystalline form before it is exposed to the imaging effect of energy. It has been found that the crystalline storage material can sometimes appear in various morphological forms. By evenly treating an amorphous layer of storage material with a measured average amount of energy, the storage material increases

A crystalline structure with a smooth surface over the entire surface, a so-called planar structure to form crystalline layer. The planar crystalline layer of storage material obtained in this way is, can be used as a starting maierial for the invention Process serve. As mentioned above, selected areas of the planar crystalline layer become made of storage material exposed to the imaging effects of energy. The result of this is that the

diness results as the amorphous material of the same chemical composition and the irregular The notched form of the crystalline storage material has a higher dissolution rate than the amorphous one Material of the same chemical compositions. It was found that this difference in the rate of dissolution for these substances in the bromine solutions mentioned in methanol or greater. This shows that by controlling the energy level,

Barn structure in these areas, the additional energy to which the selected areas of storage material

adopts an irregular notched surface. The latter has a much higher dissolution rate in a given solvent for the material than the smooth planar crystalline Areas. When treated with a solvent as described above, the crystals or crystallites dissolve with the irregularly notched surface preferably forming a positive image as mentioned above.

According to another embodiment of the invention, selected areas of a layer are selected Amorphous storage material subjected to the imaging effect of energy, which is in a regulated level is applied to have a planar crystalline structure in the areas exposed to the energy to produce a smooth surface. Treatment with a suitable solvent will make the amorphous Areas preferably solved in order to produce a negative image in which the raised areas from the flat crystalline storage materials! exist.

According to a further embodiment of the method according to the invention, selected areas a layer of amorphous storage material the imaging effects of energy of a medium Ni

be subject, it is not only possible to change the nature of the Figure / u control, d. H. whether it is positive or negative, but also a control of the relative solubilities to create the energized and non-energized area of the storage material.

The invention also includes the structures which carry the relief images according to the invention Processes have been generated. This structural

have wide utility, few of which should be mentioned below. Starting from a structure according to FIG. 4, in which the substrate 30 is made There is glass and an overlying layer 28 of storage material with a high degree of opacity according to FIG Invention has, photomasks can easily and immediately with the help of a contact mask and z. B. a pulse can be made by a millisecond of a flashlight lamp. The structure exposed to the radiation becomes briefly immersed in a suitable solvent, rinsed in water and dried. Those made in this way Photomasks have many uses, e.g. B. as templates for the production of integrated Circuits according to standard procedures. The photomasks according to the invention are more durable than the usual

veaus subjected to silver halide masks used in the corresponding areas 35. And to create a planar smooth crystalline structure. On the other hand, they require fewer manufacturing steps and the imaged layer of memory material obtained in this way is subsequently used
heated to a temperature above the transition temperature of the storage material to an inverted 40
Generate image. The areas of the layer of memory material made up of the planar smooth crystalline material are formed as a result of this heating
amorphous and the areas resulting from the amorphous
Storage materials exist, become planar and crystalline. 45 consists of metallic chromium and the top layer is then the layer provided with the image becomes a storage material according to the invention. After the memory material with z. B. treated with the same solvent that was used in the above embodiment of the method for producing a positive image. It can be seen that the use of the new chrome masks process results in lower costs than switching on a heating stage.

cfMAllc? alc Αϊf * üMioh t * n PhmmmncWpn

which are also used as templates in the manufacture of integrated circuits.

The method according to the invention can also be used for the direct production of chrome masks be, wherein the starting material is a structure according to FIG. 7 is used. For this embodiment the substrate 40 is made of glass, the intermediate layer 38

Implementation of the F i g. 7 to II or 12 to 14 described steps are included slightly chrome masks. It can be seen that by

the result of the figure, which is now a positive Image is generated when a negative image would have been obtained without the means of the heating stage. So-

can be provided.

Using the structure of FIG. 4 as the starting material, the substrate 30 made of glass or a

This embodiment of the translucent or translucent art according to the invention is also represented Another possibility is the method, the types of material and the cover layer 28 is a storage material Control image between positive and negative. al is with a high degree of turbidity according to the invention, As can be seen from the above, there can be slides or glass images immediately after the im large difference in the rate of dissolution related to the fig. 4 to 6 described Verdes smooth planar crystalline storage material process steps can be produced. The slides resembled with the irregularly notched crystalline can be used in the usual way for projection or as Materials. With selective solvents, such as the printing templates for the production of copies and so on aqueous solutions of an oxidizing agent are used. As many of the storage materials that for the storage material, the amorphous form of the process according to the invention is useful Storage material are usually in terms of their resolution, have a surprisingly high degree of opacity, is The speed of resolution between the two crystallines makes it possible to achieve the highest contrast in the case of slide-type Shapes, creating the smooth planar crystalline shape of the products of the inventive method with ex-storage material a lower dissolution rate- thin layers or films from the storage

material to great savings of time and money to achieve. The high haze storage materials also easily make large copies Contrast on fabrics like paper.

The method according to the invention is also suitable for the production of copies or slides or others Objects? Halftone (gray tone) reproductions are suitable. For this purpose the exposure is made by a suitable conventional halftone line screen or grid made.

Another important application for the structures according to the invention is in the lithographic field Printing plates. Lithographic printing plates for offset printing derive their printing quality from one Difference in hydrophilic and oleophilic properties in selected areas of the printing plate away. This type of plate can easily be produced by the method of the invention, one of the Embodiments of the method described is used.

Starting from a structure according to FIG the substrate 30 e.g. B. consists of aluminum and preferably has a fine-grained surface and the Cover layer 28 is a storage material according to the invention, lithographic plates can be produced, in that in connection with the F i g. 4 to 6 described procedure is carried out. A lithographic one Printing plate is obtained in which the substrate is made of aluminum hydrophilic and the raised areas, which are formed by the remaining storage material are oleophilic. Instead of using Aluminum, other hydrophilic substances, such as cellulose acetate, can be used with equal success.

Another type of lithographic printing plate can easily be produced by the method of the present invention, assuming a structure as shown in FIG. 7 goes out, in which the substrate 40 z. B. consists of aluminum, the intermediate ^{layer 38 Ku n} fe ** ä ^c * and the cover layer 36 is a storage material according to the invention. If the process steps which are described in connection with FIGS. 7 to 11 are carried out, a lithographic printing plate is obtained which contains a relief image which consists of copper in the raised areas and aluminum in the low areas, the aluminum being the hydrophilic ones Surfaces that copper form the oleophilic pressure surfaces.

Still another type of lithographic printing plate can be made by using e.g. B. a substrate made of copper or polyethylene terephthalate in the structure of FIG. 4. If the procedural steps related to the F i g. 4 to 6 are described, a relief image is obtained in which both copper or polyterephthalate and the storage material are oleophilic. In this case it is necessary to cover the storage material of the layer 28 with a To provide special treatment that makes it hydrophilic. This can e.g. B. by treating the top layer from storage material with aqueous solutions of silver nitride, tin (II) chloride or various soluble ones Nickel salts can be achieved. It should be noted that a printing plate made in this way prints a negative image. To print a positive image with this type of lithographic plate is it is necessary to obtain a negative image from the storage material on the support by means of the relevant To produce embodiments of the method according to the invention which have been described above. Negatives lithographic printing plates can also be made by starting from a structure according to FIG F i g. 7, in which the layer carrier 40 made of copper, the intermediate layer 38 made of aluminum and the cover layer 36 consist of a storage material according to the invention. If this is in connection with FIGS. 7 to 11 The method described is carried out, a printing plate is obtained in which the parts that have run are removed from the copper substrate are formed, are oleophilic and the ίο raised areas formed by the aluminum are hydrophilic. These types of lithographic plates are commonly called deep-etched printing plates designated.

The printing properties of the raised areas containing the storage material according to the invention, can also be changed by applying a toner to the storage material, which is subsequently melted will. This embodiment of the method can accordingly also be used for the production of lithographic Printing plates are used, the raised areas formed by the storage material are hydrophilic.

The invention also relates to active electronic component assemblies, which can be produced directly by the process according to the invention.

These devices can e.g. B. by means of an initial structure according to Fi g. 4 can be generated, the in connection with the F i g. 4 to 6 described method steps are carried out. As a top layer jo 28 a storage material according to the invention is used, that is a semiconductor and has the desired electrical properties. Suitable materials are z. B. in said US Pat. No. 3,271,591. According to one mode of operation, the storage material is in the form of an amorphous layer from a Layer carrier 30 applied, which is a dielectric or insulator. The layer of amorphous storage material is exposed to energy through a stencil or mask to create a crystallized image of the various to produce electrical devices in place. After that, the amorphous, not the Areas of the top layer exposed to energy are removed by the difference in resolution as described above. The crystalline areas of storage materials that remain on the substrate are then connected by suitable electrical conductors and provided with leads to the desired circuit to create. The circuits can be used as such or after the crystalline storage material has been converted into the amorphous form by applying e.g. B. an electric current can be used. Each of the areas of the semiconducting storage materials can perform a special electrical function, so that the complete Arrangement as a prefabricated arrangement of electrical switches. Capacitors, resistors, etc. each of which is of the type described in US Pat. No. 3,271,591. This method for the immediate production of active electronic component arrangements is of particular benefit, when large numbers of extremely small electrical devices are desired in a confined space As with microcircuits, these types of devices can be manufactured at an extremely low cost permitted by simple process steps. b5 By applying the procedure, being multiple the energy is exposed, in combination with multi-layer fabrics that are more than two layers different Materials can contain exceedingly

Komniexe arrangements of electronic devices are produced by a simple process, the electrical conductors, conductive facilities. Semiconductors and suitable semiconducting devices with predetermined contain electrical values and non-conductive surfaces as required. Ali these components can be made in situ on a common carrier, eliminating the need for assembly and finishing is eliminated.

In the embodiments of the method according to the invention, wherein electrical components or component arrangements are manufactured directly, the substrate can be an insulator or an electrical non-conductor as mentioned above, or it can be another semiconducting material or an electrical conductor. The is Proper selection of electrical properties in one or more layers add to the versatility and usability of the electrical components and component assemblies, which according to the invention Process can be established. Given the electrical components can also be produced without a layer support if this is in connection procedures described in Figures 1-3 are followed will.

The method according to the invention can also be used to a large extent for the production of printed circuits and the like can be used by e.g. B. a structure according to FIG. 7 is assumed, the layer support 40 is an electrical insulator, the intermediate layer 38 is a metallic electrical conductor and the cover layer Figure 36 illustrates a storage material according to the invention. If the cover layer 36 is covered by a suitable Stencil or mask (with energy) is irradiated and if the in connection with the F i g. 7 to 11 to 14 is followed, excellent quality printed circuit boards will become low Generates costs.

The inventive method can also be used for! production be used by burr-free small parts, e.g. B. of components for small clocks and the like., using chemical micro-rolling processes using the steps and principles of the present invention Procedure.

The inventive method is also suitable for the production of objects that have an etched Have surface on glass. In this case, the structure of FIG. 4 glass as a layer support 30 and a storage material according to the invention as a cover layer 28. If the in connection with the F i g. 4 to 6 described steps are carried out, a relief image from storage material is on the Glass backing obtained. The glass is then treated with an etchant for the glass that does not have a Solvent for the storage material. A suitable The invention is illustrated by the following examples where parts are by weight unless otherwise noted.

example 1

It becomes a 5 μm thick film made of storage material 85 atomic parts of tellurium and 15 atomic parts of germanium by spraying onto a 6.3 mm thick glass plate brought.

Selected discrete areas of the film of storage material were subjected to the energy of a pulsed argon laser of 100 mW exposed. The laser focused on the image plane and it became different Spots with an intensity of 10 ^ W / qcm pulsed with a pulse width of 10 microseconds.

A solution of 25 wt .-% sodium hypochiorite (grade for chemical reagents) in deionized Water (about 6% available chlorine) was prepared, and the gas treatment with the exposed film was finished Storage material was placed in the hypochlorite solution. After rinsing with water and drying a positive slide was obtained in which the irradiated discrete areas were removed.

Example 2

It was a 0.5 μm thick film made of a storage material from 20 atomic parts tellurium, 30 atomic parts arsenic and 50 atomic parts sulfur by thermal evaporation in a vacuum on a 25.4 μm thick polyethylene ropefalate film deposited.

The film of storage material was exposed to the flash of a clear flashlight with a clearance irradiated from 7.6 cm from the image plane. The exposure was by silver halide microdisplay carried out.

The exposed structure was immersed in full strength "Roman bleach". After about a second During the immersion time, the exposed parts had detached themselves and resulted in a positive diopositive copy of the micro-reproduction with excellent resolution and sharpness.

Example 3

A 1 μm thick film made from a storage material 85 atomic parts of selenium and 15 atomic parts of tellurium was carried out on a 127 μm thick film of cellulose acetate applied a spray process.

The film made from the storage material was exposed to the radiation of an electron flash through a halftone line grid exposed to a transparent photographic negative. The flash unit was 5.1 cm from the

tes etchant is z. B. hydrofluoric acid (H ₂ F) placed 55 image plane away, and the flash had a duration of 0.5 ms to produce a relief image in the glass substrate. can be used, whereby the storage material serves as a chemical etching base. The storage material

can then be removed and a die is made exposed structure was then briefly immersed in carbon disulfide (carbon disulfide). After drying it became a sharp copy of the

Etched glass object of excellent quality with ho- bo halftone photography of excellent resolution and received forth resolution. The new method for sharpness of detail received.

is

The preparation of etched glass objects is less expensive and requires fewer steps than the usual Process for making etched glass objects.

The novel process of the invention can be used for many other practical purposes how they can be devised to produce many different useful objects.

Example 4

It was a 0.1 μm thick film made of a storage material from 30 atomic parts of antimony, 20 atomic parts of tellurium and 50 atomic parts of sulfur by thermal Evaporation in a vacuum on a commercially available binding

Depapier of about 71 μm thickness of good quality deposited.

The film of storage material was through a Mask that contained the image of a printed text, exposed to radiation from a quartz lamp of 650 W The film area from the storage material was in brought a distance of 14 inches from the lamp and the exposure time was one second.

The exposed paper was immersed in an aqueous solution obtained by dissolving 10 parts by weight of a concentrated hydrogen peroxide solution with 90 parts by weight of water. To Less than 10 seconds a positive reflection copy was formed, the excellent sharpness and contrast showed.

Example 5

It became a 1 μm thick film of storage material from 85 atomic parts of tellurium and 15 atomic parts of germanium by a spraying process on a 127 μίτι thick Polyethylene terephthalate film deposited.

The film of storage material was then made through a mask to the radiation of an electronic flash device, as described in Example 3, exposed, and the exposed structure was developed in "Roman bleach" according to Example 2.

It became 2% by volume of a saturated silver nitrate solution and 2% by volume of a gum arabic solution of 14 ° Be mixed with 96% by volume of water. The dilute aqueous solution thus obtained was used as a spray solution when the image was used as a lithographic offset printing plate. The solution made the areas of storage material hydrophilic, while the areas of the mylar substitute remain oleophilic.

When used in a conventional lithographic Presses with common inks made excellent prints of the image on common printing paper achieved.

Example 6

A 80 μm was placed on a substrate made of special glass thick film of chrome deposited in the usual way. A 0.5 μm thicker layer was then over the chrome film Film made from a storage material of 83 atomic parts tellurium, 13 atomic parts germanium,? Atomic antimony and 2 atomic parts of sulfur are deposited.

The film of storage material was exposed through a mask in the manner described in Example 3, and the exposed structure was briefly immersed in a solution of 25% by weight Nalriumhypochlorii in eniionisic-rtem Immersed in water. An image of memory material on a bare chrome background was obtained. This The image was then treated in chrome etching solution for about 1 minute and resulted in a negative photomask great durability and high optical density.

B e i s ρ i e I 7

It was a 1 μm thick film made of a storage material arsenic from 30 atomic parts. 20 atomic parts of tellurium and 50 atomic parts of sulfur by thermal vacuum evaporation on a 127 μm thick film of cellular M loose acetate deposited.

The film of storage material was exposed to the radiation of a flashlight bulb lamp, 7.1 cm from the Film of storage material was removed. A mask was placed between the piston flashlight and inserted into the storage material.

The exposed structure was briefly immersed in an aqueous solution containing 25% by weight sodium hypochlorite (pure reagent) immersed in deionized water. After rinsing with water and drying, the obtained one became Image used as a lithographic offset printing plate in a conventional offset printing machine The plate was wetted with the usual wetting solution and colored, so that the printing ink was absorbed by the surfaces which consisted of the storage material. Excellent prints were made on common printing paper obtain.

Example 8

The procedure of Example 1 was repeated, but with a suitable mask between the laser and the film of memory material was used, thereby creating a variety of electrical circuit components that consisted of the storage material, were generated than the storage material in the places with the larger Solubility was extracted. After adding suitable electrical lines, a switching device was installed obtained in place on the glass sheet for use as a component in electrical devices.

Example 9

The film of storage material, which had been deposited on the glass plate according to the method of Example 1, was ^{heated to about 200 °} C. for 1 minute after deposition, but before exposure to the laser energy.

The heat treated storage material was then exposed to the laser energy and immersed in the solvent exposed in the manner described in Example 1. A negative slide was obtained.

Numerous changes can be made in various embodiments of the invention without to deviate from the inventive idea.

Selected areas of a storage material are subjected to the imaging effect of energy, which is a physical change in structure and a difference in solubility of these selected areas in certain solvents compared to the solubility of those areas that are not exposed to energy had been subjected to causes. Then the areas are treated with a solvent for treated the more soluble areas to produce a relief image or the like. Also concerns the invention relief images and other objects produced by this method.

For this purpose 2 sheets of drawings

Claims (1)

Patent claims: 1. A method for producing an image, in which a layer of an imaging material, the one Semiconductors with at least one element of main group 6, excluding oxygen, contains Energy corresponding to the desired image or its negative is applied so that the solubility of the exposed layer areas to in relation to the non-exposed layer parts change towards certain solvents,