DE2757830C2 - Process for the production of a recording material which is sensitive to electromagnetic and corpuscular radiation - Google Patents

Description

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The invention relates to a method for producing an opposite electromagnetic and Recording material sensitive to corpuscular radiation according to the preamble of claim 1. Such materials are used to manufacture * 5 information carriers for optical storage devices, Image signal recording devices, laser recording devices and other recording devices are used.

A method is known for producing a recording material which is sensitive to electromagnetic and corpuscular radiation from the following operations: application of a metal layer to a layer support, application of a Semiconductor layer on a metal layer, the semiconductor layer being able to interact with the metal layer under the action of the activity radiation to form reaction products, the physical and have chemical properties that differ from the physical and chemical properties of the w Differentiate between metal and semiconductor layers.

The material produced by this method has a high contrast level of 10 to 20 (ratio between the reflection coefficient of the non-irradiated recording material and the reflection coefficient coefficient of the irradiated material) only when exposed from the side of the semiconductor layer.

The semiconductor layer in this recording medium

rial, however, remains unprotected from the influence of outside mechanical influences (contamination by dust particles, scratches), which cause distortion of the recorded information

It is known that the surface of an opposite electromagnetic and corpuscular radiation sensitive recording material as well as that on it recorded information when recording and reading the information through a transparent one Medium can be effectively protected, the strength of which is many times greater than the depth of field of a In the above-mentioned method for producing a recording material sensitive to electromagnetic and corpuscular radiation, a metal layer is arranged on the side of the layer support. The change the order in which the semiconductor and metal layers are applied creates certain difficulties which can be attributed to the fact that when a metal layer is sputtered onto the semiconductor layer a a substantial increase in the effective temperature of the shark layer can be observed, which occurs in the Production of the recording material leads to diffusion of the metal into the semiconductor layer the range of usable semiconductor compounds and metals is limited by those whose at Formation of new connections resulting amount of heat exceeds the amount of heat, which is in the Manufacture of the material developed

Semiconductor compounds and alloys of the type As-S, As-Sc, As-S-Se, Sb-S, Sb-S-Se, which are the Making it possible to produce a highly sensitive material can be used in the above-mentioned production process practically not used.

Also known is a method for producing a recording material sensitive to electromagnetic and corpuscular radiation, comprising the application of a semiconductor layer a transparent substrate, application of a barrier layer on the half-cover, the opposite the semiconductor layer is inert and in the application of a metal layer on the barrier layer the under Exposure to electromagnetic or corpuscular radiation is capable with the semiconductor layer under Formation of reaction products to interact chemically, which have physical and chemical properties that differ from the physical and Differentiate chemical properties of the metal and semiconductor layer (DE-OS 26 00 207).

After this procedure you can be sensitive to electromagnetic and corpuscular radiation Recording materials are produced in which as a semiconductor layer a comprehensive range of Semiconductors can be used. However, such materials have due to the presence of a Barrier layer between the semiconductor and the metal layer on a reduced sensitivity.

The invention is based on the object of a method for producing a device that is sensitive to electromagnetic and corpuscular radiation To specify recording material that enables to produce a high-sensitivity, high-contrast recording material.

Based on the generic method, this object is achieved according to the invention by the im characterizing part of claim 1 measures described solved

Preferred developments and refinements

of the method of the invention are the subject matter of claims 2 fcjs 4,

The inventive method for producing a recording material sensitive to electromagnetic and corpuscular radiation makes it possible to produce materials which protect the recorded information from the influence of external mechanical influences by a ensure transparent substrate and have a high sensitivity

The invention is explained in more detail below with reference to the drawings

F ί g. 1 an opposite electromagnetic and Corpuscular radiation-sensitive recording material in a production stage before annealing, im Cross-section,

Fig.2 an opposite electromagnetic and Corpuscular radiation sensitive recording material after annealing until the partial dissolution of the Barrier layer in cross section,

Fig. 3 an opposite electromagnetic and Recording material sensitive to corpuscular radiation after annealing to complete Dissolution of the barrier layer, in cross section, and

Fig. 4 an opposite electromagnetic and Corpuscular radiation sensitive recording material with protective layer, in cross section

The method according to the invention for producing a material sensitive to electromagnetic and corpuscular radiation consists in the following. On a transparent substrate 1 (Fig. 1) - as transparent dielectrics (glass, quartz) and organic light-permeable plates can be used - a semiconductor layer 2, a barrier layer 3 and a metal layer 4 are applied successively by sputtering in a vacuum, the capable is to react chemically with the semiconductor layer 2 under the action of electromagnetic and corpuscular radiation. The thickness of the substrate 1 exceeds the depth of field of the system for generating the image which is registered on the recording material and amounts to 1 to 10 mm.

Metals such as Ag, Cu, Tl, can be used as the metal layer 4, in which, when Compounds in chemical interaction with sulfides, selenides and tellurides of arsenic, antimony and bismuth under the action of electromagnetic and corpuscular radiation low amounts of heat develop. The thickness of the metal layer 4 is selected in a range from 40 to 1000 nm

As the semiconductor layer 2, compounds and alloys of the At-S, As-Se, As-S-Se, Sb-S, Sb-Se, Sb-S-Se can be used in Formation of new compounds when interacting with silver, copper and thallium under the influence the electromagnetic and corpuscular radiation release small amounts of heat, which is the production of recording materials with high sensitivity.

Particularly useful as semiconductor alloys and compounds that make it possible, when interacting with the metal layer, compounds with a stoichiometric composition or in a glass-like state close to it, e.g. B. AsS * AsSe ₂ , SbS ₂ , SbSe ₂ , AsS ₂ -X, Se, where 0 < χ < 2 and so on. The thickness of the layer 2 made of the semiconductor material is in a range from 10 to 500 nm tJPU / counts

• Various metals and their alloys can be used as the material for the barrier layer 3, for example Mo, Au, Cr, Pt ₁ Fe, Pb, Ni, Cd, Al, Mn, Zn, Mg, As, Bi, Ga, In, Sb, Sn, Co, with the exception of Cu, Ag, TI - etemental elements Si, Ge and dielectrics C and B as well as sulphides, tellurides and selenides of the metals mentioned can be used.

However, it is advisable to choose metals for the barrier layer 3, since the barrier layer 3, which consists of a

ίο such substance is carried out at a lower level Thickness compared to the barrier layer 3 made of sulfides, tellurides and selenides of the metals mentioned Semiconductor layer 2 before interacting with the metal (Ag, Cu Te) of layer 4 during application

the latter protects during the production of the recording material and at least in one of the adjacent layers 2 and 4 can be easily dissolved at a lower temperature. The thickness of the Barrier layer 3 becomes sufficient for prevention of the chemical interaction between the Semiconductor layer 2 and the metal layer 4 during the production of the recording material under the action of electromagnetic radiation of varying intensity and increasing the effective temperature of the Semiconductor layer 2 selected The optimal thickness of the Barrier layer 3 is 2 to 20 nm.

As the material for the barrier layer 3, it is desirable to use alloys with a fine crystalline structure use on which the metal layer 4 is epitaxial sedimented In this case, the production of a to electromagnetic and corpuscular radiation sensitive recording material with maximum resolving power because the Metal layer 4 condensed in a finely crystalline phase

For the application of layers, different shapes of the vacuum application of thin foils, such as thermal sputtering, electron beam sputtering, cathode sedimentation methods, and others are used that have a high degree of purity films to be produced, the uniformity of the thickness and ensure the reproducibility of the results.

After application of the metal layer 4 to the barrier layer 3, the recording material produced for dissolving the barrier layer 3 is either in the Layer 2 or in layer 4 or in layers 2 and 4 annealed at the same time. The annealing temperature is the same or higher than the diffusion temperature of the substance of the barrier layer 3 in one of the adjacent layers 2 and 4 selected The glow time is sufficient for the

Vi partial or complete dissolution of the barrier layer 3 chosen

In the partial solution (as shown in Figure 2) The presence of part of the barrier layer 3 in the fabric does not allow a recording material with maximum sensitivity for the given pair of flalfieiiers and metal, it assures however, the generation of a linear exposure characteristic of the recording material which is sensitive to electromagnetic and corpuscular radiation.

To produce a recording material with maximum sensitivity, up to the complete Annealed solution of the barrier layer.

F i g. 3 shows a recording material sensitive to electromagnetic and corpuscular radiation in section after annealing until the barrier layer 3 has completely dissolved. Further annealing does not lead to an increase in sensitivity.

For the solution of a barrier layer 3 made of gold, germanium. Lead, tin and gallium are said to be the annealing temperature 60 "C. 1 for the resolution of a Barrier layer 3 made of chromium, molybdenum. For nickel and iron, the annealing temperature should be 100 ° C or more.

The necessary condition for performing the aisglow of an opposite electromagnetic and corpuscular radiation-sensitive recording material is the hermetic sealing of it free surface with a varnish coating that partially excludes modification processes in the structure.

If iiU semiconductor layer 2 As-S or As-Se. Sb-S. Sb-> c. As-S-Sc. SIi -S-Sc are chosen, the glow temperature higher than the diffusion temperature di. Taking into account the above, the annealing temperature for the named group of substances should be in a range of 100 u .. _; jun (. "scv / ahl! VT ' ¹ -; ¹

D.is annealing '. :. · Ι the temperature mentioned leads ■ ii! l.r / eugung a more homogeneous semiconductor layer 2. ■ Aas / ur manufacture e: ncs Auf / cichniingsmatenals with constant sensitivity on the material surface and 'iir lines':;,!:,: Jos area of Spcktralsehenheb.L-ii contribution;.

/ ',.' in school /; Ilt! lalbleiterschicht 2 before F. penetrate v.or Nieialiaii'nv.; n the barrier layer 3 in the same during annealing ν- irc: uif the semiconductor layer 2 before application Je Sner ^ schi-'h ! A difiusionshin.d'jnvde school / layer was applied to the latter. On the Schut / schiv '''v. c _; The barrier layer 3 ¹ IiKi dl ·. · Metal layer 4 is applied across the wall. Then success: ei,! - 'Vngiiihen.

In Fig. 4 i ·. ', A recording material sensitive to electromagnetic and corpuscular radiation with: a diffusion-preventing protective layer 5 shown in section after' in annealing, which is completely stable '. ¹ ! .-! ·: 'Solution of the barrier layer 3 was performed. The Sen it / sehich; 5 enables an aligned dissolution of the barrier layer 3 only in the metal layer 4 dur.'h / i! ^f can not be excluded in the Halbleiicrschicht 2 iihri'n and the partial solution will lock 3, whereby the Hereich the .Spektralempfindlichkeit are ten of Aufzeichniir.gsmaterials invariably main- k.ii.n.

• \ N üfiusionshindemdc protective layer! 5, metal oxides, which are used as barrier layer 3, can b / v. Germanium oxide, organic polymeric polyacrylate and Polvrne'hvlsiloxanfolien, that means' against the semiconductors? : 2 substances which are inert when heated up to the heating temperature are not used. The diameter of the protective layer 5 is selected to be sufficient to prevent the diffusion of the metal of a barrier 3 into the semiconductor layer 2 during annealing. The thickness of the protective layer 5 is equal to 5 to ^ G nrn sxewshlt

The protective layer 5 allows the barrier layer 3 to be selected thinner (: m 25 to 50%), which contributes to an easier removal of this layer 3 during annealing t . The protective layer 5, which plays the role of a diffusion-preventing barrier during annealing, prevents the metal of the layer 4 from diffusing through the same. under the action of the actinity radiation ;; even after the removal of the barrier layer 3. The layer 5: is, however, ^{easily destructible under the action of short (10 ~ "3} ice IQ- ¹¹ S) laser impulses, which are on the surface of the opposite Radiation-sensitive material ensure a power density> 10 'W / cm ^? Such a combination of the protective layer 5 and the barrier layer 3 makes it possible to produce a radiation-sensitive recording material with the required range of spectral sensitivity, which is highly sensitive to radiation with a Has a power density that is sufficient for the destruction of the diffusion-preventing protective layer 5.

To further explain the invention, specific examples are given below for the implementation of the proposed method for producing recording materials that are sensitive to electromagnetic and corpuscular radiation.

Example I.

On a layer substrate 1 (I ig. 1) made of hot-polished glass with a thickness of 5 mm were in a vacuum (! 33. In-ι Pa) aiifrinanilerfnlgrnd in the thermal A layer 2 of AsSi -, - Sen., with a thickness of 30 nm. a barrier layer 3 made of gold with a thickness of 4 nm and a metal layer 4 Silver applied with a thickness of 400 nm. The material prepared in this way was made using a l.acküberzugcs sealed and thermally under vacuum (133 10-'Pa) for 3 hours at a Temperature of 80 "C until complete dissolution the barrier layer 3 annealed. Γ'The sensitivity of the Material after annealing increased 20-fold when exposed to radiation corresponding to the area of Self-absorption of the shark layer 2 corresponds. That further annealing at the temperature mentioned did not increase the sensitivity of the Recording material.

The sputtering of a metal layer 4 made of silver under the same conditions directly on a Semiconductor layer 2 AsSiiScoi led to their chemical Interaction in vacuum build-up of the metal layer 4 and made the production of a recording material sensitive to the activity radiation not possible.

Example 2

Of hot polished glass were mm with a thickness of 3 (1 g Fi.) On a substrate 1 under vacuum (133 · 10 ^J Pa) successively in thermal sputtering a layer 2 of SbSI iSeo.5 having a thickness of 30 nm and a Barrier layer 3 made of gold applied with a thickness of 4 nm. A metal layer 4 was applied by electron beam sputtering, the thickness of the metal layer ¹ .; 4 of silver was 400 nm. The material prepared in this way was sealed with the aid of a lacquer coating and thermally under vacuum (133 · 10 ^-3 Pa) for 3 hours at a temperature of 80 ^° C. until the barrier layer 3 was completely dissolved annealed to a maximum sensitivity of the recording material. The sensitivity increased 20-fold compared to a material with a barrier layer.

The sputtering of the metal layer 4 made of silver under the same conditions directly on the layer 2 of the semiconductor SbSi.jSenj led to their chemical Cooperation during the vacuum sputtering of the metal layer 4 and made the manufacture of one recording material that is not sensitive to electromagnetic and corpuscular radiation

possible.

Example 3

The recording material sensitive to electromagnetic and corpuscular radiation with the layers 2, 3 and 4 sputtered as in Example 1 was annealed under the same conditions as in Examples 1 and 2, but the duration of the annealing was reduced by 30%. Such a reduction of the duration of Ausgliihens led to a partial solution of the barrier layer 3 (Fig. 2) and caused the lowering of the sensitivity by twice in comparison / u the recording material, wherein the barrier layer was dissolved 3 \ ollständig.

The material with the partially removed barrier layer λ is characterized by a more linear exposure curve (the initial section of the exposure curve was "balanced") compared to the recording material for which the annealing was carried out until the thermal layers 3 were permanently dissolved. The application of a barrier layer 3 of less thickness (2 nm) to produce a recording material with the same sensitivity as after the partial annealing led to a partial chemical interaction of the semiconductor layer 2 and the metal layer 4 during the sputtering of the latter, what caused the reduction of the initial reflection coefficient of the Maienal (by 50%). The reading of the information that was recorded on this drawing material, which is sensitive to electromagnetic and corpuscular radiation, takes place, a smaller signal-to-noise ratio that is used. that the reliability of reading the information has been reduced.

Example 4

A layer 2 of the semiconductor As> S, with a thickness of 30 nm. A barrier layer 3 of chromium with a Thickness of 3 nm and a metal layer 4 made of silver with a thickness of 3u0 nm applied. The material prepared in this way was sealed with an organosilicon lacquer and placed in the medium of an inert gas (argon) at a pressure of 133 Pa and a temperature of I2O ⁼ C, which was 0.9 times the vitrification temperature of the semiconductor layer 4, for 4 hours thermally annealed until the barrier layer 3 has completely dissolved. Annealing at such a temperature resulted in a 25-fold increase in the sensitivity of the recording material after the annealing to radiation with a wavelength of 488.0 nm, the sensitivity of the recording material outside the range of self-absorption of the semiconductor layer 2 to radiation with one wavelength from 632.8 nm only enlarged by 4 times. The reduction in the sensitivity of the recording material outside the range of self-absorption promotes the increase in the reliable storage of information. The production of a recording material sensitive to electromagnetic and corpuscular radiation with the semiconductor layer 2 and the metal layer 4 led to a partial interaction of the semiconductor layer 2 and metal layer 4 during the sputtering of the metal layer 4. The partial chemical interaction of the layers 2 and 4 during the sputtering of the layer 4 caused the reflection coefficient of the recording material to be doubled before irradiation. Carrying out the '' stabilizing annealing of the recording material to reduce the sensitivity appears to be impossible (Or radiation with wavelengths outside the area of self-absorption in the absence of the barrier layer 3 for the layers 2 and 4 mentioned,
κι

Example 5

On a polished substrate I (Fig. 1) Quartz with a thickness of 5 mm were successively in the thermal under vacuum (UJ-IO-'Pa) A layer 2 of As: Si nut a thickness of 30 nm, a barrier layer 3 made of an alloy Mo-Au in the electron beam evaporation method with one; Thickness of 4 nm and one

- '' Metal layer 4 made of silver in the thermal sputtering process applied with a thickness of 400 nm. The recording material prepared in this way was sealed with an organosilicon varnish that was applied to the surface of the metal layer 4

- was applied by means of centrifugation, and the annealing was carried out under vacuum (133 × 10 ^J ) for three hours at a temperature of 100 ° C until the barrier layer 3 was completely dissolved. The sensitivity of the recording material after annealing increased by 30 times when exposed to radiation which corresponds to the range of self-absorption of the I lalblcitcrs of layer 2 (Λ - 488.0 nm). The direct dusting of the metal layer 4 onto a vitreous semiconductor layer 2 of the semiconductor As ₂ Si

: causes the condensation of silver in a coarse crystalline structure with the dimensions of the crystals, which are comparable to the thickness of the layer 4, and consequently also the reduction in resolving power.

Example 6

On a hot-polished substrate 1 (Fig. 4) Glass with a thickness of 3 mm under vacuum

: (I x 10 ^-5 Torr) were successively in thermal sputtering a layer 2 of the semiconductor alloy AsSiiSeo.5 nm with a thickness of 40, a protective layer 5 with a thickness of 6 nm from Germaniummonooxid, a barrier layer 3 of gold

i "nm with a thickness of 2 and a metal layer 4 made of silver having a thickness of 400 nm is applied. The thus prepared material was sealed with a La ^ küberzug and in argon (133 Pa) for 2.5 hours at a temperature of 80 ⁰ C to

5ϊ for the complete dissolution of the barrier layer 3 in the Metal layer 4 annealed.

The protective layer 5 prevented the barrier layer 3 from dissolving in the semiconductor layer 2, as a result of which the range of the spectral sensitivity of the recording material was invariably preserved. After annealing, the protective layer 5 was obtained in the structure of the material, it was, however, slightly under the action of radiation pulses with a duration of 10 ^-5 destructible which secure a power density of> 1 (P Wt / cm ² at the surface of the carrier. Opposite Lower intensity radiation, the recording material had a very low sensitivity (100 to 200 times lower than the sensitivity

compared to radiation with a power density of> 1 (PWt / cm ² ).

Example 7

On a substrate 1 (Fig. 1) of heat-polished glass having a thickness of 3 me were (133-10- ³ Pa) successively nm under vacuum in thermal Aufstäubungsve.fahren a layer 2 of aces having a thickness of 40, a barrier layer 3 of arsenic with a thickness of 20 nm and a metal layer 4 made of silver with a thickness of 400 nm. The recording material prepared in this way was sealed with an organosilicon varnish. The material was for six months with no dimming of the ambient radiation at a power density of 0.5 10 ³ W / cm ² (such an illuminance corresponding to the illumination intensity of 10 ³ lux outdoors in the day without sun) stored without change in the reflection coefficient. Immediately before the information was recorded, the record was

10

Example 8

iiuiigsniaici iai «rani ciiu τ otuiiucn uct cinci ι οπμν: Γ <ιιϋι annealed from 110 ° C. to complete dissolution of the barrier layer 3. The annealing achieved a sensitivity which allowed electromagnetic radiation pulses with a power density of 0.5 · 10- ^J W / cm ² and a duration of 100 s to be recorded.

(G F i. 1) on a support 1 of heat-polished glass having a thickness of 3 mm were successively in thermal sputtering under vacuum (133 ■ I0- ³ Pa) a layer 2 of arsenic sulfide As2S3 having a thickness of 30 nm, a barrier layer 3 made of an alloy Cr-Au with a thickness of 4 nm, a metal layer 4 made of silver with a thickness of 400 nm. The speed of the sputtering of the metal layer 4 was optimally chosen for generating a finely crystalline structure of the layer 4 on the surface of the barrier layer 3 (~ 10 nm / s).

The recording material was covered with an organosilicon varnish and annealed in an inert gas (argon) under a pressure of 33 Pa for three hours at a temperature of 100.degree. After the annealing, the sensitivity to the radiation with a wavelength of 488.0 nm increased to a constant 30-fold. The immediate sputtering of the metal (silver) of the layer 4 on the layer 2 of A ^ S ₁ is

Sputtering possible (a film with a thickness of 400 nm was sputtered in five seconds). However, a foil of the metal condensed at such a rate was distinguished by a coarsely crystalline structure. which caused a decrease in the resolution of the recording material.

1 sheet of drawings

Claims (4)

Claims; 1. Method of making an opposite recording material sensitive to electromagnetic and corpuscular radiation, in which successively on a transparent substrate (1) a semiconductor layer (2), one Barrier layer (3), which is inert with respect to the semiconductor layer, and a metal layer (4) is applied be, with the metal under the action of electromagnetic and corpuscular radiation with the semiconductor layer (2) reacts chemically to form reaction products whose physical and chemical properties differ from those the metal layer (4) and the semiconductor layer (2) is_ differentiate, characterized in that the recording material is additionally based on the Metal layer (4) contains a lacquer layer of thickness 20 to 100 nm, and that the barrier layer (3) through Annealing is at least partially dissolved in one of the two adjacent layers (2, 4). 2. The method according to claim 1, characterized in that until the complete solution Barrier layer (3) is annealed. 3. The method according to claim 1, characterized in that prior to application of the barrier layer (3) applies a protective layer (5) to the semiconductor layer (2), which acts as a diffusion-preventing barrier between the barrier layer (3) and the semiconductor layer (2) serves » 4. The method according to claim 1 or 2, characterized gekennzeici.net that at 0.7 to 0.9 times the glazing temperature of the material of the semiconductor layer (2) is borehole when the semiconductor layer from As- S, as -5 "t; Sb-S, As-S-Se or Sb-S-Se is